Fe-binding organic ligands in coastal and frontal regions of the western Antarctic Peninsula

Organic ligands are a key factor determining the availability of dissolved iron (DFe) in the high-nutrient low-chlorophyll (HNLC) areas of the Southern Ocean. In this study, organic speciation of Fe is investigated along a natural gradient of the western Antarctic Peninsula, from an ice-covered shelf to the open ocean. An electrochemical approach, competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV), was applied. Our results indicated that organic ligands in the surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea ice. Organic ligands in the deeper shelf water are supplied via the resuspension of slope or shelf sediments. Further offshore, organic ligands are most likely related to the development of phytoplankton blooms in open ocean waters. On the shelf, total ligand concentrations ([Lt]) were between 1.2 and 6.4 nM eq. Fe. The organic ligands offshore ranged between 1.0 and 3.0 nM eq. Fe. The southern boundary of the Antarctic Circumpolar Current (SB ACC) separated the organic ligands on the shelf from bloom-associated ligands offshore. Overall, organic ligand concentrations always exceeded DFe concentrations (excess ligand concentration, [L′] = 0.8–5.0 nM eq. Fe). The [L′] made up to 80 % of [Lt], suggesting that any additional Fe input can be stabilized in the dissolved form via organic complexation. The denser modified Circumpolar Deep Water (mCDW) on the shelf showed the highest complexation capacity of Fe (αFe'L; the product of [L′] and conditional binding strength of ligands, KFe'Lcond). Since Fe is also supplied by shelf sediments and glacial discharge, the high complexation capacity over the shelf can keep Fe dissolved and available for local primary productivity later in the season upon sea-ice melting.</p

Acoustic imaging of the Dvurechenskii mud volcano in the Black Sea

In the CRIMEA project submarine gas emitting sites in the Black Sea are investigated in order to quantify methane transfer through the water column into the atmosphere. One target area is the Dvurechenskii mud volcano (DMV) in the Sorokin Trough south-east of the Crimea peninsula. The occurrence of gas hydrates and high methane concentrations in the sediment of this mud volcano are known. A seismic wide-angle experiment was performed at the DMV with twelve Ocean Bottom Hydrophones and Seismometers and a GI gun source with frequencies around 100 Hz. By using Kirchhoff depth migration the seismogram sections are transformed to images, which extent to 4 km laterally and 600 metres in depth. The images show the conduit of the DMVand the nearby sediment layers. The DMV has a diameter of 800-1000 m at the sea floor and its conduit has the same form and diameter up to 600 m depth. Several plane sediment layers are disrupted by the conduit, and strong reflectors are identified in 100 m and 400 m depth in the conduit. The lower bowl shaped reflectors are interpreted as collapsed parts of the disrupted sediment layers, which sunk in the lighter material of the conduit. This is also a possible explanation for the upper reflections. Compressional wave velocities are obtained from Kirchhoff migration, and the model is refined by using seismic ray tracing. Bulk density and shear wave velocity can also be obtained by analyzing the data. With the help of these elastic parameters and by using the Frenkel-Gassmann theory, the free gas saturation of the sediment pore space and the gas hydrate saturation can be quantified

The Distribution of Nickel in the West-Atlantic Ocean, Its Relationship With Phosphate and a Comparison to Cadmium and Zinc

Nickel (Ni) is a bio-essential element required for the growth of phytoplankton. It is the least studied bio-essential element, mainly because surface ocean Ni concentrations are never fully depleted and Ni is not generally considered to be a limiting factor. However, stimulation of growth after Ni addition has been observed in past experiments when seemingly ample ambient dissolved Ni was present, suggesting not all dissolved Ni is bio-available. This study details the distribution of Ni along the GEOTRACES GA02 Atlantic Meridional section. Concentrations of Ni were lowest in the surface ocean and the lowest observed concentration of 1.7 nmol kg(-1) was found in the northern hemisphere (NH). The generally lower surface concentrations in the NH subtropical gyre compared to the southern hemisphere (SH), might be related to a greater Ni uptake by nitrogen fixers that are stimulated by iron (Fe) deposition. The distribution of Ni resembles the distribution of cadmium (Cd) and also features a so called kink (change in the steepness of slope) in the Ni-PO4 relationship. Like for Cd, this is caused by the mixing of Nordic and Antarctic origin water masses. The overall distribution of Ni is driven by mixing with an influence of regional remineralization. This influence of remineralization is, with a maximum remineralization contribution of 13% of the highest observed concentration, smaller than for Cd (30%), but larger than for zinc (Zn; 6%). The uptake pattern in the formation regions of Antarctic origin water masses is suggested to be more similar to Zn than to Cd, however, the surface concentrations of Ni are never fully depleted. This results in a North Atlantic concentration distribution of Ni where the trends of increasing and decreasing concentrations between water masses are similar to those observed for Cd, but the actual concentrations as well as the uptake and remineralization patterns are different between these elements

A First Global Oceanic Compilation of Observational Dissolved Aluminum Data With Regional Statistical Data Treatment

Large national and international observational efforts over recent decades have provided extensive and invaluable datasets of a range of ocean variables. Compiled large datasets, structured, or unstructured, are a powerful tool that allow scientists to access and synthesize data collected over large spatial and temporal scales. The data treatment approaches for any element in the ocean could lead to new global perspectives of their distribution patterns and to a better understanding of large-scale oceanic processes and their impact on other biogeochemical cycles, which may not be evident otherwise. Ocean chemistry Big Data analysis may not just be limited to distribution patterns, but may be used to assess how sampling efforts and analytical methodologies can be improved. Furthermore, a systematic global scale assessment of data is important to evaluate the gaps in knowledge and to provide avenues for future research. In this context, here we provide an extensive compilation of oceanic aluminum (Al) concentration data from global ocean basins, including data available in the GEOTRACES Intermediate Data product (Schlitzer et al., 2018), but also thus far unpublished data

Return of naturally sourced Pb to Atlantic surface waters

Anthropogenic emissions completely overwhelmed natural marine lead (Pb) sources during the past century, predominantly due to leaded petrol usage. Here, based on Pb isotope measurements, we reassess the importance of natural and anthropogenic Pb sources to the tropical North Atlantic following the nearly complete global cessation of leaded petrol use. Significant proportions of up to 30-50% of natural Pb, derived from mineral dust, are observed in Atlantic surface waters, reflecting the success of the global effort to reduce anthropogenic Pb emissions. The observation of mineral dust derived Pb in surface waters is governed by the elevated atmospheric mineral dust concentration of the North African dust plume and the dominance of dry deposition for the atmospheric aerosol flux to surface waters. Given these specific regional conditions, emissions from anthropogenic activities will remain the dominant global marine Pb source, even in the absence of leaded petrol combustion

Basin-scale transport of hydrothermal dissolved metals across the South Pacific Ocean

Hydrothermal venting along mid-ocean ridges exerts an important control on the chemical composition of sea water by serving as a major source or sink for a number of trace elements in the ocean(1-3). Of these, iron has received considerable attention because of its role as an essential and often limiting nutrient for primary production in regions of the ocean that are of critical importance for the global carbon cycle(4). It has been thought that most of the dissolved iron discharged by hydrothermal vents is lost from solution close to ridge-axis sources(2,5) and is thus of limited importance for ocean biogeochemistry(6). This long-standing view is challenged by recent studies which suggest that stabilization of hydrothermal dissolved iron may facilitate its longrange oceanic transport(7-10). Such transport has been subsequently inferred from spatially limited oceanographic observations(11-13). Here we report data from the US GEOTRACES Eastern Pacific Zonal Transect (EPZT) that demonstrate lateral transport of hydrothermal dissolved iron, manganese, and aluminium from the southern East Pacific Rise (SEPR) several thousand kilometres westward across the South Pacific Ocean. Dissolved iron exhibits nearly conservative (that is, no loss from solution during transport and mixing) behaviour in this hydrothermal plume, implying a greater longevity in the deep ocean than previously assumed(6,14). Based on our observations, we estimate a global hydrothermal dissolved iron input of three to four gigamoles per year to the ocean interior, which is more than fourfold higher than previous estimates(7,11,14). Complementary simulations with a global-scale ocean biogeochemical model suggest that the observed transport of hydrothermal dissolved iron requires some means of physicochemical stabilization and indicate that hydrothermally derived iron sustains a large fraction of Southern Ocean export productio

Cycling of lithogenic marine particles in the US GEOTRACES North Atlantic transect

© The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 116 (2015): 283-302, doi:10.1016/j.dsr2.2014.11.019.In this paper, we present, describe, and model the first size-fractionated (0.8–51 µm; >51 µm) water-column particulate trace metal results from the US GEOTRACES North Atlantic Zonal Transect in situ pumping survey, with a focus on the lithogenic tracer elements Al, Fe and Ti. This examination of basin-wide, full-depth distributions of particulate elements elucidates many inputs and processes—some for bulk lithogenic material, others element-specific—which are presented via concentration distributions, elemental ratios, size-fractionation dynamics, and steady-state inventories. Key lithogenic inputs from African dust, North American boundary interactions, the Mediterranean outflow, hydrothermal systems, and benthic nepheloid layers are described. Using the refractory lithogenic tracer Ti, we develop a 1-D model for lithogenic particle distributions and test the sensitivities of size-fractionated open-ocean particulate Ti profiles to biotically driven aggregation, disaggregation rates, vertical sinking speeds, and dust input rates. We discuss applications of this lithogenic model to particle cycling in general, and to POC cycling specifically.International and US GEOTRACES Offices (OCE-0850963 and OCE-1129603), and fellowship assistance from the Williams College Tyng Fellowship and MIT/WHOI Academic Programs Office to DCO

Paired dissolved and particulate phase Cu isotope distributions in the South Atlantic

© 2018 The Authors Copper (Cu) is both an essential micronutrient and toxic to photosynthesizing microorganisms at low concentrations. Its dissolved vertical distribution in the oceans is unusual, being neither a nutrient-type nor scavenged-type element. This distribution is attributed to biological uptake in the surface ocean with remineralisation at depth, combined with strong organic complexation by dissolved ligands, scavenging onto particles, and benthic sedimentary input. We present coupled dissolved and particulate phase Cu isotope data along the UK-GEOTRACES South Atlantic section, alongside higher resolution dissolved and particulate phase Cu concentration measurements. Our dissolved phase isotope data contribute to an emerging picture of homogeneous deep ocean δ65Cu, at about +0.65‰ (relative to NIST SRM 976). We identify two pools of Cu in the particulate phase: a refractory, lithogenic pool, at about 0‰, and a labile pool accessed via a weak acidic leach, at about +0.4‰. These two pools are comparable to those previously observed in sediments. We observe deviations towards lighter δ65Cu values in the dissolved phase associated with local enrichments in particulate Cu concentrations along the continental slopes, and in the surface ocean. Copper isotopes are thus a sensitive indicator of localised particle-associated benthic or estuarine Cu inputs. The measurement of Cu isotopes in seawater is analytically challenging, and we call for an intercalibration exercise to better evaluate the potential impacts of UV-irradiation, storage time, and different analytical procedures