Description: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.

Description: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.

Description: Dissolved Fe(II) in seawater is deemed an important micronutrient for microbial organisms, but its analysis is challenging due to its transient nature. We conducted a series of Fe(II) method comparison experiments, where spikes of 5 to 31 nM Fe(II) were added to manipulated seawaters with varying dissolved oxygen (37 to 156 μM) concentrations. The observed Fe(II) concentrations from four analytical methods were compared: spectrophotometry with ferrozine, stripping voltammetry, and flow injection analysis using luminol (with, and without, a pre-concentration column). Direct comparisons between the different methods were undertaken from the derived apparent Fe(II) oxidation rate constant (k1). Whilst the two luminol based methods produced the most similar concentrations throughout the experiments, k1 was still subject to a 20–30% discrepancy between them. Contributing factors may have included uncertainty in the calibration curves, and different responses to interferences from Co(II) and humic/fulvic organic material. The difference in measured Fe(II) concentrations between the luminol and ferrozine methods, from 10 min–2 h after the Fe(II) spikes were added, was always relatively large in absolute terms (〉4 nM) and relative to the spike added (〉20% of the initial Fe(II) concentration). k1 derived from ferrozine observed Fe(II) concentrations was 3–80%, and 4–16%, of that derived from luminol observed Fe(II) with, and without, pre-concentration respectively. The poorest comparability of k1 was found after humic/fulvic material was added to raise dissolved organic carbon to 120 μM. A luminol method without pre-concentration then observed Fe(II) to fall below the detection limit (〈0.49 nM) within 10 min of a 17 nM Fe(II) spike addition, yet other methods still observed Fe(II) concentrations of 2.7 to 3.7 nM 30 min later. k1 also diverged accordingly with the ferrozine derived value 4% of that derived from luminol without pre-concentration. These apparent inconsistencies suggest that some inter-dataset differences in measured Fe(II) oxidation rates in natural waters may be attributable to differences in the analytical methods used rather than arising solely from substantial shifts in Fe(II) speciation.

Description: A realistic estimation of uncertainty is an essential requirement for all analytical measurements. It is common practice, however, for the uncertainty estimate of a chemical measurement to be based on the instrumental precision associated with the analysis of a single or multiple samples, which can lead to underestimation. Within the context of chemical oceanography such an underestimation of uncertainty could lead to an over interpretation of the result(s) and hence impact on, e.g., studies of biogeochemical cycles, and the outputs from oceanographic models. Getting high quality observational data with a firm uncertainty assessment is therefore essential for proper model validation. This paper describes and compares two recommended approaches that can give a more holistic assessment of the uncertainty associated with such measurements, referred to here as the “bottom up” or modeling approach and the “top down” or empirical approach. “Best practice” recommendations for the implementation of these strategies are provided. The “bottom up” approach combines the standard uncertainties associated with each stage of the entire measurement procedure. The “top down” approach combines the uncertainties associated with day to day reproducibility and possible bias in the complete data set and is easy to use. For analytical methods that are routinely used, laboratories will have access to the information required to calculate the uncertainty from archived quality assurance data. The determination of trace elements in seawater is a significant analytical challenge and iron is used as an example for the implementation of both approaches using real oceanographic data. Relative expanded uncertainties of 10 – 20% were estimated for both approaches compared with a typical short term precision (rsd) of≤5%.

Description: We used a combined ion pairing - organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑Fe(OH)i3−i)) and apparent Fe(III) solubility (SFe(III)app) at ambient pH and temperature in the water column of the Celtic Sea. SFe(III)app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). SFe(III)app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters 〉1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations.

Description: Dissolved (〈0.2 μm) trace metals (dTMs) including iron (Fe), manganese (Mn), and cobalt (Co) are micronutrients that (co-) limit phytoplankton growth in many ocean regions. Here, we present the spatial and seasonal distributions of dFe, dMn, and dCo on the Northeast Atlantic continental margin (Celtic Sea), along a transect across the shelf and two off-shelf transects along a canyon and a spur. Waters on the continental shelf showed much higher dTM concentrations (dFe 0.07–6.50 nmol L−1, average 1.41 ± 0.96 nmol L−1, n = 138; dMn 0.868–14.8 nmol L−1, 2.75 ± 2.37 nmol L−1, n = 148; dCo 54.8–217 pmol L−1, 109 ± 32 pmol L−1, n = 144) than on the slope (dFe 0.03–1.90 nmol L−1, 0.65 ± 0.43 nmol L−1, n = 454; dMn 0.223–1.14 nmol L−1, 0.58 ± 0.20 nmol L−1, n = 458; dCo 27.3–122 pmol L−1, 71.7 ± 11.7 pmol L−1, n = 441), attributed to strong dTM contributions from a low-salinity endmember, i.e., riverine discharge. Benthic sedimentary input via reductive dissolution (especially for dFe and dMn), delineated by short-lived radium (Ra) isotopic activities (223Raxs and 224Raxs), was only prominent at a station (Site A) characterized by fine sediments. On the continental slope, dMn levels at depth were mainly determined by the formation of insoluble Mn oxides and the intrusion of Mediterranean Outflow Waters. In contrast, dFe and dCo concentrations at depth were balanced by the regeneration from remineralization of sinking organic particles and scavenging removal. In addition, bottom and intermediate nepheloid layers along the slope illustrated both elevated dTM concentrations and Ra isotopic activities. The presence of nepheloid layers is especially significant along the canyon transect relative to the spur transect, demonstrating the importance of slope topography on the off-shelf transport of dTMs into the Northeast Atlantic Ocean. As a seasonal stratified shelf sea, dTMs and nutrients showed synchronized seasonal variations on the shelf, indicating the influence of biological processes in addition to source effects. Surface dFe and dCo were depleted in summer due to enhanced biological uptake, while sub-surface dFe and dCo were elevated in summer and autumn ascribed to the remineralization of sinking organic particles. In contrast, surface dMn levels were predominantly controlled by the seasonal variations in photoreduction, while sub-surface dMn concentrations were relatively constant throughout the year. The combined effects of fluvial and benthic sources, topographical controls, and biological processes shape the seasonal variations of dTM distributions. Such seasonal variations in dTMs and biological activities can affect the biological carbon pump on the Northeast Atlantic continental margin, and may further influence the carbon cycle in the Atlantic Ocean via the dynamic dTM exchange between continental margins and the open ocean.

Description: Nutrients and nutrient-like dissolved trace metals (dTMs) are essential for the functioning of marine organisms and therefore form an important part of ocean biogeochemical cycles. Here, we report on the seasonal distributions of dissolved zinc (dZn), nickel (dNi), copper (dCu), cadmium (dCd), aluminum (dAl), and nutrients on the Northeast Atlantic continental margin (Celtic Sea), which is representative for temperate shelf seas globally. Variations in surface water dTM and nutrient concentrations were mainly regulated by seasonal changes in biological processes. The stoichiometry of dTMs (especially for dCu and dZn) and nutrients on the continental shelf was additionally affected by fluvial inputs. Nutrients and dTMs at depth on the continental slope were determined by water mass mixing driven by ocean circulation, without an important role for local remineralization processes. The Mediterranean Outflow Waters are especially important for delivering Mediterranean-sourced dTMs to the Northeast Atlantic Ocean and drive dTM:nutrient kinks at a depth of ~1000 m. These results highlight the importance of riverine inputs, seasonality of primary production and ocean circulation on the distributions of nutrients and nutrient-like dTMs in temperate continental margin seas. Future climate related changes in the forcing factors may impact the availability of nutrients and dTMs to marine organisms in highly productive continental shelf regions and consequently the regional carbon cycle.