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: Anthropogenic activities have resulted in enhanced lead (Pb) emissions to the environment over the past century, mainly through the combustion of leaded gasoline. Here, we present the first combined dissolved (DPb), labile (LpPb) and particulate (PPb) Pb dataset from the Northeast Atlantic (Celtic Sea) since the phasing out of leaded gasoline in Europe. Concentrations of DPb in surface waters have decreased by 4-fold over the last four decades. We demonstrate that anthropogenic Pb is transported from the Mediterranean Sea over long distances (〉2500 km). Benthic DPb fluxes exceeded the atmospheric Pb flux in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study provides insights into Pb biogeochemical cycling and demonstrates the potential of Pb in constraining ocean circulation patterns.

Description: Highlights • A rapid automated analytical method for simultaneous analysis of multiple trace metals in small volumes of seawater. • Isotope dilution is utilized for concentration quantification, eliminating sensitivity to variation in recovery. • Minimal variability in automated sample loading and elution volumes allows precise quantification via standard addition for monoisotopic elements. • High accuracy was confirmed by analysis of reference seawaters SAFe S, D1 and D2. • The utilized resin (WAKO) demonstrated improved recoveries for most tested trace metals in comparison to a NOBIAS Chelate-PA1 resin. A rapid, automated, high-throughput analytical method capable of simultaneous analysis of multiple elements at trace and ultratrace levels is required to investigate the biogeochemical cycle of trace metals in the ocean. Here we present an analytical approach which uses a commercially available automated preconcentration device (SeaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto a chelating resin (WAKO) and subsequent simultaneous analysis of iron (Fe), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), lead (Pb), cobalt (Co) and manganese (Mn) by high-resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS). Quantification of sample concentration was undertaken using isotope dilution for Fe, Zn, Cu, Ni, Cd and Pb, and standard addition for Co and Mn. The chelating resin is shown to have a high affinity for all analyzed elements, with recoveries between 83 and 100% for all elements, except Mn (60%) and Ni (48%), and showed higher recoveries for Ni, Cd, Pb, Co and Mn in direct comparison to an alternative resin (NOBIAS Chelate-PA1). The reduced recoveries for Ni and Mn using the WAKO resin did not affect the quantification accuracy. A relatively constant retention efficiency on the resin over a broad pH range (pH 5–8) was observed for the trace metals, except for Mn. Mn quantification using standard addition required accurate sample pH adjustment with optimal recoveries at pH 7.5 ± 0.3. UV digestion was necessary to increase recovery of Co and Cu in seawater by 15.6% and 11.4%, respectively, and achieved full break-down of spiked Co-containing vitamin B12 complexes. Low blank levels and detection limits could be achieved (e.g., 0.029 nmol L⁻¹ for Fe and 0.028 nmol L⁻¹ for Zn) with the use of high purity reagents. Precision and accuracy were assessed using SAFe S, D1, and D2 reference seawaters, and results were in good agreement with available consensus values. The presented method is ideal for high throughput simultaneous analysis of trace elements in coastal and oceanic seawaters. We present a successful application of the analytical method to samples collected in June 2014 in the Northeast Atlantic Ocean.

Description: Siderophores are low molecular weight high affinity iron chelates found at low concentrations in seawater. In this study we determined the total concentrations and identities of siderophores in extracts isolated from a shelf sea environment on the Northwest European shelf by high performance liquid chromatography coupled to high resolution inductively coupled plasma mass spectrometry (ICP-MS) in parallel to high resolution electrospray ionisation mass spectrometry (ESI-MS). We identified a total of 24 different siderophores in our samples via metal isotope profiling of masses detected by ESI-MS. Twenty three of the identified siderophores could be assigned to three siderophore families – ferrioxamines, amphibactins and marinobactins. In contrast, only 12 peaks could be resolved in iron chromatograms obtained via ICP-MS analysis. Comparison of results obtained by the two mass spectrometry detectors showed that neither method was able to detect and identify all siderophores present in the samples on its own. We assessed the impact of our observed total siderophore concentrations on iron speciation by calculating the distribution of iron species as a function of total siderophore concentrations at different iron concentrations representative of our study area. We considered competition for iron between siderophores, a humic like dissolved organic matter (DOM) fraction and hydroxide ions by combining an ion-pair model with a non-ideal competitive interaction (NICA)-Donnan model. We found that the overall impact of siderophores on iron biogeochemistry is low at concentrations of siderophore 〈100 pmol L-1, and that the dominant iron species present at siderophore concentrations of the order of a few tens of pmol L-1 will be iron bound to the humic like DOM fraction. Furthermore the heterogeneity of binding sites in the humic like DOM fraction means that other binding sites present in organic matter could be effective competitors for siderophores, especially at low iron concentrations. Our findings highlight the importance of binding site heterogeneity when considering the influence of different iron binding groups on iron speciation in the marine environment.

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.

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.