ALBERT

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: High dissolved iron (dFe) concentrations of the order of 10-100 nmol L-1 are a feature of waters influenced by sedimentary inputs in oxygen minimum zones (OMZ). However, the temporal development of dFe concentrations is poorly defined due to a general reliance on snapshot cross-shelf sections to study marine trace metal dynamics. Multiple cruise campaigns since the 1980s have investigated Fe dynamics over the Peruvian shelf, particularly between 9-17°S where the shelf is broad, extremely productive and known to feature benthic dFe effluxes which are amongst the highest measured globally. This extensive long-term dataset uniquely allows us to study the interannual variability in dFe concentrations and their response to El Niño–Southern Oscillation (ENSO) events. By combining data from 11 cruises during the period 1984-2017 we are able to evaluate dFe dynamics on interannual timescales in a major OMZ. The region where average dFe concentrations are sensitive to variations in ENSO is confined to a subsurface layer at depths between 50-150 m, particularly in the narrow coastal region within 50 km of the coastline. Subsurface dFe concentrations were generally low during El Niño events (0.7-15.4 nmol L-1) and relatively high with a wider range of variability during the cold ENSO phase (1.1-52.1 nmol L-1). Inverse relationships between wind speed and surface/subsurface dFe were evident. In the subsurface layer, this may be attributable to enhanced dFe offshore transport along isopycnals when upwelling-favorable winds relax in accordance with previously outlined theories. Surface layer (〈40 m) dFe variability was likely associated with a dilution and/or oxidation effect depending on the strength of wind driven water column mixing. Upwelling brings macronutrient-rich water into the euphotic zone, but its intensity had a limited impact on upper layer dFe concentrations possibly due to the influence of an onshore geostrophic flow. Interannual variability in surface chlorophyll-a (Chl-a) was found to correlate with dFe concentration in the offshore zone of northern Peru. This is consistent with bioassay experiments and climatological residual nitrate concentrations which both indicate proximal Fe limitation of phytoplankton growth over and beyond the northern Peruvian shelf. Overall, our work highlights the importance of physical factors driving short-term variations in Fe availability in one of the world’s most economically important fishery regions and suggests that, despite pronounced spatial and temporal variability in dFe concentrations, the ENSO phase has an impact on dFe availability.