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: Meteor Cruise M121 was dedicated to the investigation of the distribution of dissolved and particulate trace metals and their isotopic compositions (TEIs) in the full water column of the Angola Basin and the northernmost Cape Basin. A key aim was to determine the driving factors for the observed distributions, which includes the main external inputs, as well as internal cycling and ocean circulation. The research program of the cruise is official part of the international GEOTRACES program (www.geotraces.org) and cruise M121 corresponds to GEOTRACES cruise GA11. Subject of the cruise was the trace metal clean and contamination-free sampling of waters and particulates for subsequent analyses of the TEIs in the home laboratories of the national and international participants. Besides a standard rosette for the less contaminant prone metals, trace metal clean sampling was realized by using for the first time a new dedicated, coated trace metal clean rosette equipped with Teflon-coated GO-FLO bottles operated via a plastic coated cable from a mobile winch of GEOMAR Kiel. The particulate samples were collected under trace metal clean conditions using established in-situ pump systems operated from Meteor’s Aramid line. The cruise track led from Walvis Bay northwards along the West African margin until 3°S, then turned west until the Zero Meridian, which was followed southwards until 30°S. Then the cruise track turned east again until the Namibian margin was reached and then completed the near shore track northwards until Walvis Bay. The track crossed areas of major external inputs including dust from the Namib Desert and exchange with the west African continental margin and with the oxygen depleted shelf sediments of the Benguela upwelling, as well as with the plume of the Congo outflow, that was followed from its mouth northwards. Our investigations of internal cycling included the extremely high productivity associated with the Benguela Upwelling and the elevated productivity of the Congo plume contrasting with the extremely oligotrophic waters of the southeastern Atlantic Gyre. The links between TEI biogeochemistry and the nitrogen cycle forms an important aspect of our study. The major water masses contributing the Atlantic Meridional Overturning Circulation were sampled in order to investigate if particular TEI signatures are suitable as water mass tracers, in particular near the ocean margin and in the restricted deep Angola Basin. A total of 51 full water column stations were sampled for the different dissolved TEIs, which were in most cases accompanied by sampling for particulates and radium isotopes using the in-situ pumps. In addition, surface waters were continuously sampled under trace metal clean conditions using a towed fish and aerosol and rain samples were continuously collected.

Description: Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

Description: Hydrogen peroxide (H2O2) is present ubiquitously in marine surface waters where it is a reactive intermediate in the cycling of many trace elements. Photochemical processes are considered the dominant natural H2O2 source, yet cannot explain nanomolar H2O2 concentrations below the photic zone. Here, we determined the concentration of H2O2 in full depth profiles across three ocean basins (Mediterranean Sea, South Atlantic and South Pacific Oceans). To determine the accuracy of H2O2 measurements in the deep ocean we also re-assessed the contribution of interfering species to ‘apparent H2O2’, as analysed by the luminol based chemiluminescence technique. Within the vicinity of coastal oxygen minimum zones, accurate measurement of H2O2 was not possible due to interference from Fe(II). Offshore, in deep (〉1000 m) waters H2O2 concentrations ranged from 0.25 ± 0.27 nM (Mediterranean, Balearics-Algeria) to 2.9 ± 2.2 nM (Mediterranean, Corsica-France). Our results indicate that a dark, pelagic H2O2 production mechanism must occur throughout the deep ocean. A bacterial source of H2O2 is the most likely origin and we show that this source is likely sufficient to account for all of the observed H2O2 in the deep ocean.

Description: The supply and bioavailability of iron (Fe) controls primary productivity and N2-fixation in large parts of the global ocean. An important, yet poorly quantified, source to the ocean is particulate Fe (pFe). Here we present the first combined dataset of particulate, labile-particulate (L-pFe) and dissolved Fe (dFe) from the (sub)-tropical North Atlantic. We show a strong relationship between L-pFe and dFe, indicating a dynamic equilibrium between these two phases whereby particles ‘buffer’ dFe and maintain the elevated concentrations observed. Moreover, L-pFe can increase the overall ‘available’ (L-pFe + dFe) Fe pool by up to 55%. The lateral shelf flux of this available Fe was similar in magnitude to observed soluble aerosol-Fe deposition, a comparison that has not been previously considered. These findings demonstrate that L-pFe is integral to Fe cycling and hence plays a role in regulating carbon cycling, warranting its’ inclusion in Fe budgets and biogeochemical models.

Description: The island of South Georgia is situated in the iron (Fe) depleted Antarctic Circumpolar Current of the Southern Ocean. Iron emanating from its shelf system fuels large phytoplankton blooms downstream of the island, but the actual supply mechanisms are unclear. To address this we present the first inventory of Fe, manganese (Mn) and aluminium (Al) in shelf sediments, pore waters and the water column in the vicinity of South Georgia, alongside data on zooplankton-mediated Fe cycling processes. The seafloor sediments were the main particulate Fe source to shelf bottom waters as indicated by Fe / Mn and Fe / Al ratios for shelf sediments and suspended particles in the water column. Less than 1 % of the total particulate Fe pool was leachable surface adsorbed (labile) Fe, and therefore potentially available to organisms. Pore waters formed the primary dissolved Fe (DFe) source to shelf bottom waters supplying 0.1–4 μmol DFe m−2 d−1. However, only 0.41 ± 0.26 μmol DFe m−2 d−1 was transferred to the surface mixed layer by vertical diffusive and advective mixing. Other trace metal sources to surface waters included glacial flour released by melting glaciers and zooplankton excretion processes. On average 6.5 ± 8.2 μmol m−2 d−1 of labile particulate Fe was supplied to the surface mixed layer via krill faecal pellets, with further DFe released by krill at around 1.1 ± 2.2 μmol m−2 d−1. The faecal pellets released by krill constituted of seafloor derived lithogenic material and settled algae debris, in addition to freshly ingested suspended phytoplankton specimen. The phytoplankton Fe requirement in the blooms ca. 1250 km downstream the island of South Georgia was 0.33 ± 0.11 μmol m−2 d−1, with the DFe supply by horizontal/vertical mixing, deep winter mixing and via aeolian dust estimated as ~ 0.12 μmol m−2 d−1. We suggest that additionally required DFe was provided through recycling of biogenically stored Fe following luxury Fe uptake by phytoplankton on the Fe rich shelf. This process would allow Fe to be retained in the surface mixed layer of waters downstream of South Georgia through continuous recycling and biological uptake, and facilitate the large scale blooms.

Description: The distribution of dissolved aluminium (dAl) in the water column of the North Atlantic and Labrador Sea was studied along GEOTRACES section GA01 to unravel the sources and sinks of this element. Surface water dAl concentrations were low (median of 2.5 nM) due to low aerosol deposition and removal by phytoplankton. However, surface water dAl concentrations were enhanced on the Iberian and Greenland shelves (up to 30.9 nM) due to continental inputs (rivers, glacial flour and ice melt). A negative correlation was observed between dAl in surface waters and primary production, phytoplankton community structure and biogenic opal production. The abundance of diatoms exerted a significant (p 〈 0.01) control on the surface particulate Al (pAl) to dAl ratios by decreasing dAl levels and increasing pAl levels. Dissolved Al concentrations generally increased with depth and correlated strongly with silicate (R2 〉 0.76) west of the Iberian Basin, suggesting net release of dAl at depth during remineralization of sinking biogenic opal containing particles. Enrichment of dAl at near-bottom depths was observed due to resuspension of sediments near the sediment-water interface. The highest dAl (up to 38.7 nM) concentrations were observed in Mediterranean Overflow Waters which act as a major source of dAl to mid depth waters of the eastern North Atlantic. This study clearly shows that the vertical and lateral distribution of dAl in the North Atlantic differs when compared to other regions of the North Atlantic and global ocean due to the large spatial differences both in the main source of Al, atmospheric deposition, and the main sink for Al, particle scavenging, between different oceanic regions.

Description: Coastal marine environments are contaminated globally with a vast quantity of unexploded ordnance and munitions from intentional disposal. These munitions contain organic explosive compounds as well as a variety of metals, and represent point sources of chemical pollution to marine waters. Most underwater munitions originate from World Wars at the beginning of the twentieth century, and metal munitions housings have been impacted by extensive corrosion over the course of the following decades. As a result, the risk of munitions-related contaminant release to the water column is increasing. The behavior of munitions compounds is well-characterized in terrestrial systems and groundwater, but is only poorly understood in marine systems. Organic explosive compounds, primarily nitroaromatics and nitramines, can be degraded or transformed by a variety of biotic and abiotic mechanisms. These reaction products exhibit a range in biogeochemical characteristics such as sorption by particles and sediments, and variable environmental behavior as a result. The reaction products often exhibit increased toxicity to biological receptors and geochemical controls like sorption can limit this exposure. Environmental samples typically show low concentrations of munitions compounds in water and sediments (on the order of ng/L and μg/kg, respectively), and ecological risk appears generally low. Nonetheless, recent work demonstrates the possibility of sub-lethal genetic and metabolic effects. This review evaluates the state of knowledge on the occurrence, fate, and effect of munition-related chemical contaminants in the marine environment. There remain a number of knowledge gaps that limit our understanding of munitions-related contaminant spread and effect, and the need for additional work is made all the more urgent by increasing risk of release to the environment.

Description: Vivaspin6® ultrafiltration units with molecular weight “cut-off” membranes of 5, 10, 30, 50, and 100 kDa were used together to examine the size distribution of newly formed iron (Fe) colloids in natural seawater samples and in the presence of several different Fe chelators with varying Fe binding strength. Artificial Fe chelators, such as TAC, and 2 kDG, when added at equimolar levels to Fe, supported the formation of a continuum of Fe-ligand colloids between 5 and 100 kDa. More than 90% of the added 55Fe in these solutions occurred in Fe aggregates/particles larger than 100 kDa. The strong siderophore DFO held the majority of the added 55Fe in the “truly” soluble fraction ≤ 5 kDa, whereas 90% of 55Fe added to UV-irradiated seawater was converted into Fe colloids with a size between 50 to 100 kDa (5–6 nm). Membranes with ≥ 10 kDa showed similar “cut-off” properties on natural seawater samplescollected in the water column off the Peruvian coast. Fe solubility determined with these membranes was approximately six times greater than Fe solubility determined with the 5 kDa membrane and the 0.02 μm syringe filters. This suggests that a seamless size continuum of organic chelators (≤5 kDa–10 kDa) is present in these seawaters and that estimates of ligand production based on 0.02 μm Anotop solubility experiments underestimates the abundance of soluble/colloidal ligands. Regarding these results, we recommend the use of Vivaspin 5 kDa membranes to separate the “truly” soluble from the colloidal Fe fraction.