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: 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: 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: The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 22 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.

Description: Oxygen minimum zones (OMZs) cover extensive areas of eastern boundary ocean regions and play an important role in the cycling of the essential micronutrient iron (Fe). The isotopic composition of dissolved Fe (dFe) in shelf and slope waters on the Senegalese margin was determined to investigate the processes leading to enhanced dFe concentrations (up to 2 nM) in this tropical North Atlantic OMZ. On the shelf, the delta Fe-56 value of dFe (relative to the reference material IRMM-014) was as low as -0.33 parts per thousand, which can be attributed to input of dFe from both reductive and nonreductive dissolution of sediments. Benthic inputs of dFe are subsequently upwelled to surface waters and recycled in the water column by biological uptake and remineralisation processes. Remineralised dFe is characterised by relatively high delta Fe-56 values (up to + 0.41 parts per thousand), and the contribution of remineralised Fe to the total dFe pool increases with distance from the shelf. Remineralisation plays an important role in the redistribution of dFe that is mainly supplied by benthic and atmospheric inputs, although dust inputs, estimated from dissolved aluminium concentrations, were low at the time of our study (2-9 nmol dFe m(-2) d(-1)). As OMZs are expected to expand as climate warms, our data provide important insights into Fe sources and Fe cycling in the tropical North Atlantic Ocean.

Description: Iron (Fe), cobalt (Co), and vitamin B12 addition experiments were performed in the eastern Equatorial Pacific/Peruvian upwelling zone during the 2015 El Niño event. Near the Peruvian coastline, apparent photosystem II photochemical efficiencies (Fv/Fm) were unchanged by nutrient addition and chlorophyll‐a tripled in untreated controls over two days, indicating nutrient replete conditions. Conversely, Fe amendment further away from the coastline in the high nitrate, low Fe zone significantly increased Fv/Fm and chlorophyll‐a concentrations. Mean chlorophyll‐a was further enhanced following supply of Fe+Co and Fe+B12 relative to Fe alone, but this was not statistically significant; further offshore, reported Co depletion relative to Fe could enhance responses. The persistence of Fe limitation in this system under a developing El Niño, as previously demonstrated under non‐El Niño conditions, suggests that diminished upwelled Fe is likely an important factor driving reductions in offshore phytoplankton productivity during these events.

Description: 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.

Description: Dissolved iron (DFe) concentrations in oxygen minimum zones (OMZs) of Eastern Boundary Upwelling Systems are enhanced as a result of high supply rates from anoxic sediments. However, pronounced variations in DFe concentrations in anoxic coastal waters of the Peruvian OMZ indicate that there are factors in addition to dissolved oxygen concentrations (O2) that control Fe cycling. Our study demonstrates that sediment-derived reduced Fe (Fe(II)) forms the main DFe fraction in the anoxic/euxinic water column off Peru, which is responsible for DFe accumulations of up to 200 nmol L-1. Lowest DFe values were observed in anoxic shelf waters in the presence of nitrate and nitrite. This reflects oxidation of sediment-sourced Fe(II) associated with nitrate/nitrite reduction and subsequent removal as particulate Fe(III) oxyhydroxides. Unexpectedly, the highest DFe levels were observed in waters with elevated concentrations of hydrogen sulfide (up to 4 µmol L-1) and correspondingly depleted nitrate/nitrite concentrations (〈0.18 µmol L-1). Under these conditions, Fe removal was reduced through stabilization of Fe(II) as aqueous iron sulfide (FeSaqu) which comprises complexes (e.g., FeSH+) and clusters (e.g., Fe2S2|4H2O). Sulfidic events on the Peruvian shelf consequently enhance Fe availability, and may increase in frequency in future due to projected expansion and intensification of OMZs.

Description: Iron solubility (cFeS) ranged from 0.4 to 1.5 nmol L−1, decreasing from south to north in three different Southern Ocean zones (the Coastal Zone, the Antarctic Zone, and the Polar Frontal Zone plus the Subantarctic Zone). This decrease was at times correlated with an increase in temperature. Organic Fe solubility (cFeS,org), which was obtained by subtracting from total measured Fe solubility the solubility of inorganic species of iron (Fe) at the measurement temperature (20°C), ranged from 0.3 to 1.3 nmol L−1, representing an average of 32 ± 14% of the concentration of ligands in the dissolved size fraction as determined via competitive ligand exchange–absorptive cathodic stripping voltammetry (barring a handful of extremely high values from a transect run to the east of Prydz Bay). Values of cFeS were mainly lower than the predicted value for inorganic Fe solubility at the in situ temperature. Total in situ Fe solubility (cFeS,adj) was therefore estimated by adjusting for inorganic Fe solubility at in situ temperatures (between −2°C and +18°C). Because in situ temperatures in the Antarctic Circumpolar Current were mostly lower than +3°C, such cFeS,adj values, ranging from 0.5 to 1.8 nmol L−1, were roughly twice as large as cFeS,org. The adjustment relies heavily on model calculations of inorganic Fe solubility but, if correct, indicates that the bulk of the solubility of Fe in the cold waters of the Southern Ocean is tied to the solubility of inorganic Fe rather than to Fe ligands in the soluble size fraction.