ALBERT

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: 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 pH of aqueous solutions is known to impact the chemical speciation of trace metals. In this study we conducted titrations of coastal seawaters with iron and copper at pH 7.91, 7.37 and 6.99 (expressed on the total pH scale). Changes in the concentration of iron and copper that complexed with the added ligands 1-nitroso-2-napthol and salicylaldoxime respectively were determined by adsorptive cathodic stripping voltammetry - competitive ligand equilibrium (AdCSV-CLE). Interpretation of the results, assuming complexation by a low concentration of discrete ligands, showed that conditional stability constants for iron complexes increased relative to inorganic iron complexation as pH decreased by approximately 1 log unit per pH unit, whilst those for copper did not change. No trend was observed for concentrations of iron and copper complexing ligands over the pH range examined. We also interpreted our titration data by describing chemical binding and polyelectrolytic effects using non-ideal competitive adsorption in Donnan-like gels (NICA-Donnan model) in a proof of concept study. The NICA-Donnan approach allows for the development of a set of model parameters that are independent of ionic strength and pH, and thus calculation of metal speciation can be undertaken at ambient sample pH or the pH of a future, more acidic ocean. There is currently a lack of basic NICA-Donnan parameters applicable to marine dissolved organic matter (DOM) so we assumed that the measured marine dissolved organic carbon could be characterized as terrestrial fulvic acids. Generic NICA-Donnan parameters were applied within the framework of the software program visual MINTEQ and the metal –added ligand concentrations [MeAL] calculated for the AdCSV-CLE conditions. For copper, calculated [MeAL] using the NICA-Donnan model for DOM were consistent with measured [MeAL], but for iron an inert fraction with kinetically inhibited dissolution was required in addition to the NICA-Donnan model in order to approximate the trends observed in measured [MeAL]. We calculated iron and copper speciation in Northwest European shelf water samples at ambient alkalinity and projected increased pCO2 concentrations as a demonstration of the potential of the approach.

Description: The cyanobacterium Trichodesmium is responsible for a significant proportion of the annual "new" nitrogen introduced into the global ocean. Despite being arguably the best studied marine diazotroph, the factors controlling the distribution and growth of Trichodesmium remain a subject of debate, with sea surface temperature, the partial pressure of CO2, and nutrients including iron (Fe) and phosphorus (P), all suggested to be important. Synthesizing data from seven cruises collectively spanning large temporal and spatial scales across the Atlantic Ocean, including two previously unreported studies crossing the largely undersampled South Atlantic gyre, we assessed the relationship between proposed environmental drivers and both community N2 fixation rates and the distribution of Trichodesmium. Simple linear regression analysis would suggest no relationship between any of the sampled environmental variables and N2 fixation rates. However, considering the concentrations of iron and phosphorus together within a simplified resource-ratio framework, illustrated using an idealized numerical model, indicates the combined effects these nutrients have on Trichodesmium and broader diazotroph biogeography, alongside the reciprocal maintenance of different biogeographic provinces of the (sub)tropical Atlantic in states of Fe or P oligotrophy by diazotrophy. The qualitative principles of the resource-ratio framework are argued to be consistent with both the previously described North-South Atlantic contrast in Trichodesmium abundance and the presence and consequence of a substantial non-Trichodesmium diazotrophic community in the western South Atlantic subtropical gyre. A comprehensive, observation-based explanation of the interactions between Trichodesmium and the wider diazotrophic community with iron and phosphorus in the Atlantic Ocean is thus revealed.

Description: Volcanic eruptions have been hypothesized as an iron supply mechanism for phytoplankton blooms; however, little direct evidence of stimulatory responses has been obtained in the field. Here we present the results of twenty-one 1-2day bottle enrichment experiments from cruises in the South Atlantic and Southern Ocean which conclusively demonstrated a photophysiological and biomass stimulation of phytoplankton communities following supply of basaltic or rhyolitic volcanic ash. Furthermore, experiments in the Southern Ocean demonstrated significant phytoplankton community responses to volcanic ash supply in the absence of responses to addition of dissolved iron alone. At these sites, dissolved manganese concentrations were among the lowest ever measured in seawater, and we therefore suggest that the enhanced response to ash may have been a result of the relief of manganese (co)limitation. Our results imply that volcanic ash deposition events could trigger extensive phytoplankton blooms, potentially capable of significant impacts on regional carbon cycling.

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: Upwelling ocean currents associated with oxygen minimum zones (OMZs) supply nutrients fuelling intense marine productivity. Perturbations in the extent and intensity of OMZs are projected in the future, but it is currently uncertain how this will impact fluxes of redox‐sensitive trace metal micronutrients to the surface ocean. Here we report seawater concentrations of Fe, Mn, Co, Cd, and Ni alongside the redox indicator iodide/iodate in the Peruvian OMZ during the 2015 El Niño event. The El Niño drove atypical upwelling of oxygen‐enriched water over the Peruvian Shelf, resulting in oxidized iodine and strongly depleted Fe (II), total dissolved Fe, and reactive particulate Fe concentrations relative to non‐El Niño conditions. Observations of Fe were matched by the redox‐sensitive micronutrients Co and Mn, but not by non‐redox‐sensitive Cd and Ni. These observations demonstrate that oxygenation of OMZs significantly reduces water column inventories of redox‐sensitive micronutrients, with potential impacts on ocean productivity. Plain Language Summary Some trace metals, including iron, are essential micronutrients for phytoplankton growth. However, the solubility of iron is very low under oxygenated conditions. Consequently, restricted iron availability in oxygen‐rich seawater can limit phytoplankton growth in the ocean, including in the Eastern Tropical South Pacific. Under typical conditions, depleted oxygen on the South American continental shelf is generally thought to enhance iron supply to the ocean, fuelling phytoplankton productivity in overlying waters. However, the impact of changes in oxygenation, which are predicted to occur in the future, are not known. The 2015 El Niño event led to unusually high oxygen on the Peruvian shelf, offering a system‐scale test on how oxygen influences seawater iron concentrations. We show that El Niño‐driven oxygenation resulted in marked decreases in iron and other metals sensitive to oxygen (cobalt and manganese), whilst metals not sensitive to oxygen (cadmium and nickel) were unaffected. The measured reductions in iron may have led to decreased phytoplankton productivity.