Trace metal sources and cycling in tropical oxygen minimum zones

This thesis discusses sources and cycling of trace metals in tropical oxygen minimum zones. This thesis presents a new developed method for the analysis of a range of trace metals (iron, cadmium, nickel, zinc, copper, lead, cobalt and manganese) at trace levels in seawater. In the following chapters trace metal data from two distinct oxygen minimum zones are presented, one in the Eastern Tropical North Atlantic off the coast of Mauritania and one in the Eastern Tropical South Pacific off the coast of Peru. The work has a particular focus on the redox-sensitive trace metals, iron, cobalt and manganese and the influence of seawater oxygen concentrations on the sources and distribution of these trace metals. Finally differences in trace metal distributions between the two study regions are discussed

Hydrogen peroxide in deep waters from the Mediterranean Sea, South Atlantic and South Pacific Oceans

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

Automated preconcentration of Fe, Zn, Cu, Ni, Cd, Pb, Co, and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry

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

El Niño‐driven oxygenation impacts Peruvian shelf iron supply to the South Pacific Ocean

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

Effects of 238U variability and physical transport on water column 234Th downward fluxes in the coastal upwelling system off Peru

The eastern boundary region of the southeastern Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use vessel-mounted acoustic Doppler current profiler (VmADCP) current velocities, satellite wind speed and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11 to 16∘ S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind speed during our cruises induced low upwelling rates and minimal upwelled 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Horizontal advective and diffusive 234Th fluxes were negligible because of small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40 % in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone and cautioned future carbon export studies to take these temporal variabilities into consideration while evaluating carbon export efficiency

A mosaic of phytoplankton responses across Patagonia, the SE Pacific and SW Atlantic Ocean to ash deposition and trace metal release from the Calbuco 2015 volcanic eruption

Following the April 2015 eruption of the Calbuco volcano, an extensive ash plume spread across northern Patagonia and into the SE Pacific and SW Atlantic Ocean. Here we report the results of field surveys conducted in the marine region receiving the highest ash load following the eruption (Reloncaví Fjord). The fortuitous location of a long-term monitoring station in Reloncaví Fjord provided data to evaluate inshore phytoplankton bloom dynamics and carbonate chemistry during April–May 2015. Satellite derived chlorophyll-a measurements over the ocean regions affected by the ash plume in May 2015 were obtained to determine the spatial-temporal gradient in offshore phytoplankton response to ash. Additionally, leaching experiments were performed to quantify the release of total alkalinity, trace elements (Fe, Mn, Pb, Co, Cu, Ni and Cd) and major ions (Fl, Cl, SO4, NO3, Li, Na, NH4, K, Mg, Ca) from ash into solution. Within Reloncaví Fjord, integrated peak diatom abundances during the May 2015 austral bloom were higher than usual (up to 1.4 × 1011 cells m−2, integrated to 15 m depth), with the bloom intensity perhaps moderated due to high ash loadings in the two weeks following the eruption. In the offshore SE Pacific, a short duration phytoplankton bloom corresponded closely in space and time to the maximum observed ash plume, potentially in response to Fe-fertilization of a region where phytoplankton growth is typically Fe-limited at this time of year. Conversely, no clear fertilization was found in the area subject to an ash plume over the SW Atlantic where the availability of fixed nitrogen is thought to limit phytoplankton growth which was consistent with no significant release of fixed nitrogen from ash. In addition to release of nanomolar concentrations of dissolved Fe from ash suspended in seawater, it was observed that low loadings (< 5 mg L−1) of freshly deposited ash were an unusually prolific source of Fe(II) into solution (up to 1.0 µmol Fe g−1), suggesting that the release of bioaccessible Fe from ash sources may generally be under-estimated when quantified from aged ash. This release of Fe(II) may make freshly deposited ash an unusually efficient dissolved Fe source with the 18–38 % fraction of dissolved Fe released as Fe(II) from Calbuco ash roughly comparable to literature values for Fe released into seawater from aerosols collected over the Pacific Ocean

Iron limitation of microbial phosphorus acquisition in the tropical North Atlantic

In certain regions of the predominantly nitrogen limited ocean, microbes can become co-limited by phosphorus. Within such regions, a proportion of the dissolved organic phosphorus pool can be accessed by microbes employing a variety of alkaline phosphatase (APase) enzymes. In contrast to the PhoA family of APases that utilize zinc as a cofactor, the recent discovery of iron as a cofactor in the more widespread PhoX and PhoD implies the potential for a biochemically dependant interplay between oceanic zinc, iron and phosphorus cycles. Here we demonstrate enhanced natural community APase activity following iron amendment within the low zinc and moderately low iron Western North Atlantic. In contrast we find no evidence for trace metal limitation of APase activity beneath the Saharan dust plume in the Eastern Atlantic. Such intermittent iron limitation of microbial phosphorus acquisition provides an additional facet in the argument for iron controlling the coupling between oceanic nitrogen and phosphorus cycles

Controls on redox-sensitive trace metals in the Mauritanian oxygen minimum zone

The availability of the micronutrient iron (Fe) in surface waters determines primary production, N2 fixation, and microbial community structure in large parts of the world's ocean, and thus it plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling systems and the connected oxygen minimum zones (OMZs) are typically associated with elevated concentrations of redox-sensitive trace metals (e.g., Fe, manganese (Mn), and cobalt (Co)), with shelf sediments typically forming a key source. Over the last 5 decades, an expansion and intensification of OMZs has been observed and this trend is likely to proceed. However, it is unclear how trace-metal (TM) distributions and transport are influenced by decreasing oxygen (O2) concentrations. Here we present dissolved (d; 0.2 µm) TM data collected at seven stations along a 50 km transect in the Mauritanian shelf region. We observed enhanced concentrations of Fe, Co, and Mn corresponding with low O2 concentrations (<50 µmol kg−1), which were decoupled from major nutrients and nutrient-like and scavenged TMs (cadmium (Cd), lead (Pb), nickel (Ni), and copper (Cu)). Additionally, data from repeated station occupations indicated a direct link between dissolved and leachable particulate Fe, Co, Mn, and O2. An observed dFe (dissolved iron) decrease from 10 to 5 nmol L−1 coincided with an O2 increase from 30 to 50 µmol kg−1 and with a concomitant decrease in turbidity. The changes in Fe (Co and Mn) were likely driven by variations in their release from sediment pore water, facilitated by lower O2 concentrations and longer residence time of the water mass on the shelf. Variations in organic matter remineralization and lithogenic inputs (atmospheric deposition or sediment resuspension; assessed using Al as indicator for lithogenic inputs) only played a minor role in redox-sensitive TM variability. Vertical dFe fluxes from O2-depleted subsurface-to-surface waters (0.08–13.5 µmol m−2 d−1) driven by turbulent mixing and vertical advection were an order of magnitude larger than atmospheric deposition fluxes (0.63–1.43 µmol m−2 d−1; estimated using dAl inventories in the surface mixed layer) in the continental slope and shelf region. Benthic fluxes are therefore the dominant dFe supply to surface waters on the continental margins of the Mauritanian upwelling region. Overall, our results indicated that the projected future decrease in O2 concentrations in OMZs may result in increases in Fe, Mn, and Co concentrations

Influence of iron, cobalt, and vitamin B12 supply on phytoplankton growth in the tropical East Pacific during the 2015 El Niño

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

Trace metal data from water samples during SONNE cruise SO243

The file contains dissolved and total dissolvable trace metal concentrations (Fe, Co, Mn, Ni, Cd, Cu, Pb, Zn and V), hydrogen peroxide (H2O2), Fe(II), and iodide and iodate concentrations of surface water samples and station depth profiles. Trace metal concentrations were measured by ICP-MS after preconcentration (Rapp et al. 2017, Anal. Chim. Acta). Fe(II) and H2O2 were analyzed on-board using chemiluminescence flow injection analysis (Hopwood et al. 2017, Sci. Rep.). Iodide concentrations were analyzed by cathodic stripping square wave voltammetry (Luther et al. 1988, Anal. Chem.) and Iodate concentrations were measured spectrophotometrically (Chapman and Liss 1977, Mar. Chem