Toward a regional classification to provide a more inclusive examination of the ocean biogeochemistry of iron-binding ligands

© 2017 Hassler, van den Berg and Boyd. Iron-binding ligands are paramount to understanding iron biogeochemistry and its potential to set the productivity and the magnitude of the biological pump in > 30% of the ocean. However, the nature of these ligands is largely uncharacterized and little is known about their sources, sensitivity to photochemistry and biological transformation, or scavenging behavior. Despite many uncertainties, there is no doubt that ligands are produced by a wide range of biotic and abiotic processes, and that the bulk ligand pool encompasses a diverse range of molecules. Despite widespread recognition of the likelihood of a continuum of ligand classes making up the bulk ligand pool, studies to date largely focused on the dominant ligand. Thus, most studies have overlooked the need to assess where these targeted molecules fit across the spectrum of ligands that comprise the bulk ligand pool. Here we summarize present knowledge to critically assess the source(s), function(s), production pathways, and loss mechanisms of three important iron-binding organic ligand groups in order to assess their distinctive characteristics and how they link with observed ligand distributions. We considered that ligands are contained in broad groupings of exopolymer substances (EPS), humic substances (HS), and siderophores; using literature data for speciation modeling suggested that this adequately described the iron speciation reported in the ocean. We hypothesize that a holistic viewpoint of the multi-faceted controls on ligands dynamics is essential to begin to understand why some ligands can be expected to dominate in particular oceanic regions, depth strata, or exhibit seasonality and/or lateral gradients. We advocate that the development of a regional classification will enhance our understanding of the changing composition of the bulk ligand pool across the global ocean and to help address to what extent seasonality influences the makeup of this pool. This classification, based on selected functional ligand classes, can act as a bridge to use future ligand datasets to fill in the gaps in the continuum

Biotic and abiotic retention, recycling and remineralization of metals in the ocean

Trace metals shape both the biogeochemical functioning and biological structure of oceanic provinces. Trace metal biogeochemistry has primarily focused on modes of external supply of metals from aeolian, hydrothermal, sedimentary and other sources. However, metals also undergo internal transformations such as abiotic and biotic retention, recycling and remineralization. The role of these internal transformations in metal biogeochemical cycling is now coming into focus. First, the retention of metals by biota in the surface ocean for days, weeks or months depends on taxon-specific metal requirements of phytoplankton, and on their ultimate fate: that is, viral lysis, senescence, grazing and/or export to depth. Rapid recycling of metals in the surface ocean can extend seasonal productivity by maintaining higher levels of metal bioavailability compared to the influence of external metal input alone. As metal-containing organic particles are exported from the surface ocean, different metals exhibit distinct patterns of remineralization with depth. These patterns are mediated by a wide range of physicochemical and microbial processes such as the ability of particles to sorb metals, and are influenced by the mineral and organic characteristics of sinking particles. We conclude that internal metal transformations play an essential role in controlling metal bioavailability, phytoplankton distributions and the subsurface resupply of metals

Iron availability influences the tolerance of Southern Ocean phytoplankton to warming and elevated irradiance

The Southern Ocean is responsible for approximately 40% of oceanic carbon uptake through biological and physical processes. In the Southern Ocean, phytoplankton growth is limited by low iron (Fe) and light supply. Climate model projections for the Southern Ocean indicate that temperature, underwater irradiance and Fe supply are likely to change simultaneously in the future due to increasing anthropogenic carbon dioxide emissions. The individual effects of these environmental properties on phytoplankton physiology have been extensively researched, and culturing studies using Southern Ocean phytoplankton have shown that temperature and Fe will play a key role on setting growth under future conditions. To explore the potential responses of Southern Ocean phytoplankton to these environmental changes, we cultured the haptophyte Phaeocystis antarctica and the diatoms Chaetoceros flexuosus, Proboscia inermis, and Thalassiosira antarctica under two light and iron combinations and over a range of temperatures. Our study revealed that the thermal response curves of key Southern Ocean phytoplankton are diverse, with the highest growth rates measured at 5°C (the annual temperature range at the isolation sites is currently 1–4°C). Warming had species-specific effects on the photochemical efficiency of photosystem II (PSII; Fv/Fm), the functional absorption cross-section of PSII (σPSII), carbon:nitrogen ratio and cellular Chlorophyll a concentrations. Iron availability increased species’ ability to tolerate warmer conditions by increasing the upper limit for growth and subsequently increasing the thermal niche that each species inhabit

Some observations on the biogeochemical cycling of zinc in the Australian sector of the Southern Ocean: a dedication to Keith Hunter

In this study we investigated the distribution of dissolved and particulate zinc (dZn and pZn respectively) and its isotopes in the Subantarctic Zone as part of a Geotraces Process voyage. dZn and pZn depth profiles contrasted each other, with dZn showing depletion within the euphotic zone while pZn profiles showed enrichment. Fitting a power law equation to the pZn profiles produced an attenuation factor of 0.82, which contrasted values for particulate phosphorus, cadmium and copper. The results indicate that zinc has a longer regeneration length scale than phosphorus and cadmium, but shorter than copper. The differential regeneration of pZn relative to that of particulate phosphorus likely explains why dZn appears to have a deeper regeneration profile than that of phosphate. The dZn isotope (δ66Zndissolved) profiles collected across the Subantarctic Zone showed differing profile structures. For one station collected within an isolated cold-core eddy (CCE), δ66Zndissolved showed surface enrichment relative to deep waters. The corresponding pZn isotope profiles within the CCE did not show enrichment; rather, they were subtly depleted in surface waters and then converged to similar values at depth. Zinc isotope fractionation can be explained through a combination of fractionation processes associated with uptake by phytoplankton, zinc complexation by natural organic ligands and zinc regeneration from particulate matter

Distinct iron cycling in a Southern Ocean eddy

Mesoscale eddies are ubiquitous in the iron-limited Southern Ocean, controlling ocean-atmosphere exchange processes, however their influence on phytoplankton productivity remains unknown. Here we probed the biogeochemical cycling of iron (Fe) in a cold-core eddy. In-eddy surface dissolved Fe (dFe) concentrations and phytoplankton productivity were exceedingly low relative to external waters. In-eddy phytoplankton Fe-to-carbon uptake ratios were elevated 2–6 fold, indicating upregulated intracellular Fe acquisition resulting in a dFe residence time of ~1 day. Heavy dFe isotope values were measured for in-eddy surface waters highlighting extensive trafficking of dFe by cells. Below the euphotic zone, dFe isotope values were lighter and coincident with peaks in recycled nutrients and cell abundance, indicating enhanced microbially-mediated Fe recycling. Our measurements show that the isolated nature of Southern Ocean eddies can produce distinctly different Fe biogeochemistry compared to surrounding waters with cells upregulating iron uptake and using recycling processes to sustain themselves

Relationship between FEV1 change and patient-reported outcomes in randomised trials of inhaled bronchodilators for stable COPD: a systematic review.

BACKGROUND: Interactions between spirometry and patient-reported outcomes in COPD are not well understood. This systematic review and study-level analysis investigated the relationship between changes in FEV1 and changes in health status with bronchodilator therapy. METHODS: Six databases (to October 2009) were searched to identify studies with long-acting bronchodilator therapy reporting FEV1 and health status, dyspnoea or exacerbations. Mean and standard deviations of treatment effects were extracted for each arm of each study. Relationships between changes in trough FEV1 and outcomes were assessed using correlations and random-effects regression modelling. The primary outcome was St George's Respiratory Questionnaire (SGRQ) total score. RESULTS: Thirty-six studies (≥ 3 months) were included. Twenty-two studies (23,654 patients) with 49 treatment arms each contributing one data point provided SGRQ data. Change in trough FEV1 and change in SGRQ total score were negatively correlated (r = -0.46, p < 0.001); greater increases in FEV1 were associated with greater reductions (improvements) in SGRQ. The correlation strengthened with increasing study duration from 3 to 12 months. Regression modelling indicated that 100 mL increase in FEV1 (change at which patients are more likely to report improvement) was associated with a statistically significant reduction in SGRQ of 2.5 (95% CI 1.9, 3.1), while a clinically relevant SGRQ change (4.0) was associated with 160.6 (95% CI 129.0, 211.6) mL increase in FEV1. The association between change in FEV1 and other patient-reported outcomes was generally weak. CONCLUSIONS: Our analyses indicate, at a study level, that improvement in mean trough FEV1 is associated with proportional improvements in health status

Atmospheric trace metal deposition from natural and anthropogenic sources in Western Australia

Aerosols from Western Australia supply micronutrient trace elements including Fe into the western shelf of Australia and further afield into the Southern and Indian Oceans. However, regional observations of atmospheric trace metal deposition are limited. Here, we applied a series of leaching experiments followed by total analysis of bulk aerosol samples to a unique time-series of aerosol samples collected in Western Australia to determine atmospheric concentrations and solubilities of Fe and V, Mn, Co, Zn, and Pb. Positive matrix factorisation analysis indicated that mineral dust, biomass burning particulates, sea salt, and industrial emissions were the major types of aerosols. Overall, natural sources dominated Fe deposition. Higher atmospheric concentrations of mineral dust (sixfold) and biomass burning emissions were observed in warmer compared to cooler months. The fraction of labile Fe (0.6–6.0%) was lower than that reported for other regions of Australia. Bushfire emissions are a temporary source of labile Fe and may cause a peak in the delivery of its more easily available forms to the ocean. Increased labile Fe deposition may result in higher ocean productivity in regions where Fe is limiting, and the effect of aerosol deposition on ocean productivity in this region requires further study