Authigenic mineral phases as a driver of the upper-ocean iron cycle.

Iron is important in regulating the ocean carbon cycle1. Although several dissolved and particulate species participate in oceanic iron cycling, current understanding emphasizes the importance of complexation by organic ligands in stabilizing oceanic dissolved iron concentrations2-6. However, it is difficult to reconcile this view of ligands as a primary control on dissolved iron cycling with the observed size partitioning of dissolved iron species, inefficient dissolved iron regeneration at depth or the potential importance of authigenic iron phases in particulate iron observational datasets7-12. Here we present a new dissolved iron, ligand and particulate iron seasonal dataset from the Bermuda Atlantic Time-series Study (BATS) region. We find that upper-ocean dissolved iron dynamics were decoupled from those of ligands, which necessitates a process by which dissolved iron escapes ligand stabilization to generate a reservoir of authigenic iron particles that settle to depth. When this 'colloidal shunt' mechanism was implemented in a global-scale biogeochemical model, it reproduced both seasonal iron-cycle dynamics observations and independent global datasets when previous models failed13-15. Overall, we argue that the turnover of authigenic particulate iron phases must be considered alongside biological activity and ligands in controlling ocean-dissolved iron distributions and the coupling between dissolved and particulate iron pools.

Biogeochemical extremes and compound events in the ocean.

The ocean is warming, losing oxygen and being acidified, primarily as a result of anthropogenic carbon emissions. With ocean warming, acidification and deoxygenation projected to increase for decades, extreme events, such as marine heatwaves, will intensify, occur more often, persist for longer periods of time and extend over larger regions. Nevertheless, our understanding of oceanic extreme events that are associated with warming, low oxygen concentrations or high acidity, as well as their impacts on marine ecosystems, remains limited. Compound events-that is, multiple extreme events that occur simultaneously or in close sequence-are of particular concern, as their individual effects may interact synergistically. Here we assess patterns and trends in open ocean extremes based on the existing literature as well as global and regional model simulations. Furthermore, we discuss the potential impacts of individual and compound extremes on marine organisms and ecosystems. We propose a pathway to improve the understanding of extreme events and the capacity of marine life to respond to them. The conditions exhibited by present extreme events may be a harbinger of what may become normal in the future. As a consequence, pursuing this research effort may also help us to better understand the responses of marine organisms and ecosystems to future climate change.

Multi-faceted particle pumps drive carbon sequestration in the ocean.

The ocean's ability to sequester carbon away from the atmosphere exerts an important control on global climate. The biological pump drives carbon storage in the deep ocean and is thought to function via gravitational settling of organic particles from surface waters. However, the settling flux alone is often insufficient to balance mesopelagic carbon budgets or to meet the demands of subsurface biota. Here we review additional biological and physical mechanisms that inject suspended and sinking particles to depth. We propose that these 'particle injection pumps' probably sequester as much carbon as the gravitational pump, helping to close the carbon budget and motivating further investigation into their environmental control.

A versatile look-up algorithm for mapping pH values and magnesium ion content using 31P MRSI.

31P MRSI allows for the non-invasive mapping of pH and magnesium ion content (Mg) in vivo, by translating the chemical shifts of inorganic phosphate and adenosine-5'-triphosphate (ATP) to pH and Mg via suitable calibration equations, such as the modified Henderson-Hasselbalch equation. However, the required constants in these calibration equations are typically only determined for physiological conditions, posing a particular challenge for their application to diseased tissue, where the biochemical conditions might change manyfold. In this article, we propose a multi-parametric look-up algorithm aiming at the condition-independent determination of pH and Mg by employing multiple quantifiable 31P spectral properties simultaneously. To generate entries for an initial look-up table, measurements from 114 model solutions prepared with varying chemical properties were made at 9.4 T. The number of look-up table entries was increased by inter- and extrapolation using a multi-dimensional function developed based on the Hill equation. The assignment of biochemical parameters, that is, pH and Mg, is realized using probability distributions incorporating specific measurement uncertainties on the quantified spectral parameters, allowing for an estimation of most plausible output values. As proof of concept, we applied a version of the look-up algorithm employing only the chemical shifts of γ- and ß-ATP for the determination of pH and Mg to in vivo 3D 31P MRSI data acquired at 7 T from (i) the lower leg muscles of healthy volunteers and (ii) the brains of patients with glioblastoma. The resulting volumetric maps showed plausible values for pH and Mg, partly revealing differences from maps generated using the conventional calibration equations.

Seeking natural analogs to fast-forward the assessment of marine CO2 removal.

Mitigating global climate change will require gigaton-scale carbon dioxide removal (CDR) as a supplement to rapid emissions reduction. The oceans cover 71% of the Earth surface and have the potential to provide much of the required CDR. However, none of the proposed marine CDR (mCDR) methods is sufficiently well understood to determine their real-world efficiency and environmental side effects. Here, we argue that using natural mCDR analogs should become the third interconnecting pillar in the mCDR assessment as they bridge the gap between numerical simulations (i.e., large scale/reduced complexity) and experimental studies (i.e., small scale/high complexity). Natural mCDR analogs occur at no cost, can provide a wealth of data to inform mCDR, and do not require legal permission or social license for their study. We propose four simple criteria to identify particularly useful analogs: 1) large scale, 2) abruptness of perturbation, 3) availability of unperturbed control sites, and 4) reoccurrence. Based on these criteria, we highlight four examples: 1) equatorial upwelling as a natural analog for artificial upwelling, 2) downstream of Kerguelen Island for ocean iron fertilization, 3) the Black and Caspian Seas for ocean alkalinity enhancement, and 4) the Great Atlantic Sargassum Belt for ocean afforestation. These natural analogs provide a reality check for experimental assessments and numerical modeling of mCDR. Ultimately, projections of mCDR efficacy and sustainability supported by observations from natural analogs will provide the real-world context for the public debate and will facilitate political decisions on mCDR implementation. We anticipate that a rigorous investigation of natural analogs will fast-forward the urgently needed assessment of mCDR.

The integral role of iron in ocean biogeochemistry.

The micronutrient iron is now recognized to be important in regulating the magnitude and dynamics of ocean primary productivity, making it an integral component of the ocean's biogeochemical cycles. In this Review, we discuss how a recent increase in observational data for this trace metal has challenged the prevailing view of the ocean iron cycle. Instead of focusing on dust as the major iron source and emphasizing iron's tight biogeochemical coupling to major nutrients, a more complex and diverse picture of the sources of iron, its cycling processes and intricate linkages with the ocean carbon and nitrogen cycles has emerged.

Strong seasonal patterns of DOC release by a temperate seaweed community: Implications for the coastal ocean carbon cycle.

Release of dissolved organic carbon (DOC) by seaweed underpins the microbial food web and is crucial for the coastal ocean carbon cycle. However, we know relatively little of seasonal DOC release patterns in temperate regions of the southern hemisphere. Strong seasonal changes in inorganic nitrogen availability, irradiance, and temperature regulate the growth of seaweeds on temperate reefs and influence DOC release. We seasonally surveyed and sampled seaweed at Coal Point, Tasmania, over 1 year. Dominant species with or without carbon dioxide (CO2 ) concentrating mechanisms (CCMs) were collected for laboratory experiments to determine seasonal rates of DOC release. During spring and summer, substantial DOC release (10.06-33.54 µmol C · g DW-1 · h-1 ) was observed for all species, between 3 and 27 times greater than during autumn and winter. Our results suggest that inorganic carbon (Ci ) uptake strategy does not regulate DOC release. Seasonal patterns of DOC release were likely a result of photosynthetic overflow during periods of high gross photosynthesis indicated by variations in tissue C:N ratios. For each season, we calculated a reef-scale net DOC release for seaweed at Coal Point of 7.84-12.9 g C · m-2 · d-1 in spring and summer, which was ~16 times greater than in autumn and winter (0.2-1.0 g C · m-2 · d-1 ). Phyllospora comosa, which dominated the biomass, contributed the most DOC to the coastal ocean, up to ~14 times more than Ecklonia radiata and the understory assemblage combined. Reef-scale DOC release was driven by seasonal changes in seaweed physiology rather than seaweed biomass.

Metrics that matter for assessing the ocean biological carbon pump.

The biological carbon pump (BCP) comprises wide-ranging processes that set carbon supply, consumption, and storage in the oceans' interior. It is becoming increasingly evident that small changes in the efficiency of the BCP can significantly alter ocean carbon sequestration and, thus, atmospheric CO2 and climate, as well as the functioning of midwater ecosystems. Earth system models, including those used by the United Nation's Intergovernmental Panel on Climate Change, most often assess POC (particulate organic carbon) flux into the ocean interior at a fixed reference depth. The extrapolation of these fluxes to other depths, which defines the BCP efficiencies, is often executed using an idealized and empirically based flux-vs.-depth relationship, often referred to as the "Martin curve." We use a new compilation of POC fluxes in the upper ocean to reveal very different patterns in BCP efficiencies depending upon whether the fluxes are assessed at a fixed reference depth or relative to the depth of the sunlit euphotic zone (Ez). We find that the fixed-depth approach underestimates BCP efficiencies when the Ez is shallow, and vice versa. This adjustment alters regional assessments of BCP efficiencies as well as global carbon budgets and the interpretation of prior BCP studies. With several international studies recently underway to study the ocean BCP, there are new and unique opportunities to improve our understanding of the mechanistic controls on BCP efficiencies. However, we will only be able to compare results between studies if we use a common set of Ez-based metrics.

Biogeography of Southern Ocean prokaryotes: a comparison of the Indian and Pacific sectors.

We investigated the Southern Ocean (SO) prokaryote community structure via zero-radius operational taxonomic unit (zOTU) libraries generated from 16S rRNA gene sequencing of 223 full water column profiles. Samples reveal the prokaryote diversity trend between discrete water masses across multiple depths and latitudes in Indian (71-99°E, summer) and Pacific (170-174°W, autumn-winter) sectors of the SO. At higher taxonomic levels (phylum-family) we observed water masses to harbour distinct communities across both sectors, but observed sectorial variations at lower taxonomic levels (genus-zOTU) and relative abundance shifts for key taxa such as Flavobacteria, SAR324/Marinimicrobia, Nitrosopumilus and Nitrosopelagicus at both epi- and bathy-abyssopelagic water masses. Common surface bacteria were abundant in several deep-water masses and vice-versa suggesting connectivity between surface and deep-water microbial assemblages. Bacteria from same-sector Antarctic Bottom Water samples showed patchy, high beta-diversity which did not correlate well with measured environmental parameters or geographical distance. Unconventional depth distribution patterns were observed for key archaeal groups: Crenarchaeota was found across all depths in the water column and persistent high relative abundances of common epipelagic archaeon Nitrosopelagicus was observed in deep-water masses. Our findings reveal substantial regional variability of SO prokaryote assemblages that we argue should be considered in wide-scale SO ecosystem microbial modelling.

Mapping intracellular pH in tumors using amide and guanidyl CEST-MRI at 9.4 T.

PURPOSE: In principle, non-invasive mapping of the intracellular pH (pHi ) in vivo is possible using endogenous chemical exchange saturation transfer (CEST)-MRI of the amide and guanidyl signals. However, the application for cancer imaging is still impeded, as current state-of-the-art approaches do not allow for simultaneous compensation of concomitant effects that vary within tumors. In this study, we present a novel method for absolute pHi mapping using endogenous CEST-MRI, which simultaneously compensates for concentration changes, superimposing CEST signals, magnetization transfer contrast, and spillover dilution. THEORY AND METHODS: Compensation of the concomitant effects was achieved by a ratiometric approach (i.e. the ratio of one CEST signal at different B1 ) in combination with the relaxation-compensated inverse magnetization transfer ratio MTRRex and a separate first-order polynomial-Lorentzian fit of the amide and guanidyl signals at 9.4 T. Calibration of pH values was accomplished using in vivo-like model suspensions from porcine brain lysates. Applicability of the presented method in vivo was demonstrated in n = 19 tumor-bearing mice. RESULTS: In porcine brain lysates, measurement of pH was feasible over a broad range of physiologically relevant pH values of 6.2 to 8.0, while being independent of changes in concentration. A median pHi of approximately 7.2 was found in the lesions of 19 tumor-bearing mice. CONCLUSION: The presented method enables non-invasive mapping of absolute pHi values in tumors using CEST-MRI, which was so far prevented by concomitant effects. Consequently, pre-clinical studies on pHi changes in tumors are possible allowing the assessment of pHi in vivo as a biomarker for cancer diagnosis or treatment monitoring.

Motion correction for three-dimensional chemical exchange saturation transfer imaging without direct water saturation artifacts.

In chemical exchange saturation transfer (CEST) MRI, motion correction is compromised by the drastically changing image contrast at different frequency offsets, particularly at the direct water saturation. In this study, a simple extension for conventional image registration algorithms is proposed, enabling robust and accurate motion correction of CEST-MRI data. The proposed method uses weighted averaging of motion parameters from a conventional rigid image registration to identify and mitigate erroneously misaligned images. Functionality of the proposed method was verified by ground truth datasets generated from 10 three-dimensional in vivo measurements at 3 T with simulated realistic random rigid motion patterns and noise. Performance was assessed using two different criteria: the maximum image misalignment as a measure for the robustness against direct water saturation artifacts, and the spectral error as a measure of the overall accuracy. For both criteria, the proposed method achieved the best scores compared with two motion-correction algorithms specifically developed to handle the varying contrasts in CEST-MRI. Compared with a straightforward linear interpolation of the motion parameters at frequency offsets close to the direct water saturation, the proposed method offers better performance in the absence of artifacts. The proposed method for motion correction in CEST-MRI allows identification and mitigation of direct water saturation artifacts that occur with conventional image registration algorithms. The resulting improved robustness and accuracy enable reliable motion correction, which is particularly crucial for an automated and carefree evaluation of spectral CEST-MRI data, e.g., for large patient cohorts or in clinical routines.

Forensic carbon accounting: Assessing the role of seaweeds for carbon sequestration.

Carbon sequestration is defined as the secure storage of carbon-containing molecules for >100 years, and in the context of carbon dioxide removal for climate mitigation, the origin of this CO2 is from the atmosphere. On land, trees globally sequester substantial amounts of carbon in woody biomass, and an analogous role for seaweeds in ocean carbon sequestration has been suggested. The purposeful expansion of natural seaweed beds and aquaculture systems, including into the open ocean (ocean afforestation), has been proposed as a method of increasing carbon sequestration and use in carbon trading and offset schemes. However, to verify whether CO2 fixed by seaweeds through photosynthesis leads to carbon sequestration is extremely complex in the marine environment compared to terrestrial systems, because of the need to jointly consider: the comparatively rapid turnover of seaweed biomass, tracing the fate of carbon via particulate and dissolved organic carbon pathways in dynamic coastal waters, and the key role of atmosphere-ocean CO2 exchange. We propose a Forensic Carbon Accounting approach, in which a thorough analysis of carbon flows between the atmosphere and ocean, and into and out of seaweeds would be undertaken, for assessing the magnitude of CO2 removal and robust attribution of carbon sequestration to seaweeds.

Photosynthetic adaptation to low iron, light, and temperature in Southern Ocean phytoplankton.

Phytoplankton productivity in the polar Southern Ocean (SO) plays an important role in the transfer of carbon from the atmosphere to the ocean's interior, a process called the biological carbon pump, which helps regulate global climate. SO productivity in turn is limited by low iron, light, and temperature, which restrict the efficiency of the carbon pump. Iron and light can colimit productivity due to the high iron content of the photosynthetic photosystems and the need for increased photosystems for low-light acclimation in many phytoplankton. Here we show that SO phytoplankton have evolved critical adaptations to enhance photosynthetic rates under the joint constraints of low iron, light, and temperature. Under growth-limiting iron and light levels, three SO species had up to sixfold higher photosynthetic rates per photosystem II and similar or higher rates per mol of photosynthetic iron than temperate species, despite their lower growth temperature (3 vs. 18 °C) and light intensity (30 vs. 40 µmol quanta⋅m2⋅s-1), which should have decreased photosynthetic rates. These unexpectedly high rates in the SO species are partly explained by their unusually large photosynthetic antennae, which are among the largest ever recorded in marine phytoplankton. Large antennae are disadvantageous at low light intensities because they increase excitation energy loss as heat, but this loss may be mitigated by the low SO temperatures. Such adaptations point to higher SO production rates than environmental conditions should otherwise permit, with implications for regional ecology and biogeochemistry.

Exploring biogeochemical and ecological redundancy in phytoplankton communities in the global ocean.

Climate-change-induced alterations of oceanic conditions will lead to the ecological niches of some marine phytoplankton species disappearing, at least regionally. How will such losses affect the ecosystem and the coupled biogeochemical cycles? Here, we couch this question in terms of ecological redundancy (will other species be able to fill the ecological roles of the extinct species) and biogeochemical redundancy (can other species replace their biogeochemical roles). Prior laboratory and field studies point to a spectrum in the degree of redundancy. We use a global three-dimensional computer model with diverse planktonic communities to explore these questions further. The model includes 35 phytoplankton types that differ in size, biogeochemical function and trophic strategy. We run two series of experiments in which single phytoplankton types are either partially or fully eliminated. The niches of the targeted types were not completely reoccupied, often with a reduction in the transfer of matter from autotrophs to heterotrophs. Primary production was often decreased, but sometimes increased due to reduction in grazing pressure. Complex trophic interactions (such as a decrease in the stocks of a predator's grazer) led to unexpected reshuffling of the community structure. Alterations in resource utilization may cause impacts beyond the regions where the type went extinct. Our results suggest a lack of redundancy, especially in the 'knock on' effects on higher trophic levels. Redundancy appeared lowest for types on the edges of trait space (e.g. smallest) or with unique competitive strategies. Though highly idealized, our modelling findings suggest that the results from laboratory or field studies often do not adequately capture the ramifications of functional redundancy. The modelled, often counterintuitive, responses-via complex food web interactions and bottom-up versus top-down controls-indicate that changes in planktonic community will be key determinants of future ocean global change ecology and biogeochemistry.

Resource Colimitation Drives Competition Between Phytoplankton and Bacteria in the Southern Ocean.

Across the Southern Ocean, phytoplankton growth is governed by iron and light, while bacterial growth is regulated by iron and labile dissolved organic carbon (LDOC). We use a mechanistic model to examine how competition for iron between phytoplankton and bacteria responds to changes in iron, light, and LDOC. Consistent with experimental evidence, increasing iron and light encourages phytoplankton dominance, while increasing LDOC and decreasing light favors bacterial dominance. Under elevated LDOC, bacteria can outcompete phytoplankton for iron, most easily under lower iron. Simulations reveal that bacteria are major iron consumers and suggest that luxury storage plays a key role in competitive iron uptake. Under seasonal conditions typical of the Southern Ocean, sources of LDOC besides phytoplankton exudation modulate the strength of competitive interactions. Continued investigations on the competitive fitness of bacteria in driving changes in primary production in iron-limited systems will be invaluable in refining these results.

Rate and fate of dissolved organic carbon release by seaweeds: A missing link in the coastal ocean carbon cycle.

Dissolved organic carbon (DOC) release by seaweeds (marine macroalgae) is a critical component of the coastal ocean biogeochemical carbon cycle but is an aspect of seaweed carbon physiology that we know relatively little about. Seaweed-derived DOC is found throughout coastal ecosystems and supports multiple food web linkages. Here, we discuss the mechanisms of DOC release by seaweeds and group them into passive (leakage, requires no energy) and active release (exudation, requires energy) with particular focus on the photosynthetic "overflow" hypothesis. The release of DOC from seaweeds was first studied in the 1960s, but subsequent studies use a range of units hindering evaluation: we convert published values to a common unit (µmol C · g DW-1 · h-1 ) allowing comparisons between seaweed phyla, functional groups, biogeographic region, and an assessment of the environmental regulation of DOC production. The range of DOC release rates by seaweeds from each phylum under ambient environmental conditions was 0-266.44 µmol C · g DW-1 · h-1 (Chlorophyta), 0-89.92 µmol C · g DW-1 · h-1 (Ochrophyta), and 0-41.28 µmol C · g DW-1 · h-1 (Rhodophyta). DOC release rates increased under environmental factors such as desiccation, high irradiance, non-optimal temperatures, altered salinity, and elevated dissolved carbon dioxide (CO2 ) concentrations. Importantly, DOC release was highest by seaweeds that were desiccated (<90 times greater DOC release compared to ambient). We discuss the impact of future ocean scenarios (ocean acidification, seawater warming, altered irradiance) on DOC release rates by seaweeds, the role of seaweed-derived DOC in carbon sequestration models, and how they inform future research directions.

Dynamic glucose-enhanced (DGE) MRI in the human brain at 7 T with reduced motion-induced artifacts based on quantitative R1ρ mapping.

PURPOSE: Dynamic glucose-enhanced (DGE)-MRI based on chemical exchange-sensitive MRI, that is, glucoCEST and gluco-chemical exchange-sensitive spin-lock (glucoCESL), is intrinsically prone to motion-induced artifacts because the final DGE contrast relies on the difference of images, which were acquired with a time gap of several mins. In this study, identification of different types of motion-induced artifacts led to the development of a 3D acquisition protocol for DGE examinations in the human brain at 7 T with improved robustness in the presence of subject motion. METHODS: DGE-MRI was realized by the chemical exchange-sensitive spin-lock approach based either on relaxation rate in the rotating frame (R1ρ )-weighted or quantitative R1ρ imaging. A 3D image readout was implemented at 7 T, enabling retrospective volumetric coregistration of the image series and quantification of subject motion. An examination of a healthy volunteer without administration of glucose allowed for the identification of isolated motion-induced artifacts. RESULTS: Even after coregistration, significant motion-induced artifacts remained in the DGE contrast based on R1ρ -weighted images. This is due to the spatially varying sensitivity of the coil and was found to be compensated by a quantitative R1ρ approach. The coregistered quantitative approach allowed the observation of a clear increase of the DGE contrast in a patient with glioblastoma, which did not correlate with subject motion. CONCLUSION: The presented 3D acquisition protocol enables DGE-MRI examinations in the human brain with improved robustness against motion-induced artifacts. Correction of motion-induced artifacts is of high importance for DGE-MRI in clinical studies where an unambiguous assignment of contrast changes due to an actual change in local glucose concentration is a prerequisite.

How do we overcome abrupt degradation of marine ecosystems and meet the challenge of heat waves and climate extremes?

Extreme heat wave events are now causing ecosystem degradation across marine ecosystems. The consequences of this heat-induced damage range from the rapid loss of habitat-forming organisms, through to a reduction in the services that ecosystems support, and ultimately to impacts on human health and society. How we tackle the sudden emergence of ecosystem-wide degradation has not yet been addressed in the context of marine heat waves. An examination of recent marine heat waves from around Australia points to the potential important role that respite or refuge from environmental extremes can play in enabling organismal survival. However, most ecological interventions are being devised with a target of mid to late-century implementation, at which time many of the ecosystems, that the interventions are targeted towards, will have already undergone repeated and widespread heat wave induced degradation. Here, our assessment of the merits of proposed ecological interventions, across a spectrum of approaches, to counter marine environmental extremes, reveals a lack preparedness to counter the effects of extreme conditions on marine ecosystems. The ecological influence of these extremes are projected to continue to impact marine ecosystems in the coming years, long before these interventions can be developed. Our assessment reveals that approaches which are technologically ready and likely to be socially acceptable are locally deployable only, whereas those which are scalable-for example to features as large as major reef systems-are not close to being testable, and are unlikely to obtain social licence for deployment. Knowledge of the environmental timescales for survival of extremes, via respite or refuge, inferred from field observations will help test such intervention tools. The growing frequency of extreme events such as marine heat waves increases the urgency to consider mitigation and intervention tools that support organismal and ecosystem survival in the immediate future, while global climate mitigation and/or intervention are formulated.