Peter Croot

A mesoscale phytoplankton bloom in the polar Southern Ocean stimulated by iron fertilization

Changes in iron supply to oceanic plankton are thought to have a significant effect on concentrations of atmospheric carbon dioxide by altering rates of carbon sequestration, a theory known as the ‘iron hypothesis’. For this reason, it is important to understand the response of pelagic biota to increased iron supply. Here we report the results of a mesoscale iron fertilization experiment in the polar Southern Ocean, where the potential to sequester iron-elevated algal carbon is probably greatest. Increased iron supply led to elevated phytoplankton biomass and rates of photosynthesis in surface waters, causing a large drawdown of carbon dioxide and macronutrients, and elevated dimethyl sulphide levels after 13 days. This drawdown was mostly due to the proliferation of diatom stocks. But downward export of biogenic carbon was not increased. Moreover, satellite observations of this massive bloom 30 days later, suggest that a sufficient proportion of the added iron was retained in surface waters. Our findings demonstrate that iron supply controls phytoplankton growth and community composition during summer in these polar Southern Ocean waters, but the fate of algal carbon remains unknown and depends on the interplay between the processes controlling export, remineralisation and timescales of water mass subduction.

Synthesis of iron fertilization experiments: From the Iron Age in the Age of Enlightenment

Comparison of eight iron experiments shows that maximum Chl a, the maximum DIC removal, and the overall DIC/Fe efficiency all scale inversely with depth of the wind mixed layer (WML) defining the light environment. Moreover, lateral patch dilution, sea surface irradiance, temperature, and grazing play additional roles. The Southern Ocean experiments were most influenced by very deep WMLs. In contrast, light conditions were most favorable during SEEDS and SERIES as well as during IronEx-2. The two extreme experiments, EisenEx and SEEDS, can be linked via EisenEx bottle incubations with shallower simulated WML depth. Large diatoms always benefit the most from Fe addition, where a remarkably small group of thriving diatom species is dominated by universal response of Pseudo-nitzschia spp. Significant response of these moderate (10–30 μm), medium (30–60 μm), and large (>60 μm) diatoms is consistent with growth physiology determined for single species in natural seawater. The minimum level of “dissolved” Fe (filtrate < 0.2 μm) maintained during an experiment determines the dominant diatom size class. However, this is further complicated by continuous transfer of original truly dissolved reduced Fe(II) into the colloidal pool, which may constitute some 75% of the “dissolved” pool. Depth integration of carbon inventory changes partly compensates the adverse effects of a deep WML due to its greater integration depths, decreasing the differences in responses between the eight experiments. About half of depth-integrated overall primary productivity is reflected in a decrease of DIC. The overall C/Fe efficiency of DIC uptake is DIC/Fe ∼ 5600 for all eight experiments. The increase of particulate organic carbon is about a quarter of the primary production, suggesting food web losses for the other three quarters. Replenishment of DIC by air/sea exchange tends to be a minor few percent of primary CO2 fixation but will continue well after observations have stopped. Export of carbon into deeper waters is difficult to assess and is until now firmly proven and quite modest in only two experiments.

DETERMINATION OF IRON SPECIATION BY CATHODIC STRIPPING VOLTAMMETRY IN SEAWATER USING THE COMPETING LIGAND 2-(2-THIAZOLYLAZO)-P-CRESOL (TAC)

A new sensitive competitive ligand exchange-adsorptive cathodic stripping voltammetric (CLE-ACSV) method for the determination of iron speciation in seawater has been developed using the iron binding ligand TAC 2-(2-thiazolylazo)-p-cresol. An earlier method for determining iron using TAC [1] was reexamined and optimized for measurements in seawater at pH 8.0. The sensitivity was improved by employing a fast (10.12 V/s) linear sweep scan waveform. The detection limit (3σ of blank) is 0.10 nM after an adsorption time of 300 s; the detection limit can be lowered, however, by using a longer deposition time or for the determination of total iron, by increasing the pH to 8.5. This method was applied to samples from Swedish coastal waters and the results indicate the possible efflux of iron binding ligands from sediments in coastal waters.

Deep carbon export from a Southern Ocean iron-fertilized diatom bloom

Fertilization of the ocean by adding iron compounds has induced diatom-dominated phytoplankton blooms accompanied by considerable carbon dioxide drawdown in the ocean surface layer. However, because the fate of bloom biomass could not be adequately resolved in these experiments, the timescales of carbon sequestration from the atmosphere are uncertain. Here we report the results of a five-week experiment carried out in the closed core of a vertically coherent, mesoscale eddy of the Antarctic Circumpolar Current, during which we tracked sinking particles from the surface to the deep-sea floor. A large diatom bloom peaked in the fourth week after fertilization. This was followed by mass mortality of several diatom species that formed rapidly sinking, mucilaginous aggregates of entangled cells and chains. Taken together, multiple lines of evidence—although each with important uncertainties—lead us to conclude that at least half the bloom biomass sank far below a depth of 1,000 metres and that a substantial portion is likely to have reached the sea floor. Thus, iron-fertilized diatom blooms may sequester carbon for timescales of centuries in ocean bottom water and for longer in the sediments.

Atmospheric iron deposition and sea-surface dissolved iron concentrations in the eastern Atlantic Ocean

Atmospheric iron and underway sea-surface dissolved (<0.2 μm) iron (DFe) concentrations were investigated along a north-south transect in the eastern Atlantic Ocean (27°N/16°W-19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73-97), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02-1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearmans rho = 0.862, p<0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17 ± 8 to 28 ± 16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation.

The fate of added iron during a mesoscale fertilisation experiment in the Southern Ocean

The first Southern Ocean Iron RElease Experiment (SOIREE) was performed during February 1999 in Antarctic waters south of Australia (61°S, 140°E), in order to verify whether iron supply controls the magnitude of phytoplankton production in this high nutrient low chlorophyll (HNLC) region. This paper describes iron distributions in the upper ocean during our 13-day site occupation, and presents a pelagic iron budget to account for the observed losses of dissolved and total iron from waters of the fertilised patch. Iron concentrations were measured underway during daily transects through the patch and in vertical profiles of the 65-m mixed layer. High internal consistency was noted between data obtained using contrasting sampling and analytical techniques. A pre-infusion survey confirmed the extremely low ambient dissolved (0.1 nM) and total (0.4 nM) iron concentrations. The initial enrichment elevated the dissolved iron concentration to 2.7 nM. Thereafter, dissolved iron was rapidly depleted inside the patch to 0.2-0.3 nM, necessitating three re-infusions. A distinct biological response was observed in iron-fertilised waters, relative to outside the patch, unequivocally confirming that iron limits phytoplankton growth rates and biomass at this site in summer. Our budget describing the fate of the added iron demonstrates that horizontal dispersion of fertilised waters (resulting in a quadrupling of the areal extent of the patch) and abiotic particle scavenging accounted for most of the decreases in iron concentrations inside the patch (31-58 and 12-49 of added iron, respectively). The magnitude of these loss processes altered towards the end of SOIREE, and on days 12-13 dissolved (1.1 nM) and total (2.3 nM) iron concentrations remained elevated compared to surrounding waters. At this time, the biogenic iron pool (0.1 nM) accounted for only 1-2 of the total added iron. Large pennate diatoms (> 20 μm) and autotrophic flagellates (2-20 μm) were the dominant algal groups in the patch, taking up the added iron and representing 13 and 39 of the biogenic iron pool, respectively. Iron regeneration by grazers was tightly coupled to uptake by phytoplankton and bacteria, indicating that biological Fe cycling within the bloom was self-sustaining. A concurrent increase in the concentration of iron-binding ligands on days 11-12 probably retained dissolved iron within the mixed layer. Ocean colour satellite images in late March suggest that the bloom was still actively growing 42 days after the onset of SOIREE, and hence by inference that sufficient iron was maintained in the patch for this period to meet algal requirements. This raises fundamental questions regarding the biogeochemical cycling of iron in the Southern Ocean and, in particular, how bioavailable iron was retained in surface waters and/or within the biota to sustain algal growth.

Maritime Aerosol Network as a component of Aerosol Robotic Network

The paper presents the current status of the Maritime Aerosol Network (MAN), which has been developed as a component of the Aerosol Robotic Network (AERONET). MAN deploys Microtops handheld Sun photometers and utilizes the calibration procedure and data processing (Version 2) traceable to AERONET. A web site dedicated to the MAN activity is described. A brief historical perspective is given to aerosol optical depth (AOD) measurements over the oceans. A short summary of the existing data, collected on board ships of opportunity during the NASA Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) Project is presented. Globally averaged oceanic aerosol optical depth (derived from island-based AERONET measurements) at 500 nm is similar to 0.11 and Angstrom parameter (computed within spectral range 440-870 nm) is calculated to be similar to 0.6. First results from the cruises contributing to the Maritime Aerosol Network are shown. MAN ship-based aerosol optical depth compares well to simultaneous island and near-coastal AERONET site AOD.

Retention of dissolved iron and Fe II in an iron induced Southern Ocean phytoplankton bloom

During the 13 day Southern Ocean Iron RE-lease Experiment (SOIREE), dissolved iron concentrations decreased rapidly following each of three iron-enrichments, but remained high (>1 nM, up to 80% as FeII) after the fourth and final enrichment on day 8. The former trend was mainly due to dilution (spreading of iron-fertilized waters) and particle scavenging. The latter may only be explained by a joint production-maintenance mechanism; photoreduction is the only candidate process able to produce sufficiently high FeII, but as such levels persisted overnight (8 hr dark period) —ten times the half—life for this species—a maintenance mechanism (complexation of FeII) is required, and is supported by evidence of increased ligand concentrations on day 12. The source of these ligands and their affinity for FeII is not known. This retention of iron probably permitted the longevity of this bloom raising fundamental questions about iron cycling in HNLC (High Nitrate Low Chlorophyll) Polar waters.

Subduction zone volcanic ash can fertilize the surface ocean and stimulate phytoplankton growth: Evidence from biogeochemical experiments and satellite data

Volcanoes confront Earth scientists with new fundamental questions: Can airborne volcanic ash release nutrients on contact with seawater, thereby excite the marine primary productivity (MPP); and, most notably, can volcanoes through oceanic fertilization affect the global climate in a way that is so far poorly understood? Here we present results from biogeochemical experiments showing that 1) volcanic ash from subduction zone volcanoes rapidly release an array of nutrients (co-)limiting algal growth in vast oceanic areas, 2) at a speed much faster (minute-scale) than hitherto known and that marine phytoplankton from low-iron oceanic areas can swiftly, within days, utilize iron from volcanic sources. We further present satellite data possibly indicating an increase of the MPP due to the seaward deposition of volcanic particulate matter. Our study supports the hypothesis that oceanic (iron) fertilization with volcanic ash may play a vital role for the development of the global climate.

Continuous shipboard determination of Fe(II) in Polar waters using flow injection analysis with chemiluminescence detection

A method for the continuous underway determination of Fe(II) in polar waters is reported. Surface seawater is pumped into a shipboard clean room container using a towed fish with Teflon diaphragm pump. Fe(II) was determined by flow injection analysis using a modified FeLume. The seawater is filtered in-line and the sample containing Fe(II) is mixed with luminol (buffered to pH 10) inside a flow cell and the resulting luminescence signal measured by a Hamamatsu HC-135 photon counter linked to a laptop computer. No preconcentration of the samples was applied, to reduce possible interferences and increase the sampling frequency. The system was utilised during EISENEX, a meso-scale iron enrichment experiment sample in the Atlantic sector of the Southern Ocean. In EISENEX, when surveying the iron enriched patch, a sample was analysed every 110 s (60 s loading time and 50 s for analysis). The detection limit, as determined by analysis of seawater (maintained at 4 °C to minimise oxidation) spiked with known concentrations of Fe(II), ranged from 25 to 133 pM. The system was also applied to vertical profiles of Fe(II) during EISENEX.