Sylvia G. Sander

Hydrothermal venting at pressure-temperature conditions above the critical point of seawater, 5°S on the Mid-Atlantic Ridge

Hydrothermal circulation within oceanic crust depends on pressure ( P ) and temperature ( T ); the critical point (CP) of seawater at 298 bar and 407 °C represents the threshold between subcritical and supercritical conditions. Here we present data from the first hydrothermal system in which the sampled fluids fall on and above the CP. The vent system discovered at 5°S on the Mid-Atlantic Ridge is characterized by multiple fluid emanations at variable temperatures in water depths of ~3000 m. Vigorous vapor phase bubbling, stable emanation of superhot fluid at 407 °C, and decreased salinity indicate phase separation at conditions above the CP at one site. At another site the measured maximum T of 464 °C during a 20 s interval is by far the hottest fluid ever measured at the seafloor and falls into the vapor-phase supercritical region of seawater. Besides these two separate fields with ongoing phase separation and extremely hot fluids, a third vent field emanates non-phase-separated fluids at 349 °C and is used as a reference site. Fluid chemistry shows that supercritical fluids evolve differently than subcritical fluids, making this vent system a unique natural laboratory to investigate processes at high P - T conditions. The stability of the high temperature and fluid geochemistry measured in 2005 and 2006 after the assumed seismic trigger event in 2002 supports this as an exceptional site along the Mid-Atlantic Ridge.

Remineralization of upper ocean particles: Implications for iron biogeochemistry

The role of heterotrophic bacteria in iron recycling, the influence of complexation on iron remineralization, and iron mobilization rates from lithogenic vs. biogenic particulate iron (PFe) were examined using field experiments and modeling simulations. During summer, we measured the mobilization rate of algal iron by heterotrophic bacteria in the mixed layer at a polar and a subpolar site south of Australia, and conducted shipboard incubations to track the release of dissolved iron (DFe) and iron-binding ligands from subsurface settling particles sampled from 120-m depth. Bacteria mobilized . 25% PFe d21 in surface waters relative to mobilization at depth (, 2% d21). Our incubations provide the first evidence of the concurrent release of weak iron-binding ligands and DFe from sinking particles. Simulated profiles of PFe remineralization, based on proxies, point to greater dissolution from biogenic PFe than from lithogenic PFe. Together our findings point to different biogeochemical functions for lithogenic vs. biogenic PFe: biogenic PFe is probably the main source of both DFe and ligands, whereas lithogenic PFe may contribute most to DFe scavenging and ballasting of biogenic PFe. The relative proportions of lithogenic vs. biogenic PFe flux vary regionally and set the contribution of scavenging and ballasting vs. dissolution and ligand release, and hence the fate of iron in the water column. Over the last two decades the role of iron supply on the ocean’s carbon cycle has received widespread attention because of its potential function in modulating the earth’s climate during the geological past (Martin 1990). Such attention has resulted in rapid advances in this field, with the development of distinct research themes including iron and algal physiology (Morel and Price 2003), iron chemistry (Rue and Bruland 1995), dissolved iron (DFe)

Microbial control of diatom bloom dynamics in the open ocean

[1] Diatom blooms play a central role in supporting foodwebs and sequestering biogenic carbon to depth. Oceanic conditions set bloom initiation, whereas both environmental and ecological factors determine bloom magnitude and longevity. Our study reveals another fundamental determinant of bloom dynamics. A diatom spring bloom in offshore New Zealand waters was likely terminated by iron limitation, even though diatoms consumed <1/3 of the mixed-layer dissolved iron inventory. Thus, bloom duration and magnitude were primarily set by competition for dissolved iron between microbes and small phytoplankton versus diatoms. Significantly, such a microbial mode of control probably relies both upon out-competing diatoms for iron (i.e., K-strategy), and having high iron requirements (i.e., r-strategy). Such resource competition for iron has implications for carbon biogeochemistry, as, blooming diatoms fixed three-fold more carbon per unit iron than resident non-blooming microbes. Microbial sequestration of iron has major ramifications for determining the biogeochemical imprint of oceanic diatom blooms. Citation: Boyd, P. W., et al. (2012), Microbial control of diatom bloom dynamics in the open ocean, Geophys. Res. Lett., 39, L18601, doi:10.1029/2012GL053448.

Young volcanism and related hydrothermal activity at 5°S on the slow‐spreading southern Mid‐Atlantic Ridge

The effect of volcanic activity on submarine hydrothermal systems has been well documented along fast- and intermediate-spreading centers but not from slow-spreading ridges. Indeed, volcanic eruptions are expected to be rare on slow-spreading axes. Here we report the presence of hydrothermal venting associated with extremely fresh lava flows at an elevated, apparently magmatically robust segment center on the slow-spreading southern Mid-Atlantic Ridge near 5°S. Three high-temperature vent fields have been recognized so far over a strike length of less than 2 km with two fields venting phase-separated, vapor-type fluids. Exit temperatures at one of the fields reach up to 407°C, at conditions of the critical point of seawater, the highest temperatures ever recorded from the seafloor. Fluid and vent field characteristics show a large variability between the vent fields, a variation that is not expected within such a limited area. We conclude from mineralogical investigations of hydrothermal precipitates that vent-fluid compositions have evolved recently from relatively oxidizing to more reducing conditions, a shift that could also be related to renewed magmatic activity in the area. Current high exit temperatures, reducing conditions, low silica contents, and high hydrogen contents in the fluids of two vent sites are consistent with a shallow magmatic source, probably related to a young volcanic eruption event nearby, in which basaltic magma is actively crystallizing. This is the first reported evidence for direct magmatic-hydrothermal interaction on a slow-spreading mid-ocean ridge.

Organic complexation of copper in deep-sea hydrothermal vent systems

Environmental context. Deep-sea hydrothermal vents represent a natural habitat for many extremophile organisms able to cope with extreme physical and chemical conditions, including high loads of heavy metals and reduced gases. To date, no information is available on the level and role of organic complexation of metals in these systems, which will have consequences on the bioavailability and precipitation or mineralisation of metals. In this work, we give evidence for the presence of organic molecules, including thiols, capable of forming complexes with copper strong enough to compete against sulfide present at high levels in hydrothermal systems. Abstract. Here we report, for the first time, that strong organic complexation plays an important role in the chemical speciation of copper in hydrothermal vent systems including medium temperature outlets, diffuse vents with an adjacent hydrothermal biocommunity, and local mixing zone with seawater. Samples from three deep-sea hydrothermal vent areas show a wide concentration range of organic copper-binding ligands, up to 4000 nM, with very high conditional stability constants (log K′Cu′L = 12.48 to 13.46). Measurements were usually made using voltammetric methods after removal of sulfide species under ambient seawater conditions (pH 7.8), but binding still occurs at pH 4.5 and 2.1. The voltammetric behaviour of our hydrothermal samples is compared with that of glutathione (GSH) a known strong Cu-binding ligand, as a representative of an organic thiol. Our results provide compelling evidence for the presence of organic ligands, including thiols, which form complexes strong enough to play an important role in controlling the bioavailability and geochemical behaviour of metal ions around hydrothermal vents.

Physical mixing effects on iron biogeochemical cycling: FeCycle experiment

The effects of physical processes on the distribution, speciation, and sources/sinks for Fe in a high-nutrient low-chlorophyll (HNLC) region were assessed during FeCycle, a mesoscale SF6 tracer release during February 2003 (austral summer) to the SE of New Zealand. Physical mixing processes were prevalent during FeCycle with rapid patch growth (strain rate γ = 0.17–0.20 d−1) from a circular shape (50 km2) into a long filament of ∼400 km2 by day 10. Slippage between layers saw the patch-head overlying noninfused waters while the tail was capped by adjacent surface waters resulting in a SF6 maximum at depth. As the patch developed it entrained adjacent waters containing higher chlorophyll concentrations, but similar dissolved iron (DFe) levels, than the initial infused patch. DFe was low ∼60 pmol L−1 in surface waters during FeCycle and was dominated by organic complexation. Nighttime measurements of Fe(II) ∼20 pmol L−1 suggest the presence of Fe(II) organic complexes in the absence of an identifiable fast Fe(III) reduction process. Combining residence times and phytoplankton uptake fluxes for DFe it is cycled through the biota 140–280 times before leaving the winter mixed layer (WML). This strong Fe demand throughout the euphotic zone coupled with the low Fe:NO3 − (11.9 μmol:mol) below the ferricline suggests that vertical diffusion of Fe is insufficient to relieve chronic iron limitation, indicating the importance of atmospheric inputs of Fe to this region.

Effect of UVB Irradiation on Cu2+-Binding Organic Ligands and Cu2+ Speciation in Alpine Lake Waters of New Zealand

Environmental Context. The bioavailability of dissolved metals in natural waters is directly affected by metal-sequestering agents. These agents include soil-derived matter and compounds released by microorganisms, since copper can support or inhibit aquatic microorganisms depending on concentration. During summer the levels of copper increase in surface waters, an effect intuitively attributable to increased ultraviolet light degrading the sequestering agents more effectively, leading to a concurrent release of the metal. This paper shows that the amount of degradation attributable to light is too low to explain the metal release and that a biological influence may instead be responsible. Abstract. The influence of UVB irradiation on the Cu2+ binding by natural organic ligands in six alpine lakes on the South Island, New Zealand, has been investigated using competitive ligand equilibration with salicylaldoxime and detection by cathodic stripping voltammetry (CLE-CSV). During austral summer 2002–2003 the total dissolved Cu ([Cu]T), the concentration of strong Cu2+-binding ligands ([L]T), and their conditional stability constant K´´ were determined in surface samples of all six lakes. All lakes exhibited appreciable concentrations of a strong Cu2+ binding ligand with similar K´´ values and concentrations always exceeding [CuT], thus dominating Cu2+ speciation. Four lakes (Hayes, Manapouri, Wanaka, Te Anau) showed no appreciable trend in [LT] throughout the summer, whereas in Lakes Wakatipu and Hawea [LT] increased steadily throughout this period. Laboratory UVB irradiation of lake water samples using a 400 W mercury lamp with a Pyrex glass filter (λ > 280 nm) showed that Cu2+-binding ligands are destroyed by UVB radiation, causing [L]T to decrease with a rate of –0.588 nmol L–1 h–1 (r2 0.88). From this we calculate that the in situ ligand destruction rate by UVB in summer for surface waters of these lakes is too small to significantly affect [LT], and conclude that variations in ligand concentrations must result from seasonally variable biological factors.

Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability.

Speciation affects trace metal bioavailability. One model used to describe the importance of speciation is the biotic ligand model (BLM), wherein the competition of inorganic and organic ligands with a biotic ligand for free-ion trace metal determines the ultimate metal availability to biota. This and similar models require natural ligand concentrations and conditional stability constants as input parameters. In concept, the BLM is itself an analogue of some analytical approaches to the determination of trace metal speciation. A notable example is competitive ligand equilibration/cathodic stripping voltammetry, which employs an artificial ligand for comparative assessment of natural ligand concentrations and discrete conditional stability constants (i.e., BLM parameters) in a natural sample. Here, we report a new numerical approach to voltammetric speciation and parameter estimation that employs multiple analytical windows and a two-step optimization process, simultaneously generating both parameters and a complete suite of corresponding species concentrations. This approach is more powerful, systematic, and flexible than those previously reported.

Organic iron(III) speciation in surface transects across a frontal zone: the Chatham Rise, New Zealand

Iron (Fe) is a critical nutrient in marine systems and the organic complexation of Fe is a central factor of the marine biogeochemistry of Fe. In the present study, total dissolved Fe and its organic speciation were measured in filtered seawater samples ( 99.9%) by natural organic ligands, which were found to occur in excess of the dissolved Fe concentration at 1.29 ± 0.33 nm (equivalent to an excess over Fe of ~1.0 nm), and with a complex stability of log⁡ K ′ FeL,F e 3+ --> K′FeL,Fe3+ = 22.67 ± 0.22. The total ligand concentrations were consistently higher (~0.5 nm) in the ST and STC waters than in the SA waters. Our Fe data imply that the regional currents may be an important vehicle for transporting the elevated Fe across the front.

Iron stable isotopes track pelagic iron cycling during a subtropical phytoplankton bloom

Significance The supply and bioavailability of dissolved iron sets the magnitude of surface productivity for approximately 40% of the global ocean; however, our knowledge of how it is transferred between chemical states and pools is poorly constrained. Here we utilize the isotopic composition of dissolved and particulate iron to fingerprint its transformation in the surface ocean by abiotic and biotic processes. Photochemical and biological reduction and dissolution of particulate iron in the surface ocean appear to be key processes in regulating its supply and bioavailability to marine biota. Iron isotopes offer a new window into our understanding of the internal cycling of Fe, thereby allowing us to follow its biogeochemical transformations in the surface ocean. The supply and bioavailability of dissolved iron sets the magnitude of surface productivity for ∼40% of the global ocean. The redox state, organic complexation, and phase (dissolved versus particulate) of iron are key determinants of iron bioavailability in the marine realm, although the mechanisms facilitating exchange between iron species (inorganic and organic) and phases are poorly constrained. Here we use the isotope fingerprint of dissolved and particulate iron to reveal distinct isotopic signatures for biological uptake of iron during a GEOTRACES process study focused on a temperate spring phytoplankton bloom in subtropical waters. At the onset of the bloom, dissolved iron within the mixed layer was isotopically light relative to particulate iron. The isotopically light dissolved iron pool likely results from the reduction of particulate iron via photochemical and (to a lesser extent) biologically mediated reduction processes. As the bloom develops, dissolved iron within the surface mixed layer becomes isotopically heavy, reflecting the dominance of biological processing of iron as it is removed from solution, while scavenging appears to play a minor role. As stable isotopes have shown for major elements like nitrogen, iron isotopes offer a new window into our understanding of the biogeochemical cycling of iron, thereby allowing us to disentangle a suite of concurrent biotic and abiotic transformations of this key biolimiting element.