Keith A. Hunter

TESTING THE EFFECTS OF OCEAN ACIDIFICATION ON ALGAL METABOLISM: CONSIDERATIONS FOR EXPERIMENTAL DESIGNS(1).

Ocean acidification describes changes in the carbonate chemistry of the ocean due to the increased absorption of anthropogenically released CO2. Experiments to elucidate the biological effects of ocean acidification on algae are not straightforward because when pH is altered, the carbon speciation in seawater is altered, which has implications for photosynthesis and, for calcifying algae, calcification. Furthermore, photosynthesis, respiration, and calcification will themselves alter the pH of the seawater medium. In this review, algal physiologists and seawater carbonate chemists combine their knowledge to provide the fundamental information on carbon physiology and seawater carbonate chemistry required to comprehend the complexities of how ocean acidification might affect algae metabolism. A wide range in responses of algae to ocean acidification has been observed, which may be explained by differences in algal physiology, timescales of the responses measured, study duration, and the method employed to alter pH. Two methods have been widely used in a range of experimental systems: CO2 bubbling and HCl/NaOH additions. These methods affect the speciation of carbonate ions in the culture medium differently; we discuss how this could influence the biological responses of algae and suggest a third method based on HCl/NaHCO3 additions. We then discuss eight key points that should be considered prior to setting up experiments, including which method of manipulating pH to choose, monitoring during experiments, techniques for adding acidified seawater, biological side effects, and other environmental factors. Finally, we consider incubation timescales and prior conditioning of algae in terms of regulation, acclimation, and adaptation to ocean acidification.

Impacts of atmospheric nutrient deposition on marine productivity: Roles of nitrogen, phosphorus, and iron

Nutrients are supplied to the mixed layer of the open ocean by either atmospheric deposition or mixing from deeper waters, and these nutrients drive nitrogen and carbon fixation. To evaluate the importance of atmospheric deposition, we estimate marine nitrogen and carbon fixation from present-day simulations of atmospheric deposition of nitrogen, phosphorus, and iron. These are compared with observed rates of marine nitrogen and carbon fixation. We find that Fe deposition is more important than P deposition in supporting N fixation. Estimated rates of atmospherically supported carbon fixation are considerably lower than rates of marine carbon fixation derived from remote sensing, indicating the subsidiary role atmospheric deposition plays in total C uptake by the oceans. Nonetheless, in high-nutrient, low-chlorophyll areas, the contribution of atmospheric deposition of Fe to the surface ocean could account for about 50% of C fixation. In marine areas typically thought to be N limited, potential C fixation supported by atmospheric deposition of N is only ~1%-2% of observed rates. Although these systems are N-limited, the amount of N supplied from below appears to be much larger than that deposited from above. Atmospheric deposition of Fe has the potential to augment atmospherically supported rates of C fixation in N-limited areas. In these areas, atmospheric Fe relieves the Fe limitation of diazotrophic organisms, thus contributing to the rate of N fixation. The most important uncertainties in understanding the relative importance of different atmospheric nutrients are poorly understood speciation and solubility of Fe as well as the N:Fe ratio of diazotrophic organisms.

Iron-binding ligands and their role in the ocean biogeochemistry of iron

Environmental context. It is now well accepted that iron is an essential micronutrient for phytoplankton growth in many areas of the global ocean, even though this element is present in seawater in extremely low abundance. It is also known that most of the iron in seawater is present as complexes formed with ligands of natural organic matter whose nature and origin remain largely unknown. Here we consider how these iron-complexing ligands might have evolved during geological time, what factors may have given rise to their presence and the possible roles that they play in iron biogeochemistry. Abstract. Current knowledge about the role of iron-binding organic ligands in the ocean and their role in determining the biogeochemistry of this biologically active element has been summarised. Some electrochemical measurements suggest the presence of at least two ligand types, a strong binding ligand L1 found mainly in the mixed layer and a weaker ligand L2 found mainly in deep water. Speciation of FeIII is dominated by L1 in the mixed layer and L2 in the deep ocean. There is some evidence that L1 is siderophore-like and is specifically generated by marine microbes (i.e. heterotropic bacteria and cyanobacteria). We suggest that this is a specific biological mechanism for sequestering iron in the mixed layer that developed early in the ocean’s history (Archaean period, 2500–3500 million years BP), whereas the more ubiquitous L2 ligand only arose at the close of the Proterozoic (500–2500 million years BP) when eukaryotic organisms evolved to switch on the ocean’s biological pump, allowing L2 ligands to form from the oxidation of sinking biological particles. This development coincided with the complete oxygenation of the ocean’s interior which removed the iron-binding sulfide ion and allowed maintenance of the ocean’s iron inventory. These speculations are accompanied by various suggestions about avenues for future research to better understand iron biogeochemistry.

CARBON-USE STRATEGIES IN MACROALGAE: DIFFERENTIAL RESPONSES TO LOWERED PH AND IMPLICATIONS FOR OCEAN ACIDIFICATION1

Ocean acidification (OA) is a reduction in oceanic pH due to increased absorption of anthropogenically produced CO2. This change alters the seawater concentrations of inorganic carbon species that are utilized by macroalgae for photosynthesis and calcification: CO2 and HCO3− increase; CO32− decreases. Two common methods of experimentally reducing seawater pH differentially alter other aspects of carbonate chemistry: the addition of CO2 gas mimics changes predicted due to OA, while the addition of HCl results in a comparatively lower [HCO3−]. We measured the short‐term photosynthetic responses of five macroalgal species with various carbon‐use strategies in one of three seawater pH treatments: pH 7.5 lowered by bubbling CO2 gas, pH 7.5 lowered by HCl, and ambient pH 7.9. There was no difference in photosynthetic rates between the CO2, HCl, or pH 7.9 treatments for any of the species examined. However, the ability of macroalgae to raise the pH of the surrounding seawater through carbon uptake was greatest in the pH 7.5 treatments. Modeling of pH change due to carbon assimilation indicated that macroalgal species that could utilize HCO3− increased their use of CO2 in the pH 7.5 treatments compared to pH 7.9 treatments. Species only capable of using CO2 did so exclusively in all treatments. Although CO2 is not likely to be limiting for photosynthesis for the macroalgal species examined, the diffusive uptake of CO2 is less energetically expensive than active HCO3− uptake, and so HCO3−‐using macroalgae may benefit in future seawater with elevated CO2.

Atmospheric fluxes of organic N and P to the global ocean

The global tropospheric budget of gaseous and particulate non-methane organic matter (OM) is re-examined to provide a holistic view of the role that OM plays in transporting the essential nutrients nitrogen and phosphorus to the ocean. A global 3-dimensional chemistry-transport model was used to construct the first global picture of atmospheric transport and deposition of the organic nitrogen (ON) and organic phosphorus (OP) that are associated with OM, focusing on the soluble fractions of these nutrients. Model simulations agree with observations within an order of magnitude. Depending on location, the observed water soluble ON fraction ranges from similar to 3% to 90% (median of similar to 35%) of total soluble N in rainwater; soluble OP ranges from similar to 20-83% (median of similar to 35%) of total soluble phosphorus. The simulations suggest that the global ON cycle has a strong anthropogenic component with similar to 45% of the overall atmospheric source (primary and secondary) associated with anthropogenic activities. In contrast, only 10% of atmospheric OP is emitted from human activities. The model-derived present-day soluble ON and OP deposition to the global ocean is estimated to be similar to 16 Tg-N/yr and similar to 0.35 Tg-P/yr respectively with an order of magnitude uncertainty. Of these amounts similar to 40% and similar to 6%, respectively, are associated with anthropogenic activities, and 33% and 90% are recycled oceanic materials. Therefore, anthropogenic emissions are having a greater impact on the ON cycle than the OP cycle; consequently increasing emissions may increase P-limitation in the oligotrophic regions of the worlds ocean that rely on atmospheric deposition as an important nutrient source.

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)

Diurnal fluctuations in seawater pH influence the response of a calcifying macroalga to ocean acidification

Coastal ecosystems that are characterized by kelp forests encounter daily pH fluctuations, driven by photosynthesis and respiration, which are larger than pH changes owing to ocean acidification (OA) projected for surface ocean waters by 2100. We investigated whether mimicry of biologically mediated diurnal shifts in pH—based for the first time on pH time-series measurements within a kelp forest—would offset or amplify the negative effects of OA on calcifiers. In a 40-day laboratory experiment, the calcifying coralline macroalga, Arthrocardia corymbosa, was exposed to two mean pH treatments (8.05 or 7.65). For each mean, two experimental pH manipulations were applied. In one treatment, pH was held constant. In the second treatment, pH was manipulated around the mean (as a step-function), 0.4 pH units higher during daylight and 0.4 units lower during darkness to approximate diurnal fluctuations in a kelp forest. In all cases, growth rates were lower at a reduced mean pH, and fluctuations in pH acted additively to further reduce growth. Photosynthesis, recruitment and elemental composition did not change with pH, but δ13C increased at lower mean pH. Including environmental heterogeneity in experimental design will assist with a more accurate assessment of the responses of calcifiers to OA.

On the estuarine mixing of dissolved substances in relation to colloid stability and surface properties

Abstract The estuarine mixing of dissolved Fe, Cu, Ni, Si and surface-active organic matter has been investigated in the Taieri Estuary, New Zealand, simultaneously with measurements of the electrokinetic charge on colloidal particles. Dissolved Fe showed almost quantitative removal from solution characteristic of the coagulation of iron-containing colloids by seawater electrolytes. Surface active organic matter behaved conservatively, indicating that a relatively constant fraction of estuarine organic matter is surface active, but that organic species associated with iron during removal are a minor fraction. Results for Cu, Ni and Si were scattered but offered no evidence for gross removal during estuarine mixing. The negative charge on suspended colloids was not reversed by adsorption of seawater cations, but remained uniformly negative throughout the salinity range, decreasing sharply in magnitude during the first few %. salinity.

Reduction of chromium(VI) by bacterially produced hydrogen sulphide in a marine environment

Abstract Chromium in both the Cr(III) and Cr(VI) state enters Otago Harbour in effluent from a tannery. The Cr(III) is precipitated together with organic matter from the effluent into the sediment. Chromium(VI) which might be expected from thermodynamic considerations to remain in the overlying water does not. Instead it is converted to the Cr(III) state by the hydrogen sulphide diffusing into the overlying water produced by sulphate-reducing bacteria.

Equilibrium adsorption of thorium by metal oxides in marine electrolytes

Abstract The equilibrium adsorption of Th by the hydrous oxides goethite (α-FeOOH) and δ-MnO 2 in marine electrolytes is not affected by the major cations Ca 2+ and Mg 2 , relative to NaCl electrolyte, while SO 2− 4 decreased adsorption through competitive ion pairing with Th in solution. A triple layer model of surface speciation in NaCl electrolyte suggested that adsorption of Th mainly involves the hydrolysed forms Th(OH) 2+ 2 , Th(OH) + 3 and Th(OH) 4 . Intrinsic surface binding constants for these species were determined by fitting the model calculations to experimental adsorption data. In sulphate-containing electrolytes, including seawater, the model correctly predicted the slope of the adsorption curves for both oxides, with the pH of the adsorption edge depending on values used for Th-sulphate ion-pairing equilibrium constants. Competition experiments using synthetic organic ligands to buffer the Th concentrations with δ-MnO 2 lowered the concentration free Th available for adsorption to within the range of oceanic dissolved Th concentrations. This gave rise to shifts in the adsorption edge to higher pH close to that of seawater, which were consistently predicted by the model. Application of the model to the deep ocean water column suggested that δ-MnO 2 would not be a powerful scavenger for Th because of the development of a strong negative surface charge at pH 8, while adsorption on goethite should be significant.