Surface ocean iron (Fe) fertilization can affect the marine primary productivity (MPP), thereby impacting on CO2 exchanges at the atmosphere‐ocean interface and eventually on climate. Mineral (aeolian or desert) dust is known to be a major atmospheric source for the surface ocean biogeochemical iron cycle, but the significance of volcanic ash is poorly constrained. We present the results of geochemical experiments aimed at determining the rapid release of Fe upon contact of pristine volcanic ash with seawater, mimicking their dry deposition into the surface ocean. Our data show that volcanic ash from both subduction zone and hot spot volcanoes (n = 44 samples) rapidly mobilized significant amounts of soluble Fe into seawater (35–340 nmol/g ash), with a suggested global mean of 200 ± 50 nmol Fe/g ash. These values are comparable to the range for desert dust in experiments at seawater pH (10–125 nmol Fe/g dust) presented in the literature (Guieu et al., 1996; Spokes et al., 1996). Combining our new Fe release data with the calculated ash flux from a selected major eruption into the ocean as a case study demonstrates that single volcanic eruptions have the potential to significantly increase the surface ocean Fe concentration within an ash fallout area. We also constrain the long‐term (millennial‐scale) airborne volcanic ash and mineral dust Fe flux into the Pacific Ocean by merging the Fe release data with geological flux estimates. These show that the input of volcanic ash into the Pacific Ocean (128–221 × 1015 g/ka) is within the same order of magnitude as the mineral dust input (39–519 × 1015 g/ka) (Mahowald et al., 2005). From the similarity in both Fe release and particle flux follows that the flux of soluble Fe related to the dry deposition of volcanic ash (3–75 × 109 mol/ka) is comparable to that of mineral dust (1–65 × 109 mol/ka). Our study therefore suggests that airborne volcanic ash is an important but hitherto underestimated atmospheric source for the Pacific surface ocean biogeochemical iron cycle.

Abstract. Iron is a key micronutrient for phytoplankton growth in the surface ocean. Yet the significance of volcanism for the marine biogeochemical iron-cycle is poorly constrained. Recent studies, however, suggest that offshore deposition of airborne ash from volcanic eruptions is a way to inject significant amounts of bio-available iron into the surface ocean. Volcanic ash may be transported up to several tens of kilometers high into the atmosphere during largescale eruptions and fine ash may stay aloft for days to weeks, thereby reaching even the remotest and most ironstarved oceanic regions. Scientific ocean drilling demonstrates that volcanic ash layers and dispersed ash particles are frequently found in marine sediments and that therefore volcanic ash deposition and iron-injection into the oceans took place throughout much of the Earth's history. Natural evidence and the data now available from geochemical and biological experiments and satellite techniques suggest that volcanic ash is a so far underestimated source for iron in the surface ocean, possibly of similar importance as aeolian dust. Here we summarise the development of and the knowledge in this fairly young research field. The paper Correspondence to: S. Duggen (svend duggen@skoleforeningen.de) covers a wide range of chemical and biological issues and we make recommendations for future directions in these areas. The review paper may thus be helpful to improve our understanding of the role of volcanic ash for the marine biogeochemical iron-cycle, marine primary productivity and the ocean-atmosphere exchange of CO 2 and other gases relevant for climate in the Earth's history.

Resale or republication not permitted without written consent of the publisherInorganic nitrogen and phosphorus control the competition between diazotrophs and ordinary phytoplankton, which in turn drives ambient nutrient concentrations; diazotrophs are strong competitors for P, as they can invest more energy into its acquisition.

The marine nitrogen (N) inventory is thought to be stabilized by negative feedback mechanisms that reduce N inventory excursions relative to the more slowly overturning phosphorus inventory. Using a global biogeochemical ocean circulation model we show that negative feedbacks stabilizing the N inventory cannot persist if a close spatial association of N₂ fixation and denitrification occurs. In our idealized model experiments, nitrogen deficient waters, generated by denitrification, stimulate local N₂ fixation activity. But, because of stoichiometric constraints, the denitrification of newly fixed nitrogen leads to a net loss of N. This can enhance the N deficit, thereby triggering additional fixation in a vicious cycle, ultimately leading to a runaway N loss. To break this vicious cycle, and allow for stabilizing negative feedbacks to occur, inputs of new N need to be spatially decoupled from denitrification. Our idealized model experiments suggest that factors such as iron limitation or dissolved organic matter cycling can promote such decoupling and allow for negative feedbacks that stabilize the N inventory. Conversely, close spatial co-location of N₂ fixation and denitrification could lead to net N loss

[1] Accounting for ocean currents in the bulk parameterization of the wind stress might represent a physically more plausible way to force an ocean model than ignoring their effect. We show in this study that using the air-sea velocity difference instead of the atmospheric wind in the wind stress formulation dampens both the near-surface eddy activity and the biotic carbon assimilation in a high-resolution model of the North Atlantic. The former is significant, corresponding to a reduction down to 50% in the tropical Atlantic, while in higher latitudes (in agreement with previous results) the reduction of eddy activity is only around 10%. The effect on biotically mediated new production and air-sea carbon fluxes is, on the other hand, minor. New production is reduced by less than 5% on a basin average, while simulated air-sea CO 2 fluxes are barely affected at all. The model results imply that eddy/wind interaction introduced by accounting for ocean currents in the wind stress formulation does not drive any additional (and hitherto unaccounted) nutrient fluxes to the sunlit surface of the subtropical gyre, as was recently proposed in the literature.Citation: Eden, C., and H. Dietze (2009), Effects of mesoscale eddy/wind interactions on biological new production and eddy kinetic energy,

Earth system climate models generally underestimate dissolved oxygen concentrations in the deep eastern equatorial Pacific. This problem is associated with the “nutrient trapping” problem, described by Najjar et al. [1992], and is, at least partially, caused by a deficient representation of the Equatorial Intermediate Current System (EICS). Here we emulate the unresolved EICS in the UVic earth system climate model by locally increasing the zonal isopycnal diffusivity. An anisotropic diffusivity of ∼50,000 m2 s−1 yields an improved global representation of temperature, salinity and oxygen. In addition, it (1) resolves most of the local “nutrient trapping” and associated oxygen deficit in the eastern equatorial Pacific and (2) reduces spurious zonal temperature gradients on isopycnals without affecting other physical metrics such as meridional overturning or air‐sea heat fluxes. Finally, climate projections of low‐oxygenated waters and associated denitrification change sign and apparently become more plausible.

Growing slowly, marine N2 fixers are generally expected to be competitive only where nitrogen (N) supply is low relative to that of phosphorus (P) with respect to the cellular N:P ratio (R) of nonfixing phytoplankton. This is at odds with observed high N2 fixation rates in the oligotrophic North Atlantic where the ratio of nutrients supplied to the surface is elevated in N relative to the average R (16:1). In this study, we investigate several mechanisms to solve this puzzle: iron limitation, phosphorus enhancement by preferential remineralization or stoichiometric diversity of phytoplankton, and dissolved organic phosphorus (DOP) utilization. Combining resource competition theory and a global coupled ecosystem‐circulation model, we find that the additional N and energy investments required for exoenzymatic breakdown of DOP give N2 fixers a competitive advantage in oligotrophic P‐starved regions. Accounting for this mechanism expands the ecological niche of N2 fixers also to regions where the nutrient supply is high in N relative to R, yielding, in our model, a pattern consistent with the observed high N2 fixation rates in the oligotrophic North Atlantic.

[1] We analyze an extensive set of global coupled biogeochemical ocean circulation models. The focus is on the equatorial Pacific. In all simulations, which are consistent with observed standing stocks of relevant biogeochemical species at the surface, we find spuriously enhanced (reduced) macronutrient (oxygen) concentrations in the deep eastern equatorial Pacific. This modeling problem, apparently endemic to global coupled biogeochemical ocean circulation models, was coined "nutrient trapping" by Najjar et al. (1992). In contrast to Aumont et al. (1999), we argue that "nutrient trapping" is still a persistent problem, even in eddy-permitting models and, further, that the scale of the problem retards model projections of nitrogen cycling. In line with previous work, our results indicate that a deficient circulation is at the core of the problem rather than an admittedly poor quantitative understanding of biogeochemical cycles. More specifically, we present indications that "nutrient trapping" in models is a result of a spuriously damped Equatorial Intermediate (zonal) Current System and Equatorial Deep Jets-phenomenon which await a comprehensive understanding and have, to date, not been successfully simulated.