Potential impact of DOM accumulation of fCO2 and carbonate ion computations in ocean acidification experiments

The internal consistency of measurements and computations of components of the CO2-system, namely total alkalinity (AT), total dissolved carbon dioxide (CT), CO2 fugacity (fCO2), and pH, has been confirmed repeatedly in open ocean studies when the CO2 system had been over determined. Differences between measured and computed properties, such as ΔfCO2 (=fCO2(measured) – fCO2(computed from AT and CT))/ fCO2(measured)× 100), there are usually below 5%. Recently, Hoppe et al. (2010) provided evidence of significantly larger ΔfCO2 in experimental setups. These observations are currently not well understood. Here we discuss a case from a series of phytoplankton culture experiments with ΔfCO2 of up to about 25%. ΔfCO2 varied systematically during the course of these experiments and showed a clear correlation with the accumulation of dissolved organic carbon (DOC). Culture and mesocosm experiments are often carried out under very high initial nutrient concentrations, yielding high biomass concentrations that in turn often lead to a substantial build-up of DOC. DOC can reach concentrations much higher than typically observed in the open ocean. To the extent that DOC includes organic acids and bases, it will contribute to the alkalinity of the seawater contained in the experimental device. Our analysis suggests that whenever substantial amounts of DOC are produced during the experiment, standard computer programs used to compute CO2 fugacity can underestimate true fCO2 significantly when the computation is based on AT and CT. Alternative explanations for large ΔfCO2, e.g. uncertainties of pKs, are explored as well, but are found to be of minor importance. Unless the effect of DOC-alkalinity is accounted for, this might lead to significant errors in the interpretation of the system under consideration to the experimentally applied CO2 perturbation, which could misguide the development of parameterisations used in simulations with global carbon cycle models in future CO2-scenarios

Overlooked runaway feedback in the marine nitrogen cycle: the vicious cycle

The marine nitrogen (N) inventory is controlled by the interplay of nitrogen loss processes, here referred to as denitrification, and nitrogen source processes, primarily nitrogen fixation. The apparent stability of the marine N inventory on time scales longer than the estimated N residence time, suggests some intimate balance between N sinks and sources. Such a balance may be perceived easier to achieve when N sinks and sources occur in close spatial proximity, and some studies have interpreted observational evidence for such a proximity as indication for a stabilizing feedback processes. Using a biogeochemical ocean circulation model, we here show instead that a close spatial association of N2 fixation and denitrification can, in fact, trigger destabilizing feedbacks on the N inventory and, because of stoichiometric constrains, lead to net N losses. Contrary to current notion, a balanced N inventory requires a regional separation of N sources and sinks. This can be brought about by factors that reduce the growth of diazotrophs, such as iron, or by factors that affect the fate of the fixed nitrogen remineralization, such as dissolved organic matter dynamics. In light of our findings we suggest that spatial arrangements of N sinks and sources have to be accounted for in addition to individual rate estimates for reconstructing past, evaluating present and predicting future marine N inventory imbalances

Effects of Planktonic Copepods on Transparent Exopolymeric Particles (TEP) Abundance and Size Spectra

Diatoms exude considerable quantities of polymers, mainly polysaccharides, that play an important role in the process of sestonic particle aggregation in the sea. We investigated the impact of copepods on transparent exopolymeric particles (TEP) generated by the diatom Thalassiosira weissflogii. Grazing experiments with 14C-labelled algae exudates demonstrated that copepods typical of the Baltic Sea were not actively filtering TEP. Control experiments showed that ‘uptake’ of radioactivity could be ascribed to passive uptake, such as adsorption of radioactively-labelled particles to the body surface. Furthermore, we tested the effect of copepods on TEP size spectra. The abundance and size distribution of TEP (from 1.4 to 180 μm of Equivalent Spherical Diameter) were analysed in a 4 h incubation experiment. In the presence of copepods, the proportion of larger TEP was higher. An increase in total volume of TEP in jars containing copepods (~2 × 107 μm ml–1) compared with control jars without copepods (~0.5 × 107 μm3 ml–1) was also observed. The process of aggregation of TEP demonstrated in this work, whereby copepods increase downward particle flux without consuming carbon, can have far-reaching consequences for carbon fluxes along the water column and for copepods feeding dynamics

Oxygen, carbon, and nutrients in the oligotrophic eastern subtropical North Atlantic

The Beta Triangle, a region of the oligotrophic subtropical eastern North Atlantic Ocean, is notorious for its enigmatic oxygen, carbon, and nitrogen balances, in which nutrient supply is said to explain only a fraction of production necessary for estimated carbon export. Rates of dissolved organic carbon accumulation and dissolved organic nitrogen utilization in surface water and an assessment of oxygen utilized, organic matter consumed, and nitrate and phosphate regenerated in subsurface water, show that conventional production estimates miss substantial shares of biotic production. The shallow export of total organic carbon, predominantly dissolved (DOC), by subduction is responsible for about 50–70% of apparent oxygen utilization in subsurface water between the base of the surface layer at ca. 140 m and ca. 195 m depth, but it is insignificant below. Additionally, there is an estimated accumulation of 1.0 to 1.75 mol DOC m−2 a−1 in surface water. Including DOC dynamics in its carbon balance reveals the surface of this ultra-oligotrophic part of the ocean to be net autotrophic. Increasing subsurface values of excess nitrogen (DINxs) imply the export of nitrogen from surface water stemming from production not exclusively fuelled by new nitrate supplied from below. Total organic nitrogen (almost exclusively dissolved, DON) is consumed in the surface layer at a rate estimated at 0.13 to 0.23 mol m−2 a−1. There is no variation in dissolved organic phosphorus (DOP) in the same direction. DON utilization thus contributes to the pronounced subsurface DINxs signature. DOC export and accumulation are important in the carbon balance in surface and near-surface water. DON utilization and, probably, N2 fixation contribute significant amounts to the nitrogen supply of surface water. These processes can close part of the enigmatic carbon and nitrogen balances in the Beta Triangle. There are, however, no comparable processes which can explain the equally enigmatic situation concerning phosphorus supply in this area

Side effects and accounting aspects of hypothetical large-scale Southern Ocean iron fertilization

Recent suggestions to slow down the increase in atmospheric carbon dioxide have included ocean fertilization by addition of the micronutrient iron to Southern Ocean surface waters, where a number of natural and artificial iron fertilization experiments have shown that low ambient iron concentrations limit phytoplankton growth. Using a coupled carbon-climate model with the marine biology's response to iron addition calibrated against data from natural iron fertilization experiments, we examine biogeochemical side effects of a hypothetical large-scale Southern Ocean Iron Fertilization (OIF) that need to be considered when attempting to account for possible OIF-induced carbon offsets. In agreement with earlier studies our model simulates an OIF-induced increase in local air-sea CO2 fluxes by about 60 GtC over a 100-year period, which amounts to about 40% of the OIF-induced increase in organic carbon export. Offsetting CO2 return fluxes outside the region and after stopping the fertilization at 1, 7, 10, 50, and 100 years are quantified for a typical accounting period of 100 years. For continuous Southern Ocean iron fertilization, the return flux outside the fertilized area cancels about 8% of the fertilization-induced CO2 air-sea flux within the fertilized area on a 100-yr timescale. This "leakage" effect has a similar radiative impact as the simulated enhancement of marine N2O emissions. Other side effects not yet discussed in terms of accounting schemes include a decrease in Southern Ocean oxygen levels and a simultaneous shrinking of tropical suboxic areas, and accelerated ocean acidification in the entire water column in the Southern Ocean on the expense of reduced globally averaged surface water acidification. A prudent approach to account for the OIF-induced carbon sequestration would account for global air-sea CO2 fluxes rather than for local fluxes into the fertilized area only. However, according to our model, this would underestimate the potential for offsetting CO2 emissions by about 20% on a 100 year accounting timescale. We suggest that a fair accounting scheme applicable to both terrestrial and marine carbon sequestration has to be based on emission offsets rather than on changes in individual carbon pools

Calcifying Phytoplankton Demonstrate an Enhanced Role in Greenhouse Atmospheric CO2 Regulation

The impact of calcifying phytoplankton on atmospheric CO2 concentration is determined by a number of factors, including their degree of ecological success as well as the buffering capacity of the ocean/marine sediment system. The relative importance of these factors has changed over Earth's history and this has implications for atmospheric CO2 and climate regulation. We explore some of these implications with four “Strangelove” experiments: two in which soft-tissue production and calcification is stopped, and two in which only calcite production is forced to stop, in idealized icehouse and greenhouse climates. We find that in the icehouse climate the loss of calcifiers compensates the atmospheric CO2 impact of the loss of all phytoplankton by roughly one-sixth. But in the greenhouse climate the loss of calcifiers compensates the loss of all phytoplankton by about half. This increased impact on atmospheric CO2 concentration is due to the combination of higher rates of pelagic calcification due to warmer temperatures and weaker buffering due to widespread acidification in the greenhouse ocean. However, the greenhouse atmospheric temperature response per unit of CO2 change to removing ocean soft-tissue production and calcification is only one-fourth that in an icehouse climate, owing to the logarithmic radiative forcing dependency on atmospheric CO2 thereby reducing the climate feedback of mass extinction. This decoupling of carbon cycle and temperature sensitivities offers a mechanism to explain the dichotomy of both enhanced climate stability and destabilization of the carbonate compensation depth in greenhouse climates

Particle flux, and composition of sedimenting matter, in the Greenland Sea

Vertical flux of particulate material was recorded with moored sediment traps during 1988/1989 in the Greenland Sea at 72 degrees N, 10 degrees W. This region exhibits pronounced seasonal variability in ice cover. Annual fluxes at 500 m water depth were 22.79, 8.55, 2.39, 3.81 and 0.51 g m(-2) for total flux (dry weight), carbonate, particulate biogenic silicate, particulate organic carbon and nitrogen, respectively. Fluxes increased in April, maximum rates of all compounds occurred in May-June, and consistently high total flux rates of around 100 mg m(-2)d(-1) prevailed during the summer. The increasing flux of biogenic particles measured in April is indicative of an early onset of algal growth in spring. Small pennate diatoms dominated in the trap collections during April, and were still numerous during the high flux period when Thalassiosira species were the most abundant diatoms. During May-June, up to 22% of the Thalassiosira cells collected were viable-looking cells. The faecal pellet flux increased after the May-June event. Therefore we conclude that the diatoms settled as phytodetritus, most likely in rapidly sinking aggregates. From seasonal nutrient profiles it is concluded that diatoms contribute 25% to new production during spring and 50% on an annual basis. More than 50% of newly produced silicate particles are dissolved above the 500 m horizon. High new production during spring does not lead to a pronounced sedimentation pulse of organic matter during spring but elavated vertical export is observed during the entire growth perio

Model-based Assessment of the CO2 Sequestration Potential of Coastal Ocean Alkalinization

The potential of Coastal Ocean Alkalinization (COA), a carbon dioxide removal (CDR) climate engineering strategy that chemically increases ocean carbon uptake and storage, is investigated with an Earth system model of intermediate complexity. The CDR potential and possible environmental side effects are estimated for various COA deployment scenarios, assuming olivine as the alkalinity source in ice-free coastal waters (about 8.6% of the global ocean's surface area), with dissolution rates being a function of grain size, ambient seawater temperature and pH. Our results indicate that for a large-enough olivine deployment of small-enough grain sizes (10 μm), atmospheric CO2 could be reduced by more than 800 GtC by the year 2100. However, COA with coarse olivine grains (1000 μm) has little CO2 sequestration potential on this time scale. Ambitious CDR with fine olivine grains would increase coastal aragonite saturation Ω to levels well beyond those that are currently observed. When imposing upper limits for aragonite saturation levels (Ωlim) in the grid boxes subject to COA (Ωlim = 3.4 and 9 chosen as examples), COA still has the potential to reduce atmospheric CO2 by 265 GtC (Ωlim=3.4) to 790 GtC (Ωlim=9) and increase ocean carbon storage by 290 Gt (Ωlim=3.4) to 913 Gt (Ωlim=9) by year 2100

Methods to evaluate CaCO3 cycle modules in coupled global biogeochemical ocean models

The marine CaCO3 cycle is an important component of the oceanic carbon system and directly affects the cycling of natural and the uptake of anthropogenic carbon. In numerical models of the marine carbon cycle, the CaCO3 cycle component is often evaluated against the observed distribution of alkalinity. Alkalinity varies in response to the formation and remineralization of CaCO3 and organic matter. However, it also has a large conservative component, which may strongly be affected by a deficient representation of ocean physics (circulation, evaporation, and precipitation) in models. Here we apply a global ocean biogeochemical model run into preindustrial steady state featuring a number of idealized tracers, explicitly capturing the model's CaCO3 dissolution, organic matter remineralization, and various preformed properties (alkalinity, oxygen, phosphate). We compare the suitability of a variety of measures related to the CaCO3 cycle, including alkalinity (TA), potential alkalinity and TA*, the latter being a measure of the time-integrated imprint of CaCO3 dissolution in the ocean. TA* can be diagnosed from any data set of TA, temperature, salinity, oxygen and phosphate. We demonstrate the sensitivity of total and potential alkalinity to the differences in model and ocean physics, which disqualifies them as accurate measures of biogeochemical processes. We show that an explicit treatment of preformed alkalinity (TA0) is necessary and possible. In our model simulations we implement explicit model tracers of TA0 and TA*. We find that the difference between modelled true TA* and diagnosed TA* was below 10% (25%) in 73% (81%) of the ocean's volume. In the Pacific (and Indian) Oceans the RMSE of A* is below 3 (4) mmol TA m−3, even when using a global rather than regional algorithms to estimate preformed alkalinity. Errors in the Atlantic Ocean are significantly larger and potential improvements of TA0 estimation are discussed. Applying the TA* approach to the output of three state-of-the-art ocean carbon cycle models, we demonstrate the advantage of explicitly taking preformed alkalinity into account for separating the effects of biogeochemical processes and circulation on the distribution of alkalinity. In particular, we suggest to use the TA* approach for CaCO3 cycle model evaluation

A new perspective on environmental controls of marine nitrogen fixation

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 non-fixing 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 exo-enzymatic break-down of DOP gives 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