Description: Changes to seawater inorganic carbon and nutrient concentrations in response to the deliberate CO2 perturbation of natural plankton assemblages were studied during the 2005 Pelagic Ecosystem CO2 Enrichment (PeECE III) experiment. Inverse analysis of the temporal inorganic carbon dioxide system and nutrient variations was used to determine the net community stoichiometric uptake characteristics of a natural pelagic ecosystem perturbed over a range of pCO2 scenarios (350, 700 and 1050 μatm). Nutrient uptake showed no sensitivity to CO2 treatment. There was enhanced carbon production relative to nutrient consumption in the higher CO2 treatments which was positively correlated with the initial CO2 concentration. There was no significant calcification response to changing CO2 in Emiliania huxleyi by the peak of the bloom and all treatments exhibited low particulate inorganic carbon production (~15 μmol kg−1). With insignificant air-sea CO2 exchange across the treatments, the enhanced carbon uptake was due to increase organic carbon production. The inferred cumulative C:N:P stoichiometry of organic production increased with CO2 treatment from 1:6.3:121 to 1:7.1:144 to 1:8.25:168 at the height of the bloom. This study discusses how ocean acidification may incur modification to the stoichiometry of pelagic production and have consequences for ocean biogeochemical cycling.

Description: Availability of phosphate for phytoplankton and bacteria and of glucose for bacteria at different pCO2 levels were studied in a mesocosm experiment (PeECE III). Using nutrient-depleted SW Norwegian fjord waters, three different levels of pCO2 (350 μatm: 1×CO2; 700 μatm: 2×CO2; 1050 μatm: 3×CO2) were set up, and nitrate and phosphate were added at the start of the experiment in order to induce a phytoplankton bloom. Despite similar responses of total particulate P concentration and phosphate turnover time at the three different pCO2 levels, the size distribution of particulate P and 33PO4 uptake suggested that phosphate transferred to the 〉10 μm fraction was greater in the 3×CO2 mesocosm during the first 6–10 days when phosphate concentration was high. During the period of phosphate depletion (after Day 12), specific phosphate affinity and specific alkaline phosphatase activity (APA) suggested a P-deficiency (i.e. suboptimal phosphate supply) rather than a P-limitation for the phytoplankton and bacterial community at the three different pCO2 levels. Specific phosphate affinity and specific APA tended to be higher in the 3×CO2 than in the 2×CO2 and 1×CO2 mesocosms during the phosphate depletion period, although no statistical differences were found. Glucose turnover time was correlated significantly and negatively with bacterial abundance and production but not with the bulk DOC concentration. This suggests that even though constituting a small fraction of the bulk DOC, glucose was an important component of labile DOC for bacteria. Specific glucose affinity of bacteria behaved similarly at the three different pCO2 levels with measured specific glucose affinities being consistently much lower than the theoretical maximum predicted from the diffusion-limited model. This suggests that bacterial growth was not severely limited by the glucose availability. Hence, it seems that the lower availability of inorganic nutrients after the phytoplankton bloom reduced the bacterial capacity to consume labile DOC in the upper mixed layer of the stratified mesocosms.

Description: Increasing atmospheric carbon dioxide (CO2) concentrations due to anthropogenic fossil fuel combustion are currently changing the ocean's chemistry. Increasing oceanic [CO2] and consequently decreasing seawater pH have the potential to significantly impact marine life. Here we describe and analyze the build-up and decline of a natural phytoplankton bloom initiated during the 2005 mesocosm Pelagic Ecosystem CO2 Enrichment study (PeECE III). The draw-down of inorganic nutrients in the upper surface layer of the mesocosms was reflected by a concomitant increase of organic matter until day t11, the peak of the bloom. From then on, biomass standing stocks steadily decreased as more and more particulate organic matter was lost into the deeper layer of the mesocosms. We show that organic carbon export to the deeper layer was significantly enhanced at elevated CO2. This phenomenon might have impacted organic matter remineralization leading to decreased oxygen concentrations in the deeper layer of the high CO2 mesocosms as indicated by deep water ammonium concentrations. This would have important implications for our understanding of pelagic ecosystem functioning and future carbon cycling.

Description: Eastern boundary upwelling systems (EBUS) are among the most productive marine ecosystems on Earth. The production of organic material is fueled by upwelling of nutrient-rich deep waters and high incident light at the sea surface. However, biotic and abiotic factors can modify surface production and related biogeochemical processes. Determining these factors is important because EBUS are considered hotspots of climate change, and reliable predictions of their future functioning requires understanding of the mechanisms driving the biogeochemical cycles therein. In this field experiment, we used in situ mesocosms as tools to improve our mechanistic understanding of processes controlling organic matter cycling in the coastal Peruvian upwelling system. Eight mesocosms, each with a volume of ∼55 m3, were deployed for 50 d ∼6 km off Callao (12∘ S) during austral summer 2017, coinciding with a coastal El Niño phase. After mesocosm deployment, we collected subsurface waters at two different locations in the regional oxygen minimum zone (OMZ) and injected these into four mesocosms (mixing ratio ≈1.5 : 1 mesocosm: OMZ water). The focus of this paper is on temporal developments of organic matter production, export, and stoichiometry in the individual mesocosms. The mesocosm phytoplankton communities were initially dominated by diatoms but shifted towards a pronounced dominance of the mixotrophic dinoflagellate (Akashiwo sanguinea) when inorganic nitrogen was exhausted in surface layers. The community shift coincided with a short-term increase in production during the A. sanguinea bloom, which left a pronounced imprint on organic matter C : N : P stoichiometry. However, C, N, and P export fluxes did not increase because A. sanguinea persisted in the water column and did not sink out during the experiment. Accordingly, export fluxes during the study were decoupled from surface production and sustained by the remaining plankton community. Overall, biogeochemical pools and fluxes were surprisingly constant for most of the experiment. We explain this constancy by light limitation through self-shading by phytoplankton and by inorganic nitrogen limitation which constrained phytoplankton growth. Thus, gain and loss processes remained balanced and there were few opportunities for blooms, which represents an event where the system becomes unbalanced. Overall, our mesocosm study revealed some key links between ecological and biogeochemical processes for one of the most economically important regions in the oceans.

Description: Increasing atmospheric carbon dioxide (CO2) through human activities and invasion of anthropogenic CO2 into the surface ocean alters the seawater carbonate chemistry, increasing CO2 and bicarbonate (HCO3−) at the expense of carbonate ion (CO32−) concentrations. This redistribution in the dissolved inorganic carbon (DIC) pool decreases pH and carbonate saturation state (Ω). Several components of the carbonate system are considered potential key variables influencing for instance calcium carbonate precipitation in marine calcifiers such as coccolithophores, foraminifera, corals, mollusks and echinoderms. Unravelling the sensitivities of marine organisms and ecosystems to CO2 induced ocean acidification (OA) requires well-controlled experimental setups and accurate carbonate system manipulations. Here we describe and analyse the chemical changes involved in the two basic approaches for carbonate chemistry manipulation, i.e. changing DIC at constant total alkalinity (TA) and changing TA at constant DIC. Furthermore, we briefly introduce several methods to experimentally manipulate DIC and TA. Finally, we examine responses obtained with both approaches using published results for the coccolithophore Emiliania huxleyi. We conclude that under most experimental conditions in the context of ocean acidification DIC and TA manipulations yield similar changes in all parameters of the carbonate system, which implies direct comparability of data obtained with the two basic approaches for CO2 perturbation.

Description: The influence of seawater carbon dioxide (CO2) concentration on the size distribution of suspended particles (2–60 μm) and on phytoplankton abundance was investigated during a mesocosm experiment at the large scale facility (LFS) in Bergen, Norway, in the frame of the Pelagic Ecosystem CO2 Enrichment study (PeECE II). In nine outdoor enclosures the partial pressure of CO2 in seawater was modified by an aeration system to simulate past (~190 μatm CO2), present (~370 μatm CO2) and future (~700 μatm CO2) CO2 conditions in triplicates. Due to the initial addition of inorganic nutrients, phytoplankton blooms developed in all mesocosms and were monitored over a period of 19 days. Seawater samples were collected daily for analysing the abundance of suspended particles and phytoplankton with the Coulter Counter and with Flow Cytometry, respectively. During the bloom period, the abundance of small particles (〈4 μm) significantly increased at past, and decreased at future CO2 levels. At that time, a direct relationship between the total-surface-to-total-volume ratio of suspended particles and DIC concentration was determined for all mesocosms. Significant changes with respect to the CO2 treatment were also observed in the phytoplankton community structure. While some populations such as diatoms seemed to be insensitive to the CO2 treatment, others like Micromonas spp. increased with CO2, or showed maximum abundance at present day CO2 (i.e. Emiliania huxleyi). The strongest response to CO2 was observed in the abundance of small autotrophic nano-plankton that strongly increased during the bloom in the past CO2 mesocosms. Together, changes in particle size distribution and phytoplankton community indicate a complex interplay between the ability of the cells to physiologically respond to changes in CO2 and size selection. Size of cells is of general importance for a variety of processes in marine systems such as diffusion-limited uptake of substrates, resource allocation, predator-prey interaction, and gravitational settling. The observed changes in particle size distribution are therefore discussed with respect to biogeochemical cycling and ecosystem functioning.

Description: Ocean alkalinity enhancement (OAE) is a proposed marine carbon dioxide removal (mCDR) approach that has the potential for large-scale uptake of significant amounts of atmospheric carbon dioxide (CO2). Removing anthropogenic legacy CO2 will be required to stabilise global surface temperatures below the 1.5–2 ∘C Paris Agreement target of 2015. In this chapter we describe the impacts of various OAE feedstocks on seawater carbonate chemistry, as well as pitfalls that need to be avoided during sampling, storage, and measurement of the four main carbonate chemistry parameters, i.e. dissolved inorganic carbon (DIC), total alkalinity (TA), pH, and CO2 fugacity (fCO2). Finally, we also discuss considerations in regard to calculating carbonate chemistry speciation from two measured parameters. Key findings are that (1) theoretical CO2 uptake potential (global mean of 0.84 mol of CO2 per mole of TA added) based on carbonate chemistry calculations is probably secondary in determining the oceanic region in which OAE would be best; (2) carbonate chemistry sampling is recommended to involve gentle pressure filtration to remove calcium carbonate (CaCO3) that might have been precipitated upon TA increase as it would otherwise interfere with a number of analyses; (3) samples for DIC and TA can be stabilised to avoid the risk of secondary CaCO3 precipitation during sample storage; and (4) some OAE feedstocks require additional adjustments to carbonate chemistry speciation calculations using available programs and routines, for instance if seawater magnesium or calcium concentrations are modified.

Description: Upwelling of nutrient-rich deep waters make eastern boundary upwelling systems (EBUSs), such as the Humboldt Current system, hot spots of marine productivity. Associated settling of organic matter to depth and consecutive aerobic decomposition results in large subsurface water volumes being oxygen depleted. Under these circumstances, organic matter remineralisation can continue via denitrification, which represents a major loss pathway for bioavailable nitrogen. Additionally, anaerobic ammonium oxidation can remove significant amounts of nitrogen in these areas. Here we assess the interplay of suboxic water upwelling and nitrogen cycling in a manipulative offshore mesocosm experiment. Measured denitrification rates in incubations with water from the oxygen-depleted bottom layer of the mesocosms (via 15N label incubations) mostly ranged between 5.5 and 20 nmol N2 L−1 h−1 (interquartile range), reaching up to 80 nmol N2 L−1 h−1. However, actual in situ rates in the mesocosms, estimated via Michaelis–Menten kinetic scaling, did most likely not exceed 0.2–4.2 nmol N2 L−1 h−1 (interquartile range) due to substrate limitation. In the surrounding Pacific, measured denitrification rates were similar, although indications of substrate limitation were detected only once. In contrast, anammox (anaerobic ammonium oxidation) made only a minor contribution to the overall nitrogen loss when encountered in both the mesocosms and the Pacific Ocean. This was potentially related to organic matter C / N stoichiometry and/or process-specific oxygen and hydrogen sulfide sensitivities. Over the first 38 d of the experiment, total nitrogen loss calculated from in situ rates of denitrification and anammox was comparable to estimates from a full nitrogen budget in the mesocosms and ranged between ∼ 1 and 5.5 µmol N L−1. This represents up to ∼  20 % of the initially bioavailable inorganic and organic nitrogen standing stocks. Interestingly, this loss is comparable to the total amount of particulate organic nitrogen that was exported into the sediment traps at the bottom of the mesocosms at about 20 m depth. Altogether, this suggests that a significant portion, if not the majority of nitrogen that could be exported to depth, is already lost, i.e. converted to N2 in a relatively shallow layer of the surface ocean, provided that there are oxygen-deficient conditions like those during coastal upwelling in our study. Published data for primary productivity and nitrogen loss in all EBUSs reinforce such conclusion.

Description: Oxygen minimum zones (OMZs) are characterized by enhanced carbon dioxide (CO2) levels and low pH and are being further acidified by uptake of anthropogenic atmospheric CO2. With ongoing intensification and expansion of OMZs due to global warming, carbonate chemistry conditions may become more variable and extreme, particularly in the eastern boundary upwelling systems. In austral summer (February–April) 2017, a large-scale mesocosm experiment was conducted in the coastal upwelling area off Callao (Peru) to investigate the impacts of ongoing ocean deoxygenation on biogeochemical processes, coinciding with a rare coastal El Niño event. Here we report on the temporal dynamics of carbonate chemistry in the mesocosms and surrounding Pacific waters over a continuous period of 50 d with high-temporal-resolution observations (every second day). The mesocosm experiment simulated an upwelling event in the mesocosms by addition of nitrogen (N)-deficient and CO2-enriched OMZ water. Surface water in the mesocosms was acidified by the OMZ water addition, with pHT lowered by 0.1–0.2 and pCO2 elevated to above 900 µatm. Thereafter, surface pCO2 quickly dropped to near or below the atmospheric level (405.22 µatm in 2017; Dlugokencky and Tans, 2021; NOAA/Global Monitoring Laboratory (GML)) mainly due to enhanced phytoplankton production with rapid CO2 consumption. Further observations revealed that the dominance of the dinoflagellate Akashiwo sanguinea and contamination of bird excrements played important roles in the dynamics of carbonate chemistry in the mesocosms. Compared to the simulated upwelling, natural upwelling events in the surrounding Pacific waters occurred more frequently with sea-to-air CO2 fluxes of 4.2–14.0 mmol C m−2 d−1. The positive CO2 fluxes indicated our site was a local CO2 source during our study, which may have been impacted by the coastal El Niño. However, our observations of dissolved inorganic carbon (DIC) drawdown in the mesocosms suggest that CO2 fluxes to the atmosphere can be largely dampened by biological processes. Overall, our study characterized carbonate chemistry in nearshore Pacific waters that are rarely sampled in such a temporal resolution and hence provided unique insights into the CO2 dynamics during a rare coastal El Niño event.