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Evidence for the shallow cycling of calcium carbonate in the global ocean is mounting, but the mechanisms driving the dissolution of thermodynamically stable polymorphs, like aragonite and calcite, in the surface ocean remain unconstrained. Here, we quantify how microbial metabolism creates acidic microenvironments in marine particles that enhance the local dissolution of calcite despite supersaturated conditions in bulk waters. A temporal decoupling of particle deoxygenation and acidification suggests that respiration-derived carbon dioxide is not the sole driver of the observed undersaturation. Rapid dissolution occurs in particles exhibiting bacterial growth, with rates exceeding abiotic dissolution at the same bulk saturation by more than an order of magnitude. We observe the highest particle-associated dissolution rates at intermediate settling velocities, indicating that a trade-off between elevated mass transfer due to settling and bacterial respiration governs the ensuing dissolution rates. Translation of our experiments to the water column suggests that microbially driven undersaturation in marine particles may dissolve sufficient calcite in the mesopelagic ocean to extend particle transit times by eliminating this vital ballast mineral, reducing the efficiency of organic carbon sequestration. 

Abstract Marine fish precipitate carbonates in their intestines that they subsequently excrete as part of an osmoregulatory strategy. While fish carbonates are proposed to be volumetrically significant to the global carbonate budget, no study has presented direct evidence of fish carbonates in the open ocean. Here we examine sediment trap material collected by the Oceanic Flux Program (OFP) in the North Atlantic and observe the episodic occurrence of enigmatic blue particles since 1992. The blue particles are comprised of calcite with unusually high magnesium content (up to 46 mol%) with distinctively depleted δ¹³C and enriched δ¹⁸O compared with calcite produced by common marine calcifiers. Based on the mineralogical, isotopic, and textural similarities between the blue particles and fish carbonates, we propose that the blue particles are produced by pelagic fish. Our data suggest that fish modify their intestinal fluids to create a concentrated, highly supersaturated,¹³C depleted solution capable of precipitating calcite with high magnesium content and low δ¹³C. Collectively, our data imply that fish carbonate production is an open‐ocean phenomenon, opening up the possibility that fish contribute to the production, dissolution, and export of carbonates globally. 

Abstract. Ocean alkalinity enhancement (OAE) is a carbon dioxide (CO2) removal approach that involves the addition of alkaline substances to the marine environment to increase seawater buffering capacity and allow it to absorb more atmospheric CO2. Increasing seawater alkalinity leads to an increase in the saturation state (Ω) with respect to several minerals, which may trigger mineral precipitation, consuming the added alkalinity and thus decreasing the overall efficiency of OAE. To explore mineral formation due to alkalinity addition, we present results from shipboard experiments in which an aqueous solution of NaOH was added to unfiltered seawater collected from the surface ocean in the Sargasso Sea. Alkalinity addition ranged from 500 to 2000 µmol kg−1, and the carbonate chemistry was monitored through time by measuring total alkalinity (TA) and dissolved inorganic carbon (DIC), which were used to calculate Ω. The amount of precipitate and its mineralogy were determined throughout the experiments. Mineral precipitation took place in all experiments over a timescale of hours to days. The dominant precipitate phase is aragonite with trace amounts of calcite and magnesium hydroxide (MgOH2, i.e., brucite). Aragonite crystallite size increases and its micro-strain decreases with time, consistent with Ostwald ripening. The precipitation rate (r) in our experiments and those of other OAE-related calcium carbonate precipitation studies correlate with the aragonite saturation state (ΩA), and the resulting fit of log10(r) = n × log10 (ΩA−1) + log10 (k) yields a reaction order n=2.15 ± 0.50 and a rate constant k=0.20 ± 0.10 µmol h−1. The reaction order is comparable to that derived from previous studies, but the rate constant is 1 order of magnitude lower, which we attribute to the fact that our experiments are unseeded compared with previous studies that used aragonite seeds which act as nuclei for precipitation. Observable precipitation was delayed by an induction period, the length of which is inversely correlated with the initial Ω. Mineral precipitation occurred in a runaway manner, decreasing TA to values below those of seawater prior to alkalinity addition. This study demonstrates that the highest risk of mineral precipitation is immediately following alkalinity addition and before dilution and CO2 uptake by seawater, both of which lower Ω. Aragonite precipitation will decrease OAE efficiency because aragonite is typically supersaturated in surface ocean waters. Thus, once formed, aragonite essentially permanently removes the precipitated alkalinity from the CO2 uptake process. Runaway mineral precipitation also means that mineral precipitation following OAE may not only decrease OAE efficiency at sequestering CO2 but could also render this approach counterproductive. As such, mineral precipitation should be avoided by keeping Ω below the threshold of precipitation and quantifying its consequences for OAE efficiency if it occurs. Lastly, in order to be able to quantitatively determine the impact of mineral precipitation during OAE, a mechanistic understanding of precipitation in the context of OAE must be developed. 

Abstract Coccolithophores fix organic carbon and produce calcite plates (coccoliths) that ballast organic matter and facilitate carbon export. Photosynthesis consumes carbon dioxide, while calcification produces it, raising questions about whether coccolithophores are a net sink or source of carbon. We characterized the physiology of calcified and noncalcified (“naked”) phenotypes ofEmiliania huxleyi(CCMP374) and investigated the relationship between calcification and photosynthesis across a gradient of light (25–2000 μmol photons m⁻² s⁻¹) spanning the euphotic zone. Growth and photophysiological parameters increased with light until reaching a mid‐light (150 μmol photons m⁻² s⁻¹) maximum for both phenotypes. Calcified cells were characterized by enhanced photophysiology and less photoinhibition. Further, enhanced bicarbonate transport in calcified cells led to higher rates of particulate organic carbon fixation and growth compared to naked cells at mid‐light to high light (150–2000 μmol photons m⁻² s⁻¹). Coccolith production was similarly high at mid and high light, but the rate of coccolith shedding was >3‐fold lower at high‐light (1.2 vs. 0.35 coccoliths cell⁻¹ h⁻¹). The cellular mechanims(s) of this differential shedding remain unknown and underly light‐related controls on coccosphere maintenance. Our data suggest coccoliths shade cells at high light and that enhanced bicarbonate transport associated with calcification increases internal carbon supplies available for organic carbon fixation. 

Abstract The cycling of marine particulate matter is critical for sequestering carbon in the deep ocean and in marine sediments. Biogenic minerals such as calcium carbonate (CaCO₃) and opal add density to more buoyant organic material, facilitating particle sinking and export. Here, we compile and analyze a global data set of particulate organic carbon (POC), particulate inorganic carbon (PIC, or CaCO₃), and biogenic silica (bSi, or opal) concentrations collected using large volume pumps (LVPs). We analyze the distribution of all three biogenic phases in the small (1–53 μm) and large (>53 μm) size classes. Over the entire water column 76% of POC exists in the small size fraction. Similarly, the small size class contains 82% of PIC, indicating the importance of small‐sized coccolithophores to the PIC budget of the ocean. In contrast, 50% of bSi exists in the large size fraction, reflecting the larger size of diatoms and radiolarians compared with coccolithophores. We use PIC:POC and bSi:POC ratios in the upper ocean to document a consistent signal of shallow mineral dissolution, likely linked to biologically mediated processes. Sediment trap PIC:POC and bSi:POC are elevated with respect to LVP samples and increase strongly with depth, indicating the concentration of mineral phases and/or a deficit of POC in large sinking particles. We suggest that future sampling campaigns pair LVPs with sediment traps to capture the full particulate field, especially the large aggregates that contribute to mineral‐rich deep ocean fluxes, and may be missed by LVPs. 

Abstract Planktonic calcifying organisms play a key role in regulating ocean carbonate chemistry and atmospheric CO 2 . Surprisingly, references to the absolute and relative contribution of these organisms to calcium carbonate production are lacking. Here we report quantification of pelagic calcium carbonate production in the North Pacific, providing new insights on the contribution of the three main planktonic calcifying groups. Our results show that coccolithophores dominate the living calcium carbonate (CaCO 3 ) standing stock, with coccolithophore calcite comprising ~90% of total CaCO 3 production, and pteropods and foraminifera playing a secondary role. We show that pelagic CaCO 3 production is higher than the sinking flux of CaCO 3 at 150 and 200 m at ocean stations ALOHA and PAPA, implying that a large portion of pelagic calcium carbonate is remineralised within the photic zone; this extensive shallow dissolution explains the apparent discrepancy between previous estimates of CaCO 3 production derived from satellite observations/biogeochemical modeling versus estimates from shallow sediment traps. We suggest future changes in the CaCO 3 cycle and its impact on atmospheric CO 2 will largely depend on how the poorly-understood processes that determine whether CaCO 3 is remineralised in the photic zone or exported to depth respond to anthropogenic warming and acidification. 

Identifying mechanisms driving the substantial dissolution of biogenic CaCO₃(60 to 80%) in surface and mesopelagic waters of the global ocean is critical for constraining the surface ocean’s alkalinity and inorganic carbon budgets. We examine microzooplankton grazing on coccolithophores, photosynthetic calcifying algae responsible for a majority of open-ocean CaCO₃production, as a mechanism driving shallow dissolution. We show that microzooplankton grazing dissolves 92 ± 7% of ingested coccolith calcite, which may explain 50 to 100% of the observed CaCO₃dissolution in supersaturated surface waters. Microzooplankton grazing on coccolithophores is thus a substantial, previously unrecognized biological mechanism affecting the ballasting of organic carbon to deeper waters, the ecology and fitness of microzooplankton themselves due to buffering of food vacuole pH, and ultimately the continued ability of the surface ocean to take up atmospheric carbon dioxide. 

Abstract. Barium is widely used as a proxy for dissolved silicon and particulateorganic carbon fluxes in seawater. However, these proxy applications arelimited by insufficient knowledge of the dissolved distribution of Ba([Ba]). For example, there is significant spatial variability in thebarium–silicon relationship, and ocean chemistry may influence sedimentaryBa preservation. To help address these issues, we developed 4095 models forpredicting [Ba] using Gaussian process regression machine learning. Thesemodels were trained to predict [Ba] from standard oceanographic observationsusing GEOTRACES data from the Arctic, Atlantic, Pacific, and Southernoceans. Trained models were then validated by comparing predictions againstwithheld [Ba] data from the Indian Ocean. We find that a model trained usingdepth, temperature, and salinity, as well as dissolved dioxygen, phosphate,nitrate, and silicate, can accurately predict [Ba] in the Indian Ocean with amean absolute percentage deviation of 6.0 %. We use this model tosimulate [Ba] on a global basis using these same seven predictors in theWorld Ocean Atlas. The resulting [Ba] distribution constrains the Ba budgetof the ocean to 122(±7) × 1012 mol and revealsoceanographically consistent variability in the barium–silicon relationship. We then calculate the saturation state of seawater with respect to barite. This calculation reveals systematic spatial and vertical variations in marine barite saturation and shows that the ocean below 1000 m is at equilibrium with respect tobarite. We describe a number of possible applications for our model outputs, ranging from use in mechanistic biogeochemical models to paleoproxy calibration. Ourapproach demonstrates the utility of machine learning in accurately simulatingthe distributions of tracers in the sea and provides a framework that couldbe extended to other trace elements. Our model, the data used in training and validation, and global outputs are available in Horner and Mete (2023, https://doi.org/10.26008/1912/bco-dmo.885506.2).