skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: The carbonic anhydrase activity of sinking and suspended particles in the North Pacific Ocean
Abstract The enzyme carbonic anhydrase (CA) is crucial to many physiological processes involvingCO2, from photosynthesis and respiration, to calcification andCaCO3dissolution. We present new measurements of CA activity along a North Pacific transect, on samples from in situ pumps, sediment traps, discreet plankton samples from the ship's underway seawater line, plankton tows, and surface sediment samples from multicores. CA activity is highest in the surface ocean and decreases with depth, both in suspended and sinking particles. Subpolar gyre surface particles exhibit 10× higher CA activity per liter of seawater compared to subtropical gyre surface particles. Activity persists to 4700 m in the subpolar gyre, but only to 1000 m in the subtropics. All sinking CA activity normalized to particulate organic carbon (POC) follows a single relationship (CA/POC = 1.9 ± 0.2 × 10−7mol mol−1). This relationship is consistent with CA/POC values in subpolar plankton tow material, suspended particles, and core top sediments. We hypothesize that most subpolar CA activity is associated with rapidly sinking diatom blooms, consistent with a large mat of diatomaceous material identified on the seafloor. Compared to the basin‐wide sinking CA/POC relationship, a lower subtropical CA/POC suggests that the inventory of subtropical biomass is different in composition from exported material. Pteropods also demonstrate substantial CA activity. Scaled to the volume within pteropod shells, first‐orderCO2hydration rate constants are elevated ≥ 1000× above background. This kinetic enhancement is large enough to catalyze carbonate dissolution within microenvironments, providing observational evidence for CA‐catalyzed, respiration‐drivenCaCO3dissolution in the shallow North Pacific.  more » « less
Award ID(s):
1834475
PAR ID:
10458723
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Limnology and Oceanography
Volume:
65
Issue:
3
ISSN:
0024-3590
Page Range / eLocation ID:
p. 637-651
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. Abstract The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situ coccolith and foraminiferal calcite dissolution rates. We combine these rates with solid phase fluxes, dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean. The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution rates of all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods) are too slow to explain the patterns of both CaCO3sinking flux and alkalinity regeneration in the North Pacific. Using a combination of dissolved and solid‐phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3dissolution with a combination of ambient saturation state and oxygen consumption simultaneously explains solid‐phase CaCO3flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. We do not need to invoke the presence of carbonate phases with higher solubilities. Instead, biomineralization and metabolic processes intimately associate the acid (CO2) and the base (CaCO3) in the same particles, driving the coupled shallow remineralization of organic carbon and CaCO3. The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration within degrading particle aggregates. The coupling of these cycles acts as a major filter on the export of both organic and inorganic carbon to the deep ocean. 
    more » « less
  3. Abstract Dinitrogen (N2) fixation supports marine life through the supply of reactive nitrogen. Recent studies suggest that particle-associated non-cyanobacterial diazotrophs (NCDs) could contribute significantly to N2fixation contrary to the paradigm of diazotrophy as primarily driven by cyanobacterial genera. We examine the community composition of NCDs associated with suspended, slow, and fast-sinking particles in the North Pacific Subtropical Gyre. Suspended and slow-sinking particles showed a higher abundance of cyanobacterial diazotrophs than fast-sinking particles, while fast-sinking particles showed a higher diversity of NCDs includingMarinobacter,OceanobacterandPseudomonas. Using single-cell mass spectrometry we find that Gammaproteobacteria N2fixation rates were higher on suspended and slow-sinking particles (up to 67 ± 48.54 fmol N cell⁻¹ d⁻¹), while putative NCDs’ rates were highest on fast-sinking particles (121 ± 22.02 fmol N cell⁻¹ d⁻¹). These rates are comparable to previous diazotrophic cyanobacteria observations, suggesting that particle-associated NCDs may be important contributors to pelagic N2fixation. 
    more » « less
  4. null (Ed.)
    The dissolution of CaCO 3 minerals in the ocean is a fundamental part of the marine alkalinity and carbon cycles. While there have been decades of work aimed at deriving the relationship between dissolution rate and mineral saturation state (a so-called rate law), no real consensus has been reached. There are disagreements between laboratory- and field-based studies and differences in rates for inorganic and biogenic materials. Rates based on measurements on suspended particles do not always agree with rates inferred from measurements made near the sediment–water interface of the actual ocean. By contrast, the freshwater dissolution rate of calcite has been well described by bulk rate measurements from a number of different laboratories, fit by basic kinetic theory, and well studied by atomic force microscopy and vertical scanning interferometry to document the processes at the atomic scale. In this review, we try to better unify our understanding of carbonate dissolution in the ocean via a relatively new, highly sensitive method we have developed combined with a theoretical framework guided by the success of the freshwater studies. We show that empirical curve fits of seawater data as a function of saturation state do not agree, largely because the curvature is itself a function of the thermodynamics. Instead, we show that models that consider both surface energetic theory and the complicated speciation of seawater and calcite surfaces in seawater are able to explain most of the most recent data.This new framework can also explain features of the historical data that have not been previously explained. The existence of a kink in the relationship between rate and saturation state, reflecting a change in dissolution mechanism, may be playing an important role in accelerating CaCO 3 dissolution in key sedimentary environments. 
    more » « less
  5. Planktic foraminifera test iodine to calcium ratios represent an emerging proxy method to assess subsurface seawater oxygenation states. Several core-top studies show lower planktic foraminifera I/Ca in locations with oxygen depleted subsurface waters compared to well oxygenated environments. The reasoning behind this trend is that only the oxidized species of iodine, iodate, is incorporated in foraminiferal calcite. The I/Ca of foraminiferal calcite is thought to reflect iodate contents in seawater. To test this hypothesis, we compare planktic foraminifera I/Ca ratios, obtained from plankton tows, with published and new seawater iodate concentrations from 1) the Eastern North Pacific with extensive oxygen depletion, 2) the Benguela Current System with moderately depleted oxygen concentrations, and 3) the well oxygenated North and South Atlantic. We find the lowest I/Ca ratios (0.07 µmol/mol) in planktic foraminifera retrieved from the Eastern North Pacific, and higher values for samples (up to 0.72 µmol/mol) obtained from the Benguela Current System and North and South Atlantic. The I/Ca ratios of plankton tow foraminifera from environments with well oxygenated subsurface waters, however, are an order of magnitude lower compared to core-tops from similarly well-oxygenated regions. This would suggest that planktic foraminifera gain iodine post-mortem, either when sinking through the water column, or during burial. 
    more » « less