Rate and Apparent Quantum Yield of Photodissolution

We quantified rates of photochemical dissolution (photodissolution) of organic carbon in coastal Louisiana suspended sediments, conducting experiments under well-defined conditions of irradiance and temperature. Optical properties of the suspended sediments were characterized and used in a radiative transfer model to compute irradiances within turbid suspensions. Photodissolution rate increased with temperature (T), with activation energy of 32 ± 7 kJ mol−1, which implicates indirect (non-photochemical) steps in the net reaction. In most samples, dissolved organic carbon (DOC) concentration increased approximately linearly with time over the first 4 h of irradiation under broadband simulated sunlight, after higher rates in the initial hour of irradiation. Four-hour rates ranged from 2.3 µmol DOC m−3 s−1 to 3.2 µmol DOC m−3 s−1, but showed no relation to sample origin within the study area, organic carbon or reducible iron content, or mass-specific absorption coefficient. First-hour rates were higher—from 3.5 µmol DOC m−3 s−1 to 7.8 µmol DOC m−3 s−1—and correlated well with sediment reducible iron (itself often associated with organic matter). The spectral apparent quantum yield (AQY) for photodissolution was computed by fitting DOC photoproduction rates under different spectral irradiance distributions to corresponding rates of light absorption by particles. The photodissolution AQY magnitude is similar to most published dissolved-phase AQY spectra for dissolved inorganic carbon photoproduction, which suggests that in turbid coastal waters where particles dominate light absorption, DOC photoproduction from particles exceeds photooxidation of DOC

Observations of Carbon Export by Small Sinking Particles in the Upper Mesopelagic

Carbon and nutrients are transported out of the surface ocean and sequestered at depth by sinking particles. Sinking particle sizes span many orders of magnitude and the relative influence of small particles on carbon export compared to large particles has not been resolved. To determine the influence of particle size on carbon export, the flux of both small (11–64 μm) and large (\u3e 64 μm) particles in the upper mesopelagic was examined during 5 cruises of the Bermuda Atlantic Time Series (BATS) in the Sargasso Sea using neutrally buoyant sediment traps mounted with tubes containing polyacrylamide gel layers and tubes containing a poisoned brine layer. Particles were also collected in surface-tethered, free-floating traps at higher carbon flux locations in the tropical and subtropical South Atlantic Ocean. Particle sizes spanning three orders of magnitude were resolved in gel samples, included sinking particles as small as 11 μm. At BATS, the number flux of small particles tended to increase with depth, whereas the number flux of large particles tended to decrease with depth. The carbon content of different sized particles could not be modeled by a single set of parameters because the particle composition varied across locations and over time. The modeled carbon flux by small particles at BATS, including all samples and depths, was 39 ± 20% of the modeled total carbon flux, and the percentage increased with depth in 4 out of the 5 months sampled. These results indicate that small particles (\u3c 64 μm) are actively settling in the water column and are an important contributor to carbon flux throughout the mesopelagic. Observations and models that overlook these particles will underestimate the vertical flux of organic matter in the ocean

Autonomous, High-resolution Observations of Particle Flux in the Oligotrophic Ocean

Observational gaps limit our understanding of particle flux attenuation through the upper mesopelagic because available measurements (sediment traps and radiochemical tracers) have limited temporal resolution, are labor-intensive, and require ship support. Here, we conceptually evaluate an autonomous, optical proxy-based method for high-resolution observations of particle flux. We present four continuous records of particle flux collected with autonomous profiling floats in the western Sargasso Sea and the subtropical North Pacific, as well as one shorter record of depth-resolved particle flux near the Bermuda Atlantic Time-series Study (BATS) and Oceanic Flux Program (OFP) sites. These observations illustrate strong variability in particle flux over very short (~1-day) timescales, but at longer timescales they reflect patterns of variability previously recorded during sediment trap time series. While particle flux attenuation at BATS/OFP agreed with the canonical power-law model when observations were averaged over a month, flux attenuation was highly variable on timescales of 1–3 days. Particle fluxes at different depths were decoupled from one another and from particle concentrations and chlorophyll fluorescence in the immediately overlying surface water, consistent with horizontal advection of settling particles. We finally present an approach for calibrating this optical proxy in units of carbon flux, discuss in detail the related, inherent physical and optical assumptions, and look forward toward the requirements for the quantitative application of this method in highly time-resolved studies of particle export and flux attenuation

Carbon Flux from Bio-optical Profiling Floats: Calibrating Transmissometers for Use as Optical Sediment Traps

Our mechanistic understanding of the processes controlling the ocean\u27s biological pump is limited, in part, by our lack of observational data at appropriate timescales. The “optical sediment trap” (OST) technique utilizes a transmissometer on a quasi-Lagrangian platform to collect sedimenting particles. This method could help fill the observational gap by providing autonomous measurements of particulate carbon (PC) flux in the upper mesopelagic ocean at high spatiotemporal resolution. Here, we used a combination of field measurements and laboratory experiments to test hydrodynamic and zooplankton-swimmer effects on the OST method, and we quantitatively calibrated this method against PC flux measured directly in same-platform, neutrally buoyant sediment traps (NBSTs) during 5 monthly cruises at the Bermuda Atlantic Time-series Study (BATS) site. We found a well-correlated, positive relationship (R2 = 0.66, n = 15) between the OST proxy, and the PC flux measured directly using NBSTs. Laboratory tests showed that scattering of light from multiple particles between the source and detector was unlikely to affect OST proxy results. We found that the carbon-specific attenuance of sinking particles was larger than literature values for smaller, suspended particles in the ocean, and consistent with variable carbon:size relationships reported in the literature for sinking particles. We also found evidence for variability in PC flux at high spatiotemporal resolution. Our results are consistent with the literature on particle carbon content and optical properties in the ocean, and support more widespread use of the OST proxy, with proper site-specific and platform-specific calibration, to better understand variability in the ocean biological pump

Role of Iron and Organic Carbon in Mass-specific Light Absorption by Particulate Matter from Louisiana Coastal Waters

We investigated the influences of organic content and mineralogical composition on light absorption by mostly mineral suspended particles in aquatic and coastal marine systems. Mass-specific absorption spectra of suspended particles and surface sediments from coastal Louisiana and the lower Mississippi and Atchafalaya rivers were measured with a centered sample-mount integrating sphere and analyzed in conjunction with organic carbon (OC), hydrochloric acid– (HCl-) extractable iron, and dithionite-extractable iron contents. Compositions and absorption properties were comparable to published values for similar particles. Dithionite-extractable iron was strongly correlated with absorption at ultraviolet (UV) and blue wavelengths, while OC and HCl-extractable iron were weakly but positively correlated. Oxidative removal of OC from sediments caused small and variable changes in absorption, while dithionite extraction of iron oxides strongly reduced absorption. Shoulders in the absorption spectra corresponded to absorption bands of iron oxide minerals, and their intensities were well correlated to dithionite-extractable iron contents of the samples. These findings support a primary role for iron oxide and hydroxide minerals in the mass-specific absorption of mostly inorganic particles from the terrestrially influenced coast of Louisiana. Riverine particles had higher dithionite-extractable iron contents and iron oxide–specific absorption features than did marine particles, consistent with current knowledge regarding differential transport of particulate iron oxides and hydroxides through estuarine salinity gradients and reductive alteration of these oxide phases on the Louisiana shelf. The quantifiable dependence of UV absorption features on iron oxide content suggests that, under certain conditions, in situ hyperspectral absorption measurements could be designed to monitor water-column iron mineral transport and transformation

Direct Observations of Biological Carbon Export From Profiling Floats in the Subtropical North Atlantic

The complex interplay of biological and physical mechanisms comprising the ocean\u27s biological carbon pump has not been well characterized to date, due to the difficulty of observing these mechanisms in situ at adequate spatial and temporal resolution. An annual time series is presented of direct measurements of export production and particle properties collected using optical sediment trap‐equipped profiling floats cycling every 1.5–2.5 days. The observations indicate strong variability in particle export and bio‐optical properties, influenced by the spring bloom, mesoscale eddy activity, and the mixed layer pump. Temporal and vertical decoupling of fluxes at depths ranging from 150 to 1,000 m was also observed, and remineralization length scales were more variable than predicted by temperature‐ and oxygen‐based models. Net primary production was computed from float observations using a modification of the Carbon‐based Productivity Model and used to estimate export and export (e‐) ratios, which were compared to predictions of literature export models. Mechanistic models explicitly incorporating ecosystem processes and their depth dependence may perform better at reproducing regional observations collected at high temporal resolution