A 50-Year Journey from Phosphate to Autonomous Underwater Vehicles.

This narrative is a personal account of my evolution as a student of phytoplankton and the ocean. Initially I focused on phytoplankton nutrient physiology and uptake, later switching to photosynthetic physiology. Better models of photosynthesis naturally require a better understanding of spectral underwater light fields and absorption coefficients, which precipitated my involvement in the nascent field of bio-optical oceanography. Establishment of the now 34-year-old summer graduate course in ocean optics, which continues to attract students from around the globe, is a legacy of my jumping into optics. The importance of social interactions in advancing science cannot be underestimated; a prime example is how a TGIF gathering led to my immersion in the world of autonomous underwater vehicles for the past two decades of my career. Working with people who you like and respect is also critical; I believe collegial friendship played a major role in the great success of the 2008 North Atlantic Bloom Experiment.

A multi-method autonomous assessment of primary productivity and export efficiency in the springtime North Atlantic.

Fixation of organic carbon by phytoplankton is the foundation of nearly all open-ocean ecosystems and a critical part of the global carbon cycle. But quantification and validation of ocean primary productivity at large scale remains a major challenge, due to limited coverage of ship-based measurements and the difficulty of validating diverse measurement techniques. Accurate primary productivity measurements from autonomous platforms would be highly desirable, due to much greater potential coverage. In pursuit of this goal we estimate gross primary productivity over two months in the springtime North Atlantic from an autonomous Lagrangian float using diel cycles of particulate organic carbon derived from optical beam attenuation. We test method precision and accuracy by comparison against entirely independent estimates from a locally parameterized model based on chlorophyll a and light measurements from the same float. During nutrient replete conditions (80% of the study period), we obtain strong relative agreement between the independent methods across an order of magnitude of productivities (r2=0.97), with slight under-estimation by the diel cycles method (-19±5 %). At the end of the diatom bloom, this relative difference increases to -58 % for a six-day period, likely a response to SiO4 limitation, which is not included in the model. In addition, we estimate gross oxygen productivity from O2 diel cycles and find strong correlation with diel cycles-based gross primary productivity over the entire deployment, providing further qualitative support to both methods. Finally, simultaneous estimates of net community productivity, carbon export and particle size suggest that bloom growth is halted by a combination of reduced productivity due to SiO4 limitation and increased export efficiency due to rapid aggregation. After the diatom bloom, high chlorophyll a normalized productivity indicates that low net growth during this period is due to increased heterotrophic respiration and not nutrient limitation. These findings represent a significant advance in the accuracy and completeness of upper ocean carbon cycle measurements from an autonomous platform.

Eddy-driven subduction exports particulate organic carbon from the spring bloom.

The export of particulate organic carbon (POC) from the surface ocean to depth is traditionally ascribed to sinking. Here, we show that a dynamic eddying flow field subducts surface water with high concentrations of nonsinking POC. Autonomous observations made by gliders during the North Atlantic spring bloom reveal anomalous features at depths of 100 to 350 meters with elevated POC, chlorophyll, oxygen, and temperature-salinity characteristics of surface water. High-resolution modeling reveals that during the spring transition, intrusions of POC-rich surface water descend as coherent, 1- to 10-kilometer-scale filamentous features, often along the perimeter of eddies. Such a submesoscale eddy-driven flux of POC is unresolved in global carbon cycle models but can contribute as much as half of the total springtime export of POC from the highly productive subpolar oceans.

Method for estimating mean particle size from high-frequency fluctuations in beam attenuation or scattering measurements.

The ability to estimate mean particle size using simple, low-power optical instruments promises to greatly expand coverage of particle size measurements in the ocean and advance understanding of myriad processes from sediment transport to biological carbon sequestration. Here we present a method for estimating the mean diameter of particles in suspension from high-resolution time series of simple optical measurements, such as beam attenuation or optical backscattering. Validation results from a laboratory clay aggregation experiment show a good fit with independent mean particle diameter estimates in the 10-80 µm diameter range, with relative biases of 17%-38% and relative root mean square errors of 10%-24%. In the 80-200 µm range, quantitative validation data were not available, but our mean diameter estimates correlated strongly with particle settling rates.

Eddy-driven stratification initiates North Atlantic spring phytoplankton blooms.

Springtime phytoplankton blooms photosynthetically fix carbon and export it from the surface ocean at globally important rates. These blooms are triggered by increased light exposure of the phytoplankton due to both seasonal light increase and the development of a near-surface vertical density gradient (stratification) that inhibits vertical mixing of the phytoplankton. Classically and in current climate models, that stratification is ascribed to a springtime warming of the sea surface. Here, using observations from the subpolar North Atlantic and a three-dimensional biophysical model, we show that the initial stratification and resulting bloom are instead caused by eddy-driven slumping of the basin-scale north-south density gradient, resulting in a patchy bloom beginning 20 to 30 days earlier than would occur by warming.

Fate of chiral and achiral organochlorine pesticides in the North Atlantic Bloom Experiment.

Organochlorine pesticides (OCPs) were measured in the surface seawater and lower atmosphere during the North Atlantic Bloom Experiment in the spring 2008 from samples collected on the R/V Knorr. The gaseous concentration profiles resulted from both long-range transport (LRT) from the Arctic by polar easterlies and local biogeochemical processes. Relatively constant α/γ-hexachlorocyclohexane (HCH) ratios and enantiomer fractions of α-HCH indicated that a single water mass was sampled throughout the cruise. Changes in dissolved phase concentrations were dominated by bloom processes (air-water exchange, partitioning to organic particles, and subsequent sinking) rather than LRT. α-HCH and dissolved phase trans-chlordanes showed depletion of (+) enantiomer, whereas depletion of the (-) enantiomer was observed for heptachlor exo-epoxide (HEPX) and cis-chlordanes. Fugacity ratio calculations suggest that hexachlorobenzene (HCB) and γ-HCH were depositing from air to water whereas heavier OCPs (chlordanes, HEPX) were evaporating. Dissolved phase concentrations did not decrease with time during the three-week bloom period; neither were lipophilic OCPs drawn down from air to water as previous studies hypothesized. Comparison with Arctic measurements suggested that the Arctic returned higher concentrations of α-HCH and HCB through both the atmospheric (polar easterlies) as well as oceanic transport (East Greenland Current) to the lower latitudes.

An immunoprobe to measure Rubisco concentrations and maximal photosynthetic rates of individual phytoplankton cells.

The cross-reactivity of an immunological probe to the key photosynthetic enzyme Rubisco (ribulose-1,5-bisphosphate carboxylase/oxygenase) was characterized as part of a larger effort to determine maximal photosynthetic rates of individual phytoplankton cells. Polyclonal antiserum was produced against purified Rubisco from the marine diatom Chaetoceros gracilis. The results of western immunoblotting demonstrated that the antiserum reacted positively with Rubisco from 38 species of algae and higher plants and failed to react with only three species of dinoflagellates and one prochlorophyte species. However, the binding affinity or the strength of the cross-reaction for the polyclonal antiserum with purified Rubisco varied among species. The antiserum was then affinity purified against spinach Rubisco and its binding affinity for purified Rubisco determined by ELISA. Two taxonomic groupings resulted: one with high-binding affinity (these species included chrysophytes, bacillariophytes, prymnesiophytes, and chlorophytes) and the other with low-binding affinity (dinophytes and cyanophytes). Rubisco concentration per cell and light-saturated rates of photosynthesis were highly correlated for cultures of the diatom Thalassiosira weissflogii. These results indicate that affinity-purified antiserum can be rigorously characterized for use in quantifying Rubisco concentration and for assessing the maximal photosynthetic potential of individual phytoplankton cells.