Luke J. Coletti

Long-Term Nitrate Measurements in the Ocean Using the in situ Ultraviolet Spectrophotometer: Sensor Integration into the APEX Profiling Float

AbstractReagent-free optical nitrate sensors [in situ ultraviolet spectrophotometer (ISUS)] can be used to detect nitrate throughout most of the ocean. Although the sensor is a relatively high-power device when operated continuously (7.5 W typical), the instrument can be operated in a low-power mode, where individual nitrate measurements require only a few seconds of instrument time and the system consumes only 45 J of energy per nitrate measurement. Operation in this mode has enabled the integration of ISUS sensors with Teledyne Webb Researchs Autonomous Profiling Explorer (APEX) profiling floats with a capability to operate to 2000 m. The energy consumed with each nitrate measurement is low enough to allow 60 nitrate observations on each vertical profile to 1000 m. Vertical resolution varies from 5 m near the surface to 50 m near 1000 m, and every 100 m below that. Primary lithium batteries allow more than 300 vertical profiles from a depth of 1000 m to be made, which corresponds to an endurance near f...

Nitrate Sources and Sinks in Elkhorn Slough, California: Results from Long-term Continuous in situ Nitrate Analyzers

Nitrate and water quality parameters (temperature, salinity, dissolved oxygen, turbidity, and depth) were measured continuously with in situ NO3 analyzers and water quality sondes at two sites in Elkhorn Slough in Central California. The Main Channel site near the mouth of Elkhorn Slough was sampled from February to September 2001. Azevedo Pond, a shallow tidal pond bordering agricultural fields further inland, was sampled from December 1999 to July 2001. Nitrate concentrations were recorded hourly while salinity, temperature, depth, oxygen, and turbidity were recorded every 30 min. Nitrate concentrations at the Main Channel site ranged from 5 to 65 μM. The propagation of an internal wave carrying water from ≈100 m depth up the Monterey Submarine Canyon and into the lower section of Elkhorn Slough on every rising tide was a major source of nitrate, accounting for 80–90% of the nitrogen load during the dry summer period. Nitrate concentrations in Azevedo Pond ranged from 0–20 μM during the dry summer months. Nitrate in Azevedo Pond increased to over 450 μM during a heavy winter precipitation event, and interannual variability driven by differences in precipitation was observed. At both sites, tidal cycling was the dominant forcing, often changing nitrate concentrations by 5-fold or more within a few hours. Water volume flux estimates were combined with observed nitrate concentrations to obtain nitrate fluxes. Nitrate flux calculations indicated a loss of 4 mmol NO3 m−2 d−1 for the entire Elkhorn Slough and 1 mmol NO3 m−2 d−1 at Azevedo Pond. These results suggested that the waters of Elkhorn Slough were not a major source of nitrate to Monterey Bay but actually a nitrate sink during the dry season. The limited winter data at the Main Channel site suggest that nitrate was exported from Elkhorn Slough during the wet season. Export of ammonium or dissolved organic nitrogen, which we did not monitor, may balance some or all of the NO3 flux.

Deep-Sea DuraFET: A Pressure Tolerant pH Sensor Designed for Global Sensor Networks

Increasing atmospheric carbon dioxide is driving a long-term decrease in ocean pH which is superimposed on daily to seasonal variability. These changes impact ecosystem processes, and they serve as a record of ecosystem metabolism. However, the temporal variability in pH is observed at only a few locations in the ocean because a ship is required to support pH observations of sufficient precision and accuracy. This paper describes a pressure tolerant Ion Sensitive Field Effect Transistor pH sensor that is based on the Honeywell Durafet ISFET die. When combined with a AgCl pseudoreference sensor that is immersed directly in seawater, the system is capable of operating for years at a time on platforms that cycle from depths of several km to the surface. The paper also describes the calibration scheme developed to allow calibrated pH measurements to be derived from the activity of HCl reported by the sensor system over the range of ocean pressure and temperature. Deployments on vertical profiling platforms enable self-calibration in deep waters where pH values are stable. Measurements with the sensor indicate that it is capable of reporting pH with an accuracy of 0.01 or better on the total proton scale and a precision over multiyear periods of 0.005. This system enables a global ocean observing system for ocean pH.

Biogeochemical sensor performance in the SOCCOM profiling float array

The Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) program has begun deploying a large array of biogeochemical sensors on profiling floats in the Southern Ocean. As of February 2016, 86 floats have been deployed. Here the focus is on 56 floats with quality controlled and adjusted data that have been in the water at least 6 months. The floats carry oxygen, nitrate, pH, chlorophyll fluorescence, and optical backscatter sensors. The raw data generated by these sensors can suffer from inaccurate initial calibrations and from sensor drift over time. Procedures to correct the data are defined. The initial accuracy of the adjusted concentrations is assessed by comparing the corrected data to laboratory measurements made on samples collected by a hydrographic cast with a rosette sampler at the float deployment station. The long-term accuracy of the corrected data is compared to the GLODAPv2 data set whenever a float made a profile within 20 km of a GLODAPv2 station. Based on these assessments, the fleet average oxygen data are accurate to 1±1%, nitrate to within 0.5±0.5 µmol kg−1, and pH to 0.005±0.01, where the error limit is 1 standard deviation of the fleet data. The bio-optical measurements of chlorophyll fluorescence and optical backscatter are used to estimate chlorophyll a and particulate organic carbon concentration. The particulate organic carbon concentrations inferred from optical backscatter appear accurate to with 35 mg C m−3 or 20%, whichever is larger. Factors affecting the accuracy of the estimated chlorophyll a concentrations are evaluated.

Net community production at Ocean Station Papa observed with nitrate and oxygen sensors on profiling floats

Six profiling floats equipped with nitrate and oxygen sensors were deployed at Ocean Station P in the Gulf of Alaska. The resulting six calendar years and 10 float years of nitrate and oxygen data were used to determine an average annual cycle for net community production (NCP) in the top 35 m of the water column. NCP became positive in February as soon as the mixing activity in the surface layer began to weaken, but nearly 3 months before the traditionally defined mixed layer began to shoal from its winter time maximum. NCP displayed two maxima, one toward the end of May and another in August with a summertime minimum in June corresponding to the historical peak in mesozooplankton biomass. The average annual NCP was determined to be 1.5 ± 0.6 mol C m−2 yr−1 using nitrate and 1.5 ± 0.7 mol C m−2 yr−1 using oxygen. The results from oxygen data proved to be quite sensitive to the gas exchange model used as well as the accuracy of the oxygen measurement. Gas exchange models optimized for carbon dioxide flux generally ignore transport due to gas exchange through the injection of bubbles, and these models yield NCP values that are two to three time higher than the nitrate-based estimates. If nitrate and oxygen NCP rates are assumed to be related by the Redfield model, we show that the oxygen gas exchange model can be optimized by tuning the exchange terms to reproduce the nitrate NCP annual cycle.