In situ spectrophotometric measurement of dissolved inorganic carbon in seawater.

Autonomous in situ sensors are needed to document the effects of today's rapid ocean uptake of atmospheric carbon dioxide (e.g., ocean acidification). General environmental conditions (e.g., biofouling, turbidity) and carbon-specific conditions (e.g., wide diel variations) present significant challenges to acquiring long-term measurements of dissolved inorganic carbon (DIC) with satisfactory accuracy and resolution. SEAS-DIC is a new in situ instrument designed to provide calibrated, high-frequency, long-term measurements of DIC in marine and fresh waters. Sample water is first acidified to convert all DIC to carbon dioxide (CO2). The sample and a known reagent solution are then equilibrated across a gas-permeable membrane. Spectrophotometric measurement of reagent pH can thereby determine the sample DIC over a wide dynamic range, with inherent calibration provided by the pH indicator's molecular characteristics. Field trials indicate that SEAS-DIC performs well in biofouling and turbid waters, with a DIC accuracy and precision of ∼2 µmol kg(-1) and a measurement rate of approximately once per minute. The acidic reagent protects the sensor cell from biofouling, and the gas-permeable membrane excludes particulates from the optical path. This instrument, the first spectrophotometric system capable of automated in situ DIC measurements, positions DIC to become a key parameter for in situ CO2-system characterizations.

Evaluation of reagentless pH modification for in situ ocean analysis: determination of dissolved inorganic carbon using mass spectrometry.

RATIONALE: In situ analytical techniques that require the storage and delivery of reagents (e.g., acidic or basic solutions) have inherent durability limitations. The reagentless electrolytic technique for pH modification presented here was developed primarily to ease and to extend the longevity of dissolved inorganic carbon (DIC) determinations in seawater, but can also be used for other analytical methods. DIC, a primary carbon dioxide (CO(2)) system variable along with alkalinity, controls seawater pH, carbonate saturation state, and CO(2) fugacity. Determinations of these parameters are central to an understanding of ocean acidification and global climate change. METHODS: Electrodes fabricated with electroactive materials, including manganese(III) oxide (Mn(2)O(3)) and palladium (Pd), were examined for potential use in electrolytic acidification. In-line acidification techniques were evaluated using a bench-top membrane introduction mass spectrometry (MIMS) setup to determine the DIC content of artificial seawater. Linear least-squares (LLSQ) calibrations for DIC concentration determinations over a range between 1650 and 2400 µmol kg(-1) were obtained, using both the novel electrolytic and conventional acid addition techniques. RESULTS: At sample rates of 4.5 mL min(-1), electrodes clad with Mn(2)O(3) and Pd were able to change seawater pH from 7.6 to 2.8 with a power consumption of less than 3 W. Although calibration curves were influenced by sampling rates at a flow of 4.5 mL min(-1), the 1σ measurement precision for DIC was of the order of ±20 µmol kg(-1). CONCLUSIONS: Calibrations obtained with the novel reagentless technique and the in-line addition of strong acid showed similar capabilities for DIC quantification. However, calculations of power savings for the reagentless technique relative to the mechanical delivery of stored acid demonstrated substantial advantages of the electrolytic technique for long-term deployments (>1 year).

High-resolution in situ analysis of nitrate and phosphate in the oligotrophic ocean.

Accurate, high-resolution profiles of nitrate and phosphate distributions in the open ocean are difficult to obtain using conventional techniques. Concentrations typically range from low nanomolar levels in the stratified euphotic zone to micromolar levels below the nutricline. With multiple pumps, a heating cartridge, a long-path-length cell, and a multiwavelength spectrometer, the reconfigured Spectrophotometric Elemental Analysis System (SEAS) provides the capability to fully ascertain the distributions of nitrate and phosphate in the upper 200 m of the oligotrophic ocean. By utilizing a 15 cm path length and multiple wavelength spectrophotometry, SEAS can detect nitrate concentrations from 2 nM to 20 microM and, with a 50 cm path length, can accurately measure phosphate concentrations from 1 nM to 1 microM. SEAS is capable of collecting auxiliary data from up to four separate instruments, including a CTD, a fluorometer, a PAR sensor, and a second SEAS instrument. Sampling frequency depends on peripheral instrument selection and ranges from 0.4 to 0.75 Hz.