In situ sensor technology for simultaneous spectrophotometric measurements of seawater total dissolved inorganic carbon and pH.

A new, in situ sensing system, Channelized Optical System (CHANOS), was recently developed to make high-resolution, simultaneous measurements of total dissolved inorganic carbon (DIC) and pH in seawater. Measurements made by this single, compact sensor can fully characterize the marine carbonate system. The system has a modular design to accommodate two independent, but similar measurement channels for DIC and pH. Both are based on spectrophotometric detection of hydrogen ion concentrations. The pH channel uses a flow-through, sample-indicator mixing design to achieve near instantaneous measurements. The DIC channel adapts a recently developed spectrophotometric method to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a response time of only ∼ 90 s. During laboratory and in situ testing, CHANOS achieved a precision of ±0.0010 and ± 2.5 µmol kg(-1) for pH and DIC, respectively. In situ comparison tests indicated that the accuracies of the pH and DIC channels over a three-week time-series deployment were ± 0.0024 and ± 4.1 µmol kg(-1), respectively. This study demonstrates that CHANOS can make in situ, climatology-quality measurements by measuring two desirable CO2 parameters, and is capable of resolving the CO2 system in dynamic marine environments.

Automated spectrophotometric analyzer for rapid single-point titration of seawater total alkalinity.

An automated analyzer was developed to achieve fast, precise, and accurate measurements of seawater total alkalinity (AT) based on single-point titration and spectrophotometric pH detection. The single-point titration was carried out in a circulating loop, which allowed the titrant (hydrochloric acid and bromocresol green solution) and a seawater sample to mix at a constant volume ratio. The dissolved CO2 in the sample-titrant mixture was efficiently removed by an inline CO2 remover, which consists of a gas-permeable tubing (Teflon AF2400) submerged in a sodium hydroxide (NaOH) solution. The pH of the mixture was then measured with a custom-made spectrophotometric detection system. The analyzer was calibrated against multiple certified reference materials (CRMs) with different AT values. The analyzer features a sample throughput time of 6.5 min with high precision (±0.33-0.36 µmol kg(-1); n = 48) and accuracy (-0.33 ± 0.99 µmol kg(-1); n = 10). Intercomparison to a traditional open-cell AT titrator showed overall good agreement of 0.88 ± 2.03 µmol kg(-1) (n = 22). The analyzer achieved excellent stability without recalibration over 11 days, during which time 320 measurements were made with a total running time of over 40 h. Because of its small size, low power consumption requirements, and its ability to be automated, the new analyzer can be adapted for underway and in situ measurements.

High-frequency spectrophotometric measurements of total dissolved inorganic carbon in seawater.

A new spectrophotometric method was developed to achieve continuous measurements of total dissolved inorganic carbon (DIC) in seawater. It uses a countercurrent flow design and a highly CO2-permeable membrane (Teflon AF 2400) to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a fast response time of ~22 s. This method improves the spatiotemporal resolution by more than 1 order of magnitude compared to the existing spectrophotometric method. The flow-through equilibration allows for continuous (~1 Hz) detection and real-time data smoothing. The method had a short-term precision of ± 2.0 µmol kg(-1) for a given flow-through sample. It achieved a field precision of ± 3.6 µmol kg(-1) and successfully captured high DIC variability down to minute scales. Measurements by the new method over the typical range of oceanic DIC showed good agreement with measurements made by an established method (mean differences -1.6 to 0.3 µmol kg(-1) with 1σ ± 6.0-6.7 µmol kg(-1)). This level of precision and accuracy is comparable to that of the existing spectrophotometric method. The characteristics of the new method make it particularly suitable for high-frequency, submerged measurements required for mobile observing platforms in the ocean. It can also be adapted for high-frequency, spectrophotometric measurements of seawater CO2 fugacity.