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Abstract Dissolved inorganic carbon (DIC) and its stable carbon isotope (δ¹³C‐DIC) are valuable parameters for studying the aquatic carbon cycle and quantifying ocean anthropogenic carbon accumulation rates. However, the potential of this coupled pair is underexploited as only 15% or less of cruise samples have been analyzed forδ¹³C‐DIC because the traditional isotope analysis is labor‐intensive and restricted to onshore laboratories. Here, we improved the analytical precision and reported the protocol of an automated, efficient, and high‐precision method for ship‐based DIC andδ¹³C‐DIC analysis based on cavity ring‐down spectroscopy (CRDS). We also introduced a set of stable in‐house standards to ensure accurate and consistent DIC andδ¹³C‐DIC measurements, especially on prolonged cruises. With this method, we analyzed over 1600 discrete seawater samples over a 40‐d cruise along the North American eastern ocean margin in summer 2022, representing the first effort to collect a large dataset ofδ¹³C‐DIC onboard of any oceanographic expedition. We evaluated the method's uncertainty, which was 1.2 μmol kg⁻¹for the DIC concentration and 0.03‰ for theδ¹³C‐DIC value (1σ). An interlaboratory comparison of onboard DIC concentration analysis revealed an average offset of 2.0 ± 3.8 μmol kg⁻¹between CRDS and the coulometry‐based results. The cross‐validation ofδ¹³C‐DIC in the deep‐ocean data exhibited a mean difference of only −0.03‰ ± 0.07‰, emphasizing the consistency with historical data. Potential applications in aquatic biogeochemistry are discussed. 

Here, we explicitly define a half-cell reaction approach for pH calculation using the electrode couple comprised of the solid-state chloride ion-selective electrode (Cl-ISE) as the reference electrode and the hydrogen ionselective ion-sensitive field effect transistor (ISFET) of the Honeywell Durafet as the hydrogen ion (H+)-sensitive measuring or working electrode. This new approach splits and isolates the independent responses of the Cl-ISE to the chloride ion (Cl−) (and salinity) and the ISFET to H+ (and pH), and calculates pH directly on the total scale (pHEXT total) in molinity (mol (kg-soln)−1) concentration units. We further apply and compare pHEXT total calculated using the half-cell and the existing complete cell reaction (defined by Martz et al. (2010)) approaches using measurements from two SeapHOx sensors deployed in a test tank. Salinity (on the Practical Salinity Scale) and pH oscillated between 1 and 31 and 6.9 and 8.1, respectively, over a six-day period. In contrast to established Sensor Best Practices, we employ a new calibration method where the calibration of raw pH sensor timeseries are split out as needed according to salinity. When doing this, pHEXT total had root-mean squared errors ranging between ±0.0026 and ±0.0168 pH calculated using both reaction approaches relative to pHtotal of the discrete bottle samples (pHdisc total). Our results further demonstrate the rapid response of the Cl-ISE reference to variable salinity with changes up to ±12 (30 min)−1. Final calculated pHEXT total were ≤±0.012 pH when compared to pHdisc total following salinity dilution or concentration. These results are notably in contrast to those of the few in situ field deployments over similar environmental conditions that demonstrated pHEXT total calculated using the Cl-ISE as the reference electrode had larger uncertainty in nearshore waters. Therefore, additional work beyond the correction of variable temperature and salinity conditions in pH calculation using the Cl-ISE is needed to examine the effects of other external stimuli on in situ electrode response. Furthermore, whereas past work has focused on in situ reference electrode response, greater scrutiny of the ISFET as the H+-sensitive measuring electrode for pH measurement in natural waters is also needed. 

Abstract In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (pCO₂) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be “hot-spots” for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (Ω_Ar) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, Ω_Arincreases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes. 

Abstract The southeastern Atlantic Ocean is a crucial yet understudied region for the ocean absorption of anthropogenic carbon (C_anth). Data from the A12 (2020) and A13.5 (2010) cruises offer an opportunity to examine changes in dissolved inorganic carbon (DIC), its stable isotope (δ¹³C), and C_anthover the past decade within a limited region (1∼3°E, 32∼42°S). For the decade of 2010–2020, C_anthinvasion was observed from the sea surface down to 1,200 m based on both DIC and δ¹³C data. The mean C_anthincrease rate (1.08 ± 0.26 mol m⁻² yr⁻¹) during this period accelerated from 0.87 ± 0.05 mol m⁻² yr⁻¹during the previous period (1983/84–2010). The δ¹³C‐based C_anthincrease closely matches the DIC‐based estimation below 500 m but is 26% higher in the upper ocean. This discrepancy is likely due to δ¹³C's longer air‐sea exchange timescale, seasonal variability in the upper ocean, and the chosen ratio of anthropogenically induced changes in δ¹³C and DIC. Finally, column inventory changes based on the two methods also exhibit very similar mean C_anthuptake rates. The paired DIC concentration and stable isotope dataset may enhance our ability to constrain C_anthaccumulation and its controlling mechanisms in the ocean.