On which timescales do gas transfer velocities control North Atlantic CO2 flux variability?

The North Atlantic is an important basin for the global ocean's uptake of anthropogenic and natural carbon dioxide (CO2), but the mechanisms controlling this carbon flux are not fully understood. The air-sea flux of CO2, F, is the product of a gas transfer velocity, k, the air-sea CO2 concentration gradient, ΔpCO2, and the temperature and salinity-dependent solubility coefficient, α. k is difficult to constrain, representing the dominant uncertainty in F on short (instantaneous to interannual) timescales. Previous work shows that in the North Atlantic, ΔpCO2 and k both contribute significantly to interannual F variability, but that k is unimportant for multidecadal variability. On some timescale between interannual and multidecadal, gas transfer velocity variability and its associated uncertainty become negligible. Here, we quantify this critical timescale for the first time. Using an ocean model, we determine the importance of k, ΔpCO2 and α on a range of timescales. On interannual and shorter timescales, both ΔpCO2 and k are important controls on F. In contrast, pentadal to multidecadal North Atlantic flux variability is driven almost entirely by ΔpCO2; k contributes less than 25%. Finally, we explore how accurately one can estimate North Atlantic F without a knowledge of non-seasonal k variability, finding it possible for interannual and longer timescales. These findings suggest that continued efforts to better constrain gas transfer velocities are necessary to quantify interannual variability in the North Atlantic carbon sink. However, uncertainty in k variability is unlikely to limit the accuracy of estimates of longer term flux variability

Evaluation of the National Oceanic and Atmospheric Administration/Coupled-Ocean Atmospheric Response Experiment (NOAA/COARE) air-sea gas transfer parameterization using GasEx data

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S11, doi:10.1029/2003JC001831.During the two recent GasEx field experiments, direct covariance measurements of air-sea carbon dioxide fluxes were obtained over the open ocean. Concurrently, the National Oceanic and Atmospheric Administration/Coupled-Ocean Atmospheric Response Experiment air-sea gas transfer parameterization was developed to predict gas transfer velocities from measurements of the bulk state of the sea surface and atmosphere. The model output is combined with measurements of the mean air and sea surface carbon dioxide fugacities to provide estimates of the air-sea CO2 flux, and the model is then tuned to the GasEx-1998 data set. Because of differences in the local environment and possibly because of weaknesses in the model, some discrepancies are observed between the predicted fluxes from the GasEx-1998 and GasEx-2001 cases. To provide an estimate of the contribution to the air-sea flux of gas due to wave-breaking processes, the whitecap and bubble parameterizations are removed from the model output. These results show that moderate (approximately 15 m s−1) wind speed breaking wave gas transfer processes account for a fourfold increase in the flux over the modeled interfacial processes.This work was supported by the NOAA Office of Global Programs, under the leadership of Dr. Lisa Dilling. WHOI was supported by the National Science Foundation grant OCE-9711218

Biases in the air-sea flux of CO2 resulting from ocean surface temperature gradients

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S08, doi:10.1029/2003JC001800.The difference in the fugacities of CO2 across the diffusive sublayer at the ocean surface is the driving force behind the air-sea flux of CO2. Bulk seawater fugacity is normally measured several meters below the surface, while the fugacity at the water surface, assumed to be in equilibrium with the atmosphere, is measured several meters above the surface. Implied in these measurements is that the fugacity values are the same as those across the diffusive boundary layer. However, temperature gradients exist at the interface due to molecular transfer processes, resulting in a cool surface temperature, known as the skin effect. A warm layer from solar radiation can also result in a heterogeneous temperature profile within the upper few meters of the ocean. Here we describe measurements carried out during a 14-day study in the equatorial Pacific Ocean (GasEx-2001) aimed at estimating the gradients of CO2 near the surface and resulting flux anomalies. The fugacity measurements were corrected for temperature effects using data from the ship's thermosalinograph, a high-resolution profiler (SkinDeEP), an infrared radiometer (CIRIMS), and several point measurements at different depths on various platforms. Results from SkinDeEP show that the largest cool skin and warm layer biases occur at low winds, with maximum biases of −4% and +4%, respectively. Time series ship data show an average CO2 flux cool skin retardation of about 2%. Ship and drifter data show significant CO2 flux enhancement due to the warm layer, with maximums occurring in the afternoon. Temperature measurements were compared to predictions based on available cool skin parameterizations to predict the skin-bulk temperature difference, along with a warm layer model.This material is based upon work supported by the NSF under grant OCE-9986724, and by NOAA/OGP grant GC00-226

CARINA TCO2 data in the Atlantic Ocean

Water column data of carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 cruises in the Arctic Mediterranean Seas, Atlantic and Southern Ocean have been retrieved and merged in a new data base: the CARINA (CARbon IN the Atlantic) Project. These data have gone through rigorous quality control (QC) procedures so as to improve the quality and consistency of the data as much as possible. Secondary quality control, which involved objective study of data in order to quantify systematic differences in the reported values, was performed for the pertinent parameters in the CARINA data base. Systematic biases in the data have been tentatively corrected in the data products. The products are three merged data files with measured, adjusted and interpolated data of all cruises for each of the three CARINA regions (Arctic Mediterranean Seas, Atlantic and Southern Ocean). Ninety-eight cruises were conducted in the "Atlantic" defined as the region south of the Greenland-Iceland-Scotland Ridge and north of about 30° S. Here we report the details of the secondary QC which was done on the total dissolved inorganic carbon (TCO2) data and the adjustments that were applied to yield the final data product in the Atlantic. Procedures of quality control – including crossover analysis between stations and inversion analysis of all crossover data – are briefly described. Adjustments were applied to TCO2 measurements for 17 of the cruises in the Atlantic Ocean region. With these adjustments, the CARINA data base is consistent both internally as well as with GLODAP data, an oceanographic data set based on the WOCE Hydrographic Program in the 1990s, and is now suitable for accurate assessments of, for example, regional oceanic carbon inventories, uptake rates and model validation

Data-based estimates of the ocean carbon sink variability – First results of the Surface Ocean pCO2 Mapping intercomparison (SOCOM)

Using measurements of the surface-ocean CO2 partial pressure (pCO2) and 14 different pCO2 mapping methods recently collated by the Surface Ocean pCO2 Mapping intercomparison (SOCOM) initiative, variations in regional and global sea–air CO2 fluxes are investigated. Though the available mapping methods use widely different approaches, we find relatively consistent estimates of regional pCO2 seasonality, in line with previous estimates. In terms of interannual variability (IAV), all mapping methods estimate the largest variations to occur in the eastern equatorial Pacific. Despite considerable spread in the detailed variations, mapping methods that fit the data more closely also tend to agree more closely with each other in regional averages. Encouragingly, this includes mapping methods belonging to complementary types – taking variability either directly from the pCO2 data or indirectly from driver data via regression. From a weighted ensemble average, we find an IAV amplitude of the global sea–air CO2 flux of 0.31 PgC yr−1 (standard deviation over 1992–2009), which is larger than simulated by biogeochemical process models. From a decadal perspective, the global ocean CO2 uptake is estimated to have gradually increased since about 2000, with little decadal change prior to that. The weighted mean net global ocean CO2 sink estimated by the SOCOM ensemble is −1.75 PgC yr−1 (1992–2009), consistent within uncertainties with estimates from ocean-interior carbon data or atmospheric oxygen trend

Air-sea CO2 exchange in the equatorial Pacific

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S02, doi:10.1029/2003JC002256.GasEx-2001, a 15-day air-sea carbon dioxide (CO2) exchange study conducted in the equatorial Pacific, used a combination of ships, buoys, and drifters equipped with ocean and atmospheric sensors to assess variability and surface mechanisms controlling air-sea CO2 fluxes. Direct covariance and profile method air-sea CO2 fluxes were measured together with the surface ocean and marine boundary layer processes. The study took place in February 2001 near 125°W, 3°S in a region of high CO2. The diurnal variation in the air-sea CO2 difference was 2.5%, driven predominantly by temperature effects on surface solubility. The wind speed was 6.0 ± 1.3 m s−1, and the atmospheric boundary layer was unstable with conditions over the range −1 < z/L < 0. Diurnal heat fluxes generated daytime surface ocean stratification and subsequent large nighttime buoyancy fluxes. The average CO2 flux from the ocean to the atmosphere was determined to be 3.9 mol m−2 yr−1, with nighttime CO2 fluxes increasing by 40% over daytime values because of a strong nighttime increase in (vertical) convective velocities. The 15 days of air-sea flux measurements taken during GasEx-2001 demonstrate some of the systematic environmental trends of the eastern equatorial Pacific Ocean. The fact that other physical processes, in addition to wind, were observed to control the rate of CO2 transfer from the ocean to the atmosphere indicates that these processes need to be taken into account in local and global biogeochemical models. These local processes can vary on regional and global scales. The GasEx-2001 results show a weak wind dependence but a strong variability in processes governed by the diurnal heating cycle. This implies that any changes in the incident radiation, including atmospheric cloud dynamics, phytoplankton biomass, and surface ocean stratification may have significant feedbacks on the amount and variability of air-sea gas exchange. This is in sharp contrast with previous field studies of air-sea gas exchange, which showed that wind was the dominating forcing function. The results suggest that gas transfer parameterizations that rely solely on wind will be insufficient for regions with low to intermediate winds and strong insolation.This work was performed with the support of the National Science Foundation Grant OCE-9986724 and the NOAA Global Carbon Cycle Program Grants NA06GP048, NA17RJ1223, and NA87RJ0445 in the Office of Global Programs

Direct covariance measurement of CO2 gas transfer velocity during the 2008 Southern Ocean Gas Exchange Experiment: Wind speed dependency

Direct measurements of air-sea heat, momentum, and mass (including CO2, DMS, and water vapor) fluxes using the direct covariance method were made over the open ocean from the NOAA R/V Ronald H. Brown during the Southern Ocean Gas Exchange (SO GasEx) program. Observations of fluxes and the physical processes associated with driving air-sea exchange are key components of SO GasEx. This paper focuses on the exchange of CO2 and the wind speed dependency of the transfer velocity, k, used to model the CO2 flux between the atmosphere and ocean. A quadratic dependence of k on wind speed based on dual tracer experiments is most frequently encountered in the literature. However, in recent years, bubble-mediated enhancement of k, which exhibits a cubic relationship with wind speed, has emerged as a key issue for flux parameterization in high-wind regions. Therefore, a major question addressed in SO GasEx is whether the transfer velocities obey a quadratic or cubic relationship with wind speed. After significant correction to the flux estimates (primarily due to moisture contamination), the direct covariance CO2 fluxes confirm a significant enhancement of the transfer velocity at high winds compared with previous quadratic formulations. Regression analysis suggests that a cubic relationship provides a more accurate parameterization over a wind speed range of 0 to 18 m s−1. The Southern Ocean results are in good agreement with the 1998 GasEx experiment in the North Atlantic and a recent separate field program in the North Sea