Suppression of air-sea CO2 transfer by surfactants – direct evidence from the Southern Ocean

Author(s):  
Mingxi Yang ◽  
Timothy Smyth ◽  
Vassilis Kitidis ◽  
Ian Brown ◽  
Charel Wohl ◽  
...  

<p>Uncertainty in the CO<sub>2</sub> gas transfer velocity (K<sub>660</sub>) severely limits the accuracy of air-sea CO<sub>2</sub> flux calculations and hence hinders our ability to produce realistic climate projections.  Recent field observations have suggested substantial variability in K<sub>660</sub>, especially at low and high wind speeds.  Laboratory experiments have shown that naturally occurring surface active organic materials, or surfactants, can suppress gas transfer.  Here we provide direct open ocean evidence of gas transfer suppression due to surfactants from a ~11,000 km long research expedition by making measurements of the gas transfer efficiency (GTE) along with direct observation of K<sub>660</sub>.  GTE varied by 20% during the Southern Ocean transect and was distinct in different watermasses.  Furthermore GTE correlated with and can explain about 9% of the scatter in K<sub>660</sub>, suggesting that surfactants exert a measurable influence on air-sea CO<sub>2</sub> flux.  Relative gas transfer suppression due to surfactants was ~30% at a global mean wind speed of 7 m s<sup>-1</sup> and was more important at lower wind speeds.  Neglecting surfactant suppression may result in substantial spatial and temporal biases in the computed air-sea CO<sub>2</sub> fluxes.</p>

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Mingxi Yang ◽  
Timothy J. Smyth ◽  
Vassilis Kitidis ◽  
Ian J. Brown ◽  
Charel Wohl ◽  
...  

AbstractThe flux of CO2 between the atmosphere and the ocean is often estimated as the air–sea gas concentration difference multiplied by the gas transfer velocity (K660). The first order driver for K660 over the ocean is wind through its influence on near surface hydrodynamics. However, field observations have shown substantial variability in the wind speed dependencies of K660. In this study we measured K660 with the eddy covariance technique during a ~ 11,000 km long Southern Ocean transect. In parallel, we made a novel measurement of the gas transfer efficiency (GTE) based on partial equilibration of CO2 using a Segmented Flow Coil Equilibrator system. GTE varied by 20% during the transect, was distinct in different water masses, and related to K660. At a moderate wind speed of 7 m s−1, K660 associated with high GTE exceeded K660 with low GTE by 30% in the mean. The sensitivity of K660 towards GTE was stronger at lower wind speeds and weaker at higher wind speeds. Naturally-occurring organics in seawater, some of which are surface active, may be the cause of the variability in GTE and in K660. Neglecting these variations could result in biases in the computed air–sea CO2 fluxes.


2014 ◽  
Vol 14 (21) ◽  
pp. 28453-28482
Author(s):  
T. G. Bell ◽  
W. De Bruyn ◽  
C. A. Marandino ◽  
S. D. Miller ◽  
C. S. Law ◽  
...  

Abstract. Air/sea dimethylsulfide (DMS) fluxes and bulk air/sea gradients were measured over the Southern Ocean in February/March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (>15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s−1. Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A~flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data shows no obvious modification of the gas transfer-wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments.


2015 ◽  
Vol 15 (4) ◽  
pp. 1783-1794 ◽  
Author(s):  
T. G. Bell ◽  
W. De Bruyn ◽  
C. A. Marandino ◽  
S. D. Miller ◽  
C. S. Law ◽  
...  

Abstract. Air–sea dimethylsulfide (DMS) fluxes and bulk air–sea gradients were measured over the Southern Ocean in February–March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (> 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s−1. Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer–wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments.


2013 ◽  
Vol 10 (6) ◽  
pp. 1971-1996
Author(s):  
K. E. Krall ◽  
B. Jähne

Abstract. In a pilot study conducted in October and November 2011, air–sea gas transfer velocities of the two sparingly soluble trace gases hexafluorobenzene and 1,4-difluorobenzene were measured in the unique High-Speed Wind-Wave Tank at Kyoto University, Japan. This air–sea interaction facility is capable of producing hurricane strength wind speeds of up to u10=67 m s−1. This constitutes the first lab study of gas transfer at such high wind speeds. The measured transfer velocities k600 spanned two orders of magnitude, lying between 11 cm h−1 and 1180 cm h−1 with the latter being the highest ever measured wind induced gas transfer velocity. The measured gas transfer velocities are in agreement with the only available dataset at hurricane wind speeds (McNeil and D'Asaro, 2007). The disproportionately large increase of the transfer velocities found at highest wind speeds indicates a new regime of air–sea gas transfer, which is characterized by strong wave breaking, enhanced turbulence and bubble cloud entrainment. It was found that tracers spanning a wide range of solubilities and diffusivities are needed to separate the effects of enhanced surface area and turbulence due to breaking waves from the effects of bubble and spray mediated gas transfer.


2018 ◽  
Vol 18 (6) ◽  
pp. 4297-4315 ◽  
Author(s):  
Sebastian Landwehr ◽  
Scott D. Miller ◽  
Murray J. Smith ◽  
Thomas G. Bell ◽  
Eric S. Saltzman ◽  
...  

Abstract. Parameterisation of the air–sea gas transfer velocity of CO2 and other trace gases under open-ocean conditions has been a focus of air–sea interaction research and is required for accurately determining ocean carbon uptake. Ships are the most widely used platform for air–sea flux measurements but the quality of the data can be compromised by airflow distortion and sensor cross-sensitivity effects. Recent improvements in the understanding of these effects have led to enhanced corrections to the shipboard eddy covariance (EC) measurements.Here, we present a revised analysis of eddy covariance measurements of air–sea CO2 and momentum fluxes from the Southern Ocean Surface Ocean Aerosol Production (SOAP) study. We show that it is possible to significantly reduce the scatter in the EC data and achieve consistency between measurements taken on station and with the ship underway. The gas transfer velocities from the EC measurements correlate better with the EC friction velocity (u*) than with mean wind speeds derived from shipboard measurements corrected with an airflow distortion model. For the observed range of wind speeds (u10 N = 3–23 m s−1), the transfer velocities can be parameterised with a linear fit to u*. The SOAP data are compared to previous gas transfer parameterisations using u10 N computed from the EC friction velocity with the drag coefficient from the Coupled Ocean–Atmosphere Response Experiment (COARE) model version 3.5. The SOAP results are consistent with previous gas transfer studies, but at high wind speeds they do not support the sharp increase in gas transfer associated with bubble-mediated transfer predicted by physically based models.


2018 ◽  
Author(s):  
Leila Nagel ◽  
Kerstin E. Krall ◽  
Bernd Jähne

Abstract. Heat transfer velocities measured during three different campaigns in the Baltic Sea using the Active Controlled Flux Technique (ACFT) with wind speeds ranging from 5.3 to 14.8 m s−1 are presented. Careful scaling of the heat transfer velocities to gas transfer velocities using Schmidt number exponents measured in a laboratory study allows to compare the measured transfer velocities to existing gas transfer velocity parameterizations, which use wind speed as the controlling parameter. The measured data and other field data clearly show that some gas transfer velocities are much lower than the empirical wind speed parametrizations. This indicates that the dependencies of the transfer velocity on the fetch, i.e., the history of the wind and the age of the wind wave field, and the effects of surface active material need to be taken into account.


Ocean Science ◽  
2014 ◽  
Vol 10 (2) ◽  
pp. 257-265 ◽  
Author(s):  
K. E. Krall ◽  
B. Jähne

Abstract. In a pilot study conducted in October and November 2011, air–sea gas transfer velocities of the two sparingly soluble trace gases hexafluorobenzene and 1,4-difluorobenzene were measured in the unique high-speed wind-wave tank at Kyoto University, Japan. This air–sea interaction facility is capable of producing hurricane strength wind speeds of up to u10 =67 m s−1. This constitutes the first lab study of gas transfer at such high wind speeds. The measured transfer velocities k600 spanned two orders of magnitude, lying between 11 cm h−1 and 1180 cm h−1 with the latter being the highest ever measured wind-induced gas transfer velocity. The measured gas transfer velocities are in agreement with the only available data set at hurricane wind speeds (McNeil and D'Asaro, 2007). The disproportionately large increase of the transfer velocities found at highest wind speeds indicates a new regime of air–sea gas transfer, which is characterized by strong wave breaking, enhanced turbulence and bubble cloud entrainment.


Ocean Science ◽  
2019 ◽  
Vol 15 (2) ◽  
pp. 235-247 ◽  
Author(s):  
Leila Nagel ◽  
Kerstin E. Krall ◽  
Bernd Jähne

Abstract. Heat transfer velocities measured during three different campaigns in the Baltic Sea using the active controlled flux technique (ACFT) with wind speeds ranging from 5.3 to 14.8 m s−1 are presented. Careful scaling of the heat transfer velocities to gas transfer velocities using Schmidt number exponents measured in a laboratory study allows us to compare the measured transfer velocities to existing gas transfer velocity parameterizations, which use wind speed as the controlling parameter. The measured data and other field data clearly show that some gas transfer velocities are much lower than those based on the empirical wind speed parameterizations. This indicates that the dependencies of the transfer velocity on the fetch, i. e., the history of the wind and the age of the wind-wave field, and the effects of surface-active material need to be taken into account.


Elem Sci Anth ◽  
2018 ◽  
Vol 6 ◽  
Author(s):  
M. Ribas-Ribas ◽  
L. F. Kilcher ◽  
O. Wurl

Understanding how the ocean absorbs anthropogenic CO2 is critical for predicting climate change. We designed Sniffle, a new autonomous drifting buoy with a floating chamber, to measure gas transfer velocities and air–sea CO2 fluxes with high spatiotemporal resolution. Currently, insufficient in situ data exist to verify gas transfer parameterizations at low wind speeds (<4 m s–1), which leads to underestimation of gas transfer velocities and, therefore, of air–sea CO2 fluxes. The Sniffle is equipped with a sensor to consecutively measure aqueous and atmospheric pCO2 and to monitor increases or decreases of CO2 inside the chamber. During autonomous operation, a complete cycle lasts 40 minutes, with a new cycle initiated after flushing the chamber. The Sniffle can be deployed for up to 15 hours at wind speeds up to 10 m s–1. Floating chambers often overestimate fluxes because they create additional turbulence at the water surface. We correct fluxes by measuring turbulence with two acoustic Doppler velocimeters, one positioned directly under the floating chamber and the other positioned sideways, to compare artificial disturbance caused by the chamber and natural turbulence. The first results of deployment in the North Sea during the summer of 2016 demonstrate that the new drifting buoy is a useful tool that can improve our understanding of gas transfer velocity with in situ measurements. At low and moderate wind speeds and different conditions, the results obtained indicate that the observed tidal basin was acting as a source of atmospheric CO2. Wind speed and turbulence alone could not fully explain the variance in gas transfer velocity. We suggest that other factors like surfactants, rain or tidal current will have an impact on gas transfer parameterizations.


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