Is remote sensing of the surfactant effect on gas transfer velocity possible?

Author(s):  
Jacek Piskozub ◽  
Violetta Drozdowska ◽  
Iwona Wróbel-Niedźwiecka ◽  
Przemysław Makuch ◽  
Piotr Markuszewski ◽  
...  

<p>The air-sea gas flux is proportional to the difference of partial pressure between the sea-water and the overlying atmosphere multiplied by gas transfer velocity <em>k</em>, a measure of the effectiveness of the gas exchange. Because wind is the source of turbulence making the gas exchange more effective, <em>k</em> is usually parameterized by wind speed. Unfortunately, measured values of gas transfer velocity at a given wind speed have a large spread in values. Surfactants have been long suspected as the main reason of this variability but few measurements of gas exchange and surfactants have been performed at open sea simultaneously and therefore their results were inconclusive. Only recently, it has been shown that surfactants may decrease the CO<sub>2</sub> air-sea exchange by up to 50%. However the labour intensive methods used for surfactant study make it impossible to collect enough data to map the surfactant coverage or even create a gas transfer velocity parameterization involving a measure of surfactant activity. This is why we propose to use optical fluorescence as a proxy of surfactant activity.</p><p> </p><p>Previous research done by our group showed that fluorescence parameters allow estimation the surfactant enrichment of the surface microlayer, as well as types and origin of fluorescent organic matter involved. We plan to measure, from a research ship, all the variables needed for calculation of gas transfer velocity <em>k</em> (namely CO<sub>2</sub> partial pressure both in water and in air as well as vertical flux of this trace gas) and to use mathematical optimization methods to look for a parameterization involving wind speed and one of the fluorescence parameters which will minimize the residual <em>k</em> variability. Although our research will still involve water sampling and laboratory fluorescence measurements, the knowledge of which absorption and fluorescence emission bands are the best proxy for surfactant activity may allow to create remote sensing products (fluorescence lidars) allowing continuous measurements of surfactant activity at least from the ship board, if not from aircraft and satellites. The improved parameterization of the CO<sub>2</sub> gas transfer velocity will allow better constraining of basin-wide and global air-sea fluxes, an important component of global carbon budget.</p><p> </p><p>If an improved gas transfer velocity parametrization based on surfactant fluorescence spectrum in concert with a turbulence proxy (wind) were to be found, a tantalizing possibility arises of a remote sensing estimation of <em>k</em>. Namely a UV lidar can both excite and measure the fluorescence band identified as proxy of the surfactant effect on the gas transfer velocity. Depending on the wavelength bands needed to be utilized, the effect could be measured from a moving ship (already an improvements on methods needing sampling), an aircraft or possibly even a satellite. We intend to pursue this idea in cruises to both the Baltic and the North Atlantic, possibly in cooperation with other air-sea interaction groups (this presentation is in part an invitation to cooperation).</p>

2009 ◽  
Vol 6 (6) ◽  
pp. 1105-1114 ◽  
Author(s):  
M. Ll. Calleja ◽  
C. M. Duarte ◽  
Y. T. Prairie ◽  
S. Agustí ◽  
G. J. Herndl

Abstract. Air-sea CO2 exchange depends on the air-sea CO2 gradient and the gas transfer velocity (k), computed as a function of wind speed. Large discrepancies among relationships predicting k from wind suggest that other processes also contribute significantly to modulate CO2 exchange. Here we report, on the basis of the relationship between the measured gas transfer velocity and the organic carbon concentration at the ocean surface, a significant role of surface organic matter in suppressing air-sea gas exchange, at low and intermediate winds, in the open ocean, confirming previous observations. The potential role of total surface organic matter concentration (TOC) on gas transfer velocity (k) was evaluated by direct measurements of air-sea CO2 fluxes at different wind speeds and locations in the open ocean. According to the results obtained, high surface organic matter contents may lead to lower air-sea CO2 fluxes, for a given air-sea CO2 partial pressure gradient and wind speed below 5 m s−1, compared to that observed at low organic matter contents. We found the bias in calculated gas fluxes resulting from neglecting TOC to co-vary geographically and seasonally with marine productivity. These results support previous evidences that consideration of the role of organic matter in modulating air-sea CO2 exchange may improve flux estimates and help avoid possible bias associated to variability in surface organic concentration across the ocean.


2008 ◽  
Vol 5 (6) ◽  
pp. 4209-4233
Author(s):  
M. Ll. Calleja ◽  
C. M. Duarte ◽  
Y. T. Prairie ◽  
S. Agustí ◽  
G. J. Herndl

Abstract. Air-sea CO2 exchange depends on the air-sea CO2 gradient and the gas transfer velocity (k), computed as a simple function of wind speed. Large discrepancies among relationships predicting k from wind suggest that other processes may also contribute significantly to modulate CO2 exchange. Here we report, on the basis of the relationship between the measured gas transfer velocity and the ocean surface organic carbon concentration at the ocean surface, a significant role of surface organic matter in suppressing air-sea gas exchange, at low and intermediate winds, in the open ocean. The potential role of total surface organic matter concentration (TOC) on gas transfer velocity (k) was evaluated by direct measurements of air-sea CO2 fluxes at different wind speeds and locations in the open ocean. According to the results obtained, high surface organic matter contents may lead to lower air-sea CO2 fluxes, for a given air-sea CO2 partial pressure gradient and wind speed below 5 m s−1, compared to that observed at low organic matter contents. We found the bias in calculated gas fluxes resulting from neglecting TOC to co-vary geographically and seasonally with marine productivity. These findings suggest that consideration of the role of organic matter in modulating air-sea CO2 exchange can improve flux estimates and help avoid possible bias associated to variability in surface organic concentration across the ocean.


2012 ◽  
Vol 9 (3) ◽  
pp. 957-964 ◽  
Author(s):  
A. Kock ◽  
J. Schafstall ◽  
M. Dengler ◽  
P. Brandt ◽  
H. W. Bange

Abstract. Sea-to-air and diapycnal fluxes of nitrous oxide (N2O) into the mixed layer were determined during three cruises to the upwelling region off Mauritania. Sea-to-air fluxes as well as diapycnal fluxes were elevated close to the shelf break, but elevated sea-to-air fluxes reached further offshore as a result of the offshore transport of upwelled water masses. To calculate a mixed layer budget for N2O we compared the regionally averaged sea-to-air and diapycnal fluxes and estimated the potential contribution of other processes, such as vertical advection and biological N2O production in the mixed layer. Using common parameterizations for the gas transfer velocity, the comparison of the average sea-to-air and diapycnal N2O fluxes indicated that the mean sea-to-air flux is about three to four times larger than the diapycnal flux. Neither vertical and horizontal advection nor biological production were found sufficient to close the mixed layer budget. Instead, the sea-to-air flux, calculated using a parameterization that takes into account the attenuating effect of surfactants on gas exchange, is in the same range as the diapycnal flux. From our observations we conclude that common parameterizations for the gas transfer velocity likely overestimate the air-sea gas exchange within highly productive upwelling zones.


2016 ◽  
Vol 13 (13) ◽  
pp. 3981-3989 ◽  
Author(s):  
R. Pereira ◽  
K. Schneider-Zapp ◽  
R. C. Upstill-Goddard

Abstract. Understanding the physical and biogeochemical controls of air–sea gas exchange is necessary for establishing biogeochemical models for predicting regional- and global-scale trace gas fluxes and feedbacks. To this end we report the results of experiments designed to constrain the effect of surfactants in the sea surface microlayer (SML) on the gas transfer velocity (kw; cm h−1), seasonally (2012–2013) along a 20 km coastal transect (North East UK). We measured total surfactant activity (SA), chromophoric dissolved organic matter (CDOM) and chlorophyll a (Chl a) in the SML and in sub-surface water (SSW) and we evaluated corresponding kw values using a custom-designed air–sea gas exchange tank. Temporal SA variability exceeded its spatial variability. Overall, SA varied 5-fold between all samples (0.08 to 0.38 mg L−1 T-X-100), being highest in the SML during summer. SML SA enrichment factors (EFs) relative to SSW were  ∼  1.0 to 1.9, except for two values (0.75; 0.89: February 2013). The range in corresponding k660 (kw for CO2 in seawater at 20 °C) was 6.8 to 22.0 cm h−1. The film factor R660 (the ratio of k660 for seawater to k660 for “clean”, i.e. surfactant-free, laboratory water) was strongly correlated with SML SA (r ≥ 0.70, p ≤ 0.002, each n = 16). High SML SA typically corresponded to k660 suppressions  ∼  14 to 51 % relative to clean laboratory water, highlighting strong spatiotemporal gradients in gas exchange due to varying surfactant in these coastal waters. Such variability should be taken account of when evaluating marine trace gas sources and sinks. Total CDOM absorbance (250 to 450 nm), the CDOM spectral slope ratio (SR = S275 − 295∕S350 − 400), the 250 : 365 nm CDOM absorption ratio (E2 : E3), and Chl a all indicated spatial and temporal signals in the quantity and composition of organic matter in the SML and SSW. This prompts us to hypothesise that spatiotemporal variation in R660 and its relationship with SA is a consequence of compositional differences in the surfactant fraction of the SML DOM pool that warrants further investigation.


Tellus B ◽  
1993 ◽  
Vol 45 (3) ◽  
pp. 299-300 ◽  
Author(s):  
Robert C. Upstill-Goddard ◽  
Andrew J. Watson ◽  
Peter S. Liss

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.


2012 ◽  
Vol 9 (8) ◽  
pp. 9993-10017
Author(s):  
P. Otero ◽  
X. A. Padín ◽  
M. Ruiz-Villarreal ◽  
L. M. García-García ◽  
A. F. Ríos ◽  
...  

Abstract. The estimation of sea-air CO2 fluxes are largely dependent on wind speed through the gas transfer velocity parameterization. In this paper, we quantify uncertainties in the estimation of the CO2 uptake in the Bay of Biscay resulting from using different sources of wind speed such as three different global reanalysis meteorological models (NCEP/NCAR 1, NCEP/DOE 2 and ERA-Interim), one regional high-resolution forecast model (HIRLAM-AEMet) and QuikSCAT winds, in combination with some of the most widely used gas transfer velocity parameterizations. Results show that net CO2 flux estimations during an entire seasonal cycle may differ up to 240% depending on the wind speed product and the gas exchange parameterization. The comparison of satellite and model derived winds with observations at buoys advises against the systematic overestimation of NCEP-2 and the underestimation of NCEP-1. In this region, QuikSCAT has the best performing, although ERA-Interim becomes the best choice in areas near the coastline or when the time resolution is the constraint.


2019 ◽  
Vol 16 (5) ◽  
pp. 961-978 ◽  
Author(s):  
Mingxi Yang ◽  
Thomas G. Bell ◽  
Ian J. Brown ◽  
James R. Fishwick ◽  
Vassilis Kitidis ◽  
...  

Abstract. Air–water CH4 and CO2 fluxes were directly measured using the eddy covariance technique at the Penlee Point Atmospheric Observatory on the southwest coast of the United Kingdom from September 2015 to August 2016. The high-frequency, year-long measurements provide unprecedented detail on the variability of these greenhouse gas fluxes from seasonal to diurnal and to semi-diurnal (tidal) timescales. Depending on the wind sector, fluxes measured at this site are indicative of air–water exchange in coastal seas as well as in an outer estuary. For the open-water sector when winds were off the Atlantic Ocean, CH4 flux was almost always positive (annual mean of ∼0.05 mmol m−2 d−1) except in December and January, when CH4 flux was near zero. At times of high rainfall and river flow rate, CH4 emission from the estuarine-influenced Plymouth Sound sector was several times higher than emission from the open-water sector. The implied CH4 saturation (derived from the measured fluxes and a wind-speed-dependent gas transfer velocity parameterization) of over 1000 % in the Plymouth Sound is within range of in situ dissolved CH4 measurements near the mouth of the river Tamar. CO2 flux from the open-water sector was generally from sea to air in autumn and winter and from air to sea in late spring and summer, with an annual mean flux of near zero. A diurnal signal in CO2 flux and implied partial pressure of CO2 in water (pCO2) are clearly observed for the Plymouth Sound sector and also evident for the open-water sector during biologically productive periods. These observations suggest that coastal CO2 efflux may be underestimated if sampling strategies are limited to daytime only. Combining the flux data with seawater pCO2 measurements made in situ within the flux footprint allows us to estimate the CO2 transfer velocity. The gas transfer velocity and wind speed relationship at this coastal location agrees reasonably well with previous open-water parameterizations in the mean but demonstrates considerable variability. We discuss the influences of biological productivity, bottom-driven turbulence and rainfall on coastal air–water gas exchange.


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