Observed trends of  p CO 2  and air-sea CO2 fluxes in the North Atlantic Ocean

Nsikak U. Benson<sup>1</sup>; Oladele O. Osibanjo<sup>2</sup>; Francis E. Asuquo<sup>3</sup>; Winifred U. Anake<sup>1</sup>

Observed trends of pCO₂ and air-sea CO2 fluxes in the North Atlantic Ocean

Nsikak U. Benson¹

, Oladele O. Osibanjo²

, Francis E. Asuquo³

, Winifred U. Anake¹

1. Environmental Chemistry Unit, Department of Chemistry, School of Natural and Applied Sciences, Covenant University, Ota, Nigeria
2. Department of Chemistry, University of Ibadan, Ibadan, Nigeria
3. Institute of Oceanography, Marine Chemistry Unit, University of Calabar, Nigeria

Author

Correspondence author
International Journal of Marine Science, 2014, Vol. 4, No. 72 doi: 10.5376/ijms.2014.04.0072
Received: 22 Sep., 2014 Accepted: 20 Oct., 2014 Published: 10 Dec., 2014

This is an open access article published under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Preferred citation for this article:

Benson et al., 2014, Observed trends of pCO2 and air-sea CO2 fluxes in the North Atlantic Ocean, International Journal of Marine Science, Vol.4, No.72 1-7 (doi: 10.5376/ijms.2014.04.0072)

Abstract

Observed partial pressure of carbon dioxide (pCO₂) and temperature data in surface and mixed layer seawater of the Northeast (49^oN, 16.5^oW) and Northwest (56.5^oN, 52.6^oW) Atlantic Ocean time series sites have been analyzed for seasonal variability and air-sea CO₂fluxes. The NE PAP data showed an annual mean pCO₂of 335.9 ± 89.6 matm (2003), 286.7 ± 103.5 matm (2004), and 335.9 ± 89.6 matm (2005). The annual data for NW KI deployments indicated annual pCO₂average of 336.6 ± 14.3 and 359.1 ± 25.3 matm for 2004 and 2005 respectively. The oceanic pCO₂distribution across the spatial gradients over a seasonal timescale is relatively homogeneous with marked seasonal variability. These data indicated consistently the undersaturation of oceanic surface water at the sites and thus a perennial carbon sink. Sea surface pCO₂trend is marked by summertime minimum and wintertime maximum, while depicting anti-phase patterns with the observed temperature signals. Seasonal to annual CO₂fluxes indicated a year-round CO₂ invasion of the NE and NW basins. Estimated net basin-scale CO₂ uptake fluxes of 2.96 ± 1.73 and 1.84 ± 1.3 mol m^-2 CO₂a^-1were obtained for NE PAP (2nd - 4th) and NW K1 deployments, respectively.

Keywords

pCO₂; air-sea CO2 fluxes; seasonal variability; temperature trends; North Atlantic Ocean

The North Atlantic Ocean is regarded as the largest ocean sink for atmospheric carbon dioxide (CO₂), based both on observational estimates (Schneider et al., 1992; Kuss et al., 2006; Takahashi et al., 2002; 2009), and forward and inverse modeling results (Gloor et al., 2003; McKinley et al., 2004; 2008). The strong CO₂ sink capacity of the North Atlantic Ocean is largely attributed to two principal factors vis-a-vis the counteractive effect of vertical circulation in which large volumes of surface water driven poleward by strong currents, cools and absorbs huge quantities of atmospheric CO₂ before getting sunk to mixed layer depth during the wintertime, and also to the effective and sustained carbon and nutrients (phosphorus, silica and iron) uptake (Takahashi et al., 2002, 2009; Schuster and Watson, 2007; Körtzinger et al., 2008a). However, observations have indicated substantial variability in the uptake of CO₂ spatially (Watson et al., 1991) and temporally (Gruber et al., 2002).

The exchange of CO₂ between the ocean and the atmosphere is a major biogeochemical process that regulates the fate and rate of increase of anthropogenic CO₂, which will in turn determine the rate of likely climate change. This biogeochemical process is significantly controlled by prevailing pCO₂ existing between the atmosphere and surface of the ocean. Sea surface pCO₂ is governed by physical and biological factors such as change of sea surface temperature (SST) (Schuster et al., 2009), deep convective mixing, re-stratification (Straneo, 2006), entrainment of CO₂enriched deeper water (Avsic et al., 2006; Körtzinger et al., 2008b), salinity (Dickson et al., 2002), phase of the North Atlantic Oscillation (Thomas et al., 2008), consumption by marine biota linked to the availability of surface nutrients (productivity/respiration) (Behrenfeld et al., 2006). The net CO₂ transfer is a function of the difference in the pCO₂ at the air-sea interface, and of the exchange processes in the atmosphere and the ocean (Takahashi et al., 2009; Omstedt et al., 2009).

There is a growing understanding that adequate parameterization of CO₂ flux is a significant factor in the quantification of spatially resolved air-sea CO₂ exchange (Rutgersson et al., 2008; Takahashi et al., 2009). The assessment is crucial for climate modeling owing to the fact that CO₂ is the major driver of anthropogenic climate change. Additionally, in order to understand how the changing global environment may alter the carbon cycle, it is necessary to further analyse the fluxes and examine the physicochemical and biological processes that determine them.

1 Data and methods

1.1 Sources of observed data

The observed data used for this research where obtained from the Porcupine Abyssal Plain and K1 Central Labrador Sea oceanographic mooring sites in the North Atlantic Ocean (Figure 1).

Figure 1 Map of the North Atlantic Ocean showing the Porcupine Abyssal Plain (49^oN, 16.5^oW) and Labrador Sea (56.5^oN, 52.5^oW)

1.2 Air-sea CO₂ fluxes estimation

The calculation of CO₂ flux (fCO₂) in ocean and climate models is based on the indirect bulk method. The net exchange of CO₂ (f) between the ocean surface and the atmosphere is estimated from the air-sea difference in partial pressure of CO₂(DpCO₂) and the gas transfer velocity (k) using the equation (Wanninkhof, 1992, 2007; Donelan and Wanninkhof, 2002):

fCO₂ = k × (u)K₀× DpCO₂(1)

Where k is the gas transfer velocity of CO₂ exchange, u is the wind speed, K₀ is the solubility of CO₂ in seawater and is a function of salinity and temperature (Weiss, 1974), and DpCO₂is mean air-sea pCO₂ difference,

DpCO₂= [(pCO₂-air)– (pCO₂-sw)] (2)

Where pCO₂-airand pCO₂-sw represent the respective partial pressure of carbon dioxide in the atmosphere and seawater (Rutgersson et al., 2008). The transfer velocity, k, is regarded as a function of wind speed, u, and the Schmidt number (Sc), although this is still controversial (Weiss et al., 2007; Rutgersson et al., 2008). The Schmidt number (Sc) is the ratio of the kinematic viscosity of seawater to the diffusion coefficient of the considered gas. For wind speeds larger than 5 ms^− 1, k is proportional to Sc^{− 1/2} (Liss and Merlivat, 1986). Different functions which refer to Sc = 660 (CO₂ at 20 C) have been proposed to describe k₆₆₀ as a function of wind speed at a reference height of 10 m (u₁₀). Wanninkh of (1992) suggested a quadratic equation:

k₆₆₀ = 0.31u²₁₀(3)

which gives k for any other Sc as

k= 0.31u²₁₀ (4)

A cubic dependence is given from Wanninkhof and McGillis (1999):

k = 0.0283u³₁₀ 5)

Moreover, recent investigation evaluating the transfer velocity-wind speed relationship using a long-term series of direct eddy correlation CO₂ flux measurements from the Baltic Sea suggests a combination of quadratic and linear wind speed dependence (Weiss et al., 2007; Rutgersson et al., 2008).

k = (0.365u²₁₀+ 0.46 u²₁₀) (6)

A positive flux (fCO₂) value represents a net CO₂exchange from sea to the atmosphere and a negative flux value refers to the net CO₂ exchange from the atmosphere to the sea. For the purposes of this research, 8-day averages of air-sea pCO₂ difference (ΔpCO₂), SST, wind speed at 10 m height, and mixed layer depth are produced, and calculations of 8-day CO₂ flux densities, f, were performed using equation (4).

2 Results and discussion

2.1 Seasonal to monthly pCO₂net flux in North Atlantic NW / NE basins

The emerging trend of the seasonal pCO₂ cycle at the PAP observatory site indicates high pCO₂ difference between the seawater relative to atmospheric pCO₂, showing a persistent undersaturation of surface waters by ΔpCO₂of about 70 µatm in summer of 2004 (Figure 2). This predicts an influx of CO₂ from the atmosphere into the ocean, and the trend notably followed an increasing seawater surface temperature (warming). Winter deep convection has been established as a mechanistic process of exposing CO₂-enriched subsurface water to the seawater surface (McKinley et al., 2004b). This mechanism is markedly observed during the winter months (Figure 2) where relatively low or damped ΔpCO₂were obtained.

Figure 2 Monthly ΔpCO₂ between July 2003 – March 2005 plotted as a function of SST at the PAP observatory

In other words, the time-trend ΔpCO₂ flux variability indicates relatively damped ΔpCO₂ during wintertime and enhanced ΔpCO₂ in summertime. Also, uptake of anthropogenic CO₂ from the atmosphere increases during wintertime resulting in relatively low ΔpCO₂. However, a positive ΔpCO₂was observed in early summer of 2003 (August 2003) resulting in a possible efflux of CO₂ into the atmosphere leading to a decrease in net ocean CO₂uptake during the summertime. This could be attributed to a dominant DIC-driven pCO₂.

Considering the average monthly CO₂flux variability at the NW K1 Central Labrador Sea, a relatively high sea-air ΔpCO₂ of about 60 µatm was recorded in September 2004 as a negative CO₂flux (Figure 3). However, decreasing CO₂sink of the time series location is observed following seasonal change from summertime of 2004 to wintertime. Uptake of CO₂ by the ocean almost equilibrated with the atmospheric pCO₂ during the peak period of the winter months, thereby creating a near saturated condition with relatively low sea surface temperature. Evidently, enhanced sea surface pCO₂ (high DIC) is expected following deep convective mixing and entrainment of subsurface CO₂ enriched water to the surface of the ocean. DIC supply to the surface is relatively low during summertime owing to biology and stratification of the ocean system. Additionally, sea-air ΔpCO₂ flux variability digressed towards negative flux following the outset of spring as the seawater surface starts to warm up. Thus, the ΔpCO₂ flux variability on an annual timescales generally indicates a consistent undersaturation of the NW subpolar site.

Figure 3 Monthly ΔpCO₂ between September 2004 – July 2005 plotted as a function of SST at the K1 CELAS site

Seasonal sink estimates for the wintertime of 2004 and 2005 were calculated as 4.86 ± 0.15 and 4.15 ± 0.98 mol m^-2 CO₂a^-1respectively, while 0.29 ± 0.78 and 1.65 ± 1.40 mol m^-2 a^-1 were obtained for 2003 and 2004 summertime (Table 1). The CO₂uptake of 2.36 ± 2.07 and 2.28 ± 1.34 mol m^-2 CO₂a^-1 were computed for the autumn of 2003 and 2004 respectively. Based on the in situ observed data available, the short-term interseasonal CO₂sink of the Porcupine Abyssal Plain time series site is estimated to have decreased by approximately 82.4, 3.6 and 17.2% for summer, autumn and wintertime respectively (Figure 4). Overall, there was persistent pCO₂ undersaturation of the surface seawater at the PAP site throughout the deployment periods, which approximates to annual CO₂ sink estimates of 2.06 ± 2.13, 3.21 ± 1.60 and 3.73 ± 0.84 mol m^-2 CO₂a^-1 for the 2003, 2004 and 2005 deployments respectively. A net CO₂ uptake flux during the 2nd to 4th deployments is estimated to be -2.96 ± 1.73 mol m^-2 CO₂a^-1, indicating a perennial sink for the Northeast basin. However, a significant difference influx on an interseasonal timescale took place during the wintertime, which witnessed a net invasion (strong sink) of CO₂ compared to a moderate sink during the summertime.

Table 1 Air–sea CO₂ flux estimates based on seasonal PAP data given in units of mol m^-2 a^-1

Figure 4 Interseasonal average air-sea CO₂ fluxes at PAP time series site (49 ^oN, 16.5 ^oW) between July 2003 and March 2005

The monthly air-sea CO₂ fluxes for the K1 CELAS observatory (56.5 ^oN, 52.6 ^oW) calculated based on observational data obtained between September 2004 and July 2005 is shown in Figure 5. The spatially monthly averaged air to sea fluxes indicate an oceanographic system that is perennially sequestering atmospheric CO₂ except in the peak of the wintertime (February/March 2005), when an estimated uptake of approximately 0.05 mol m^-2 CO₂a^-1 invaded the seawater system, implying a relatively weak sink. During wintertime, surface water pCO₂approached equilibrium with atmospheric CO₂. Overall, a net CO₂ uptake flux during the K1 CELAS SAMI deployments is estimated to be -1.84 ± 1.3 mol m^-2 CO₂a^-1, with a significantly strong sink capacity of 3.5 mol m^-2 CO₂a^-1 obtained during late summer of 2004.

Figure 5 Monthly air-sea CO₂ fluxes at Northwest K1 CELAS time series site

However, the monthly air-sea CO₂ fluxes at the PAP time series site indicate a temperature dependence on the flux variability. This is an indication that the fluxes are controlled by in situ SST as suggested by the near-linear correspondence between monthly average SST and monthly average flux at the site (Figure 6). In the same way, to elucidate the mechanism that drives the monthly flux variability, which in turn influences the surface oceanic carbon cycle at the K1 CELAS site, a linear plot between CO₂ fluxes and SST is presented in Figure 7. The air-sea fluxes variability as shown by the non-dependence relationship between monthly average flux and SST reveals that the exchange is not entirely dominated by temperature- induced pCO₂-sw.

Figure 6 Monthly air-sea CO₂ fluxes versus SST at PAP site

Figure 7 Monthly air-sea CO₂ fluxes versus SST at K1 CELAS site

3 Conclusions

This work indicates that the surface water pCO₂cycle is characteristically marked by minimum and maximum pCO₂ levels for the summertime and wintertime respectively. There is a significant and consistent undersaturation of the PAP site of the North Atlantic Ocean. The pCO₂concentration at the K1 CELAS demonstrated that the site is mostly undersaturated while exhibiting some degree of supersaturation between February and March 2005. Estimated net CO₂ uptake of 2.96 ± 1.73 and 1.84 ± 1.3 mol m^-2 CO₂a^-1were obtained during PAP (2nd - 4th) and K1 CELAS deployments respectively, thus indicating a regional perennial sink for CO₂. On an interseasonal timescale, significant difference in flux took place during the wintertime, which witnessed a strong pull of CO₂ compared to a moderate sink during the summertime. However, seasonal climatic changes in temperature, stratification, intense biological activities as well as convective mixing processes are identified as the primary drivers of air-sea flux variability for ocean carbon exchange in the region.

Acknowledgements

The EuroSITES Project data was used for this research. The contributions of the principal investigator and other scientists involved in the PAP project are acknowledged. The assistance of Galen McKinley and Arne Körtzingerto the first author is acknowledged. The authors would like to thank anonymous reviewers for their comments and suggestions that much improved the original manuscript.

References

Avsic T., Karstensen J., Send U., and Fischer J., 2006, Interannual variability of newly formed Labrador Sea Water from 1994 to 2005, Geophysical Research Letters, 33, L21S02, doi:10.1029/2006GL026913
http://dx.doi.org/10.1029/2006GL026913

Behrenfeld M.J., O'Malley R.T., Siegel D.A., McClain C.R., Sarmiento J.L., Feldman G.C., Milligan A.J., Falkowski P.G., Letelier R.M., and Boss E.S., 2006, Climate-driven trends in contemporary ocean productivity, Nature, 444: 752-755
http://dx.doi.org/10.1038/nature05317

Dickson B., Yashayaev I., Meincke J., Turrell B., Dye S., and Holfort J., 2002, Rapid freshening of the deep North Atlantic Ocean over the past four decades, Nature, 416: 832-837
http://dx.doi.org/10.1038/416832a

Donelan M.A., and Wanninkhof R., 2002, Gas transfer at water surfaces - concepts and issues. Chapter in Gas Transfer at Water Surfaces, Geophysical Monograph AGU 127: 1-10

Gloor M., Gruber N., Sarmiento J., Sabine C.L., Feely R.A., and Rödenbeck C., 2003, A first estimate of present and preindustrial air-sea CO₂ flux patterns based on ocean interior carbon measurements and models, Geophysical Research Letters, 30 (1): 1010
http://dx.doi.org/10.1029/2002GL015594

Gruber N., Bates N., and Keeling C.D., 2002, Interannual variability in the North Atlantic carbon sink, Science, 298: 2374-2378
http://dx.doi.org/10.1126/science.1077077

Kuss J., Roeder W., Wlost K.-P., and DeGrandpre M.D., 2006, Time-series of surface water CO₂ and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): seasonality of uptake and release, Marine Chemistry, 101: 220-232
http://dx.doi.org/10.1016/j.marchem.2006.03.004

Körtzinger A., Send U., Lampitt R.S., Hartman S., Wallace D.W.R., Karstensen J., Villagarcia M.G., Llinas O., and DeGrandpre M.D., 2008a, Seasonal pCO₂ cycle at 49°N / 6.5°W in the northeast Atlantic Ocean and what it tells us about biological productivity, Journal of Geophysical Research, 113, C04020, doi:10.1029/2007JC004347
http://dx.doi.org/10.1029/2007JC004347

Körtzinger A., Send U., Wallace D.W.R., Kartensen J., and DeGrandpre M., 2008b, Seasonal cycle of O₂ and pCO₂ in the central Labrador Sea: Atmospheric, biological, and physical implications, Global Biogeochemical Cycles, 22, GB1014, doi:10.1029/2007 GB003029

Liss P.S., and Merlivat L., 1986, Air-sea gas exchange rates: introduction and synthesis. In "The Role of Air-Sea Exchange in Geochemical Cycling", P. Buat-Menard editor, D. Reidel Publishing Co., Holland, pp. 113-127
http://dx.doi.org/10.1007/978-94-009-4738-2_5

McKinley G.A., Rödenbeck C., Gloor M., Houweling H., and Heimann M., 2004a, Pacific dominance to global air-sea CO₂ flux variability: A novel atmospheric inversion agrees with ocean models, Geophysical Research Letters, 31, L22308, doi:10.1029/2004GL021069
http://dx.doi.org/10.1029/2004GL021069

McKinley G.A., Follows M.J., and Marshall J., 2004b, Mechanisms of air-sea CO₂ flux variability in the equatorial Pacific and the North Atlantic, Global Biogeochemical Cycles, 18, GB2011, doi:10.1029/ 2003GB002179
http://dx.doi.org/10.1029/2003GB002179

McKinley G.A., Ullman D., Bennington V., Benson N., Fay A., and Dutkiewicz S., 2008, The Changing North Atlantic Carbon Sink: 1992-2006, AGU Fall Meeting Abstracts, 12/2008

Omstedt A., Gustafsson E., and Wesslander K., 2009, Modelling the uptake and release of carbon dioxide in the Baltic Sea surface water, Continental Shelf Research, 29: 870-885, doi:10.1016/j.csr. 2009.01.006
http://dx.doi.org/10.1016/j.csr.2009.01.006

Rutgersson A., Norman M., Schneider B., Pettersson H., and Sahlée E., 2008, The annual cycle of carbon dioxide and parameters influencing the air–sea carbon exchange in the Baltic Proper, Journal of Marine Systems, 74: 381-394. doi:10.1016/j.jmarsys.2008.02.005
http://dx.doi.org/10.1016/j.jmarsys.2008.02.005

Schneider B., Kremling K., and Duinker J. C., 1992, CO₂ partial pressure in Northeast Atlantic and adjacent shelf waters: Processes and seasonal variability, Journal of Marine Systems, 3(6), 453-463
http://dx.doi.org/10.1016/0924-7963(92)90016-2

Schuster U., and Watson A.J., 2007, A variable and decreasing sink for atmospheric CO₂ in the North Atlantic, Journal of Geophysical Research, 112, C11006, doi:10.1029/2006JC003941
http://dx.doi.org/10.1029/2006JC003941

Schuster U., Watson A.J., Bates N.R., Corbière A., Gonzalez-Davila M., Metzl N., Pierrot D., and Santana-Casiano, M., 2009, Trends in North Atlantic sea-surface fCO₂from 1990 to 2006, Deep-Sea Research II, doi:10.1016/j.dsr2.2008.12.011
http://dx.doi.org/10.1016/j.dsr2.2008.12.011

Straneo F., 2006, Heat and Freshwater Transport through the Central Labrador Sea, Journal of Physical Oceanography, 36 (4): 606–628. doi: 10.1175/JPO2875.1
http://dx.doi.org/10.1175/JPO2875.1

Takahashi T., Sutherland S.C., Sweeney C., Poisson A., Metzl N., Tilbrook B., Bates N., Wanninkhof R., Feely R.A., Sabine C., Olafsson J., and Nojiri Y., 2002, Global sea to air CO₂ﬂux based on climatological surface ocean pCO₂, and seasonal biological and temperature effects, Deep-Sea Research Part II: Topical Studies in Oceanography, 49: 1601-1622
http://dx.doi.org/10.1016/S0967-0645(02)00003-6

Takahashi T., Sutherland S.C., Wanninkhof R., Sweeney C., Feely R.A., Chipman D.W., Hales B., Friederich G., Chavez F., Sabine C., Watson A., et al., 2009, Climatological mean and decadal change in surface ocean pCO₂, and net sea–air CO₂ flux over the global oceans. Deep Sea Research II, doi:10.1016/j.dsr2.2008.12.009
http://dx.doi.org/10.1016/j.dsr2.2008.12.009

Thomas H., Prowe A.E., Lima I.D., Doney S.S., Wanninkhof R., Greatbatch R.J., Schuster U., and Corbière A., 2008, Changes in the North Atlantic Oscillation influence CO₂ uptake in the North Atlantic over the past two decades, Global Biogeochemical Cycles, 22, GB4027, doi:10.1029/2007GB003167
http://dx.doi.org/10.1029/2007GB003167

Wanninkhof R., 1992, Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research, 97, C5: 7373-7382
http://dx.doi.org/10.1029/92JC00188

Wanninkhof R., Olsen A., and Trinanes J., 2007, Air–sea CO₂ fluxes in the Caribbean Sea from 2002-2004, Journal of Marine Systems,66: 272-284, doi:10.1016/j.jmarsys.2005.11.014
http://dx.doi.org/10.1016/j.jmarsys.2005.11.014

Wanninkhof R., and McGillis R.W., 1999, A cubic relationship between air-sea CO₂ exchange and wind speed, Geophysical Research Letters, 26 (13): 1889-1892
http://dx.doi.org/10.1029/1999GL900363

Watson A.J., Robinson C., Robinson J.E., Williams P.J.L., and Fasham M.J.R., 1991, Spatial variability in the sink for atmospheric carbon dioxide in the North Atlantic, Nature, 350, 50-53
http://dx.doi.org/10.1038/350050a0

Weiss R.F., 1974, Carbon dioxide in water and seawater: The solubility of a non-ideal gas, Marine Chemistry, 2: 203-215
http://dx.doi.org/10.1016/0304-4203(74)90015-2

Weiss A., Kuss J., Peters G., and Schneider B., 2007, Evaluating transfer velocity wind speed relationship using a long-term series of direct eddy correlation CO₂ flux measurements, Journal of Marine Systems, 66: 130-139
http://dx.doi.org/10.1016/j.jmarsys.2006.04.011

International Journal of Marine Science

• Volume 4

View Options
. PDF(1037KB)
. FPDF(win)
. HTML
. Online fPDF
Associated material
. Readers' comments
Other articles by authors
. Nsikak U. Benson

. Oladele O. Osibanjo

. Francis E. Asuquo

. Winifred U. Anake