We show an annual overview of the sea-air CO2 exchanges and primary drivers in the Gerlache Strait, a hotspot for climate change that is ecologically important in the northern Antarctic Peninsula. In autumn and winter, episodic upwelling events increase the remineralized carbon in the sea surface, leading the region to act as a moderate or strong CO2 source to the atmosphere of up to 40 mmol m–2 day–1. During summer and late spring, photosynthesis decreases the CO2 partial pressure in the surface seawater, enhancing ocean CO2 uptake, which reaches values higher than − 40 mmol m–2 day–1. Thus, autumn/winter CO2 outgassing is nearly balanced by an only 4-month period of intense ocean CO2 ingassing during summer/spring. Hence, the estimated annual net sea-air CO2 flux from 2002 to 2017 was 1.24 ± 4.33 mmol m–2 day–1, opposing the common CO2 sink behaviour observed in other coastal regions around Antarctica. The main drivers of changes in the surface CO2 system in this region were total dissolved inorganic carbon and total alkalinity, revealing dominant influences of both physical and biological processes. These findings demonstrate the importance of Antarctica coastal zones as summer carbon sinks and emphasize the need to better understand local/regional seasonal sensitivity to the net CO2 flux effect on the Southern Ocean carbon cycle, especially considering the impacts caused by climate change.
The investigation of Antarctic coastal regions has long been neglected because they are difficult to access1,2,3,4, especially during periods other than the austral summer5,6,7,8. This occurs because of most of the year, i.e., from April to November, these regions are almost completely or completely covered by sea ice9,10. Such conditions lead to a biased representation of sampling in autumn and winter, which are likely critical periods for changes in seawater carbonate chemistry and net sea-air CO2 flux (FCO2). In fact, several studies have been conducted during the austral summer to better understand the FCO211,12,13,14,15,16 and carbonate system parameter variability17,18,19,20,21,22 in the remote Southern Ocean. It is widely known that the Antarctic coasts behave as a strong CO2 sink during the summer15,23, which has intensified during recent years14,15. Actually, the intensity of this behaviour is marked by high interannual variability, since the summer CO2 fluxes in the Gerlache Strait, for example, oscillate between periods of strong CO2 sink (i.e., < − 12 mmol m–2 day–1) and sea-air near-equilibrium conditions at inter-annual scales15. However, even when Antarctic coastal regions do not behave as a strong CO2 sink, they take up CO2 in the summer15, although eventual episodes of CO2 outgassing can occur20.
Although some studies have provided important information on the seasonality of the FCO27,8,19, they are restricted to a few specific years or localized regions, which may bias the modelled long-term trends of these regions. Hence, understanding the annual budget of sea-air CO2 exchanges remains a challenge4,24. This is particularly true for the Gerlache Strait and likely other major embayments around the Antarctic coasts, since it remains unclear whether this CO2 sink behaviour persists throughout the year or is balanced in other seasons. Moreover, little is known about the main drivers of FCO2 seasonality and their consequences for the sea surface carbonate system. Therefore, here, we present an annual overview of the FCO2 and the carbonate system properties in the Gerlache Strait, an ecologically and climatically important area of the northern Antarctic Peninsula (NAP). Furthermore, we demonstrate that this region acted as an annual net CO2 source to the atmosphere from 2002 to 2017, contrasting with previous findings for the western Antarctic Peninsula environments7,8,19 and other regions around Antarctica25,26,27.
Oceanographic features of the Gerlache Strait
The Gerlache Strait is a coastal region along the NAP that is being impacted by climate change24,28 and is essential for the health of the Antarctic food web29,30,31. The strait is a shallow basin that lies between the NAP and the Palmer Archipelago and is connected to the Bellingshausen Sea (to the west) and the Bransfield Strait (to the north) (Fig. 1a,b). Although it covers a smaller area (~ 8000 km2) than other coastal regions around the NAP, the Gerlache Strait is a highly productive coastal zone. In the Gerlache Strait, records of chlorophyll a (used as an indicator of primary producer biomass) range from ~ 2.0 mg m–331 to ~ 23 mg m–332 under distinct austral summer conditions. These concentrations have the same or a greater magnitude than those observed in more extensive regions, such as the Bransfield Strait (4.4 ± 3.84 mg m–3)32 and the northwestern Weddell Sea (1.38 ± 2.01 mg m–3)33. In addition, the Gerlache Strait has experienced intense diatom blooms reaching > 45 mg m–3 of chlorophyll a32. Although higher, this value is consistent with that recorded in the vicinity of Palmer Station, in the southernmost part of the Gerlache Strait, where the maximum chlorophyll a recorded was ~ 30 mg m–334.
The high biological productivity in this region, reflected at different trophic levels35, is mainly due to the complex interplay of its distinct water mass sources, sea ice dynamics, ocean circulation, nutrient-rich meltwater input and protection from severe weather conditions36,37. Additionally, the rapid effects of climate change24,28,38, a recent increase in glacial meltwater discharge39, and likely the advection of both organic and anthropogenic carbon around the NAP21,40,41 have influenced the coupled physical-biological processes changing the carbon biogeochemistry across the entire western Antarctic Peninsula shelf region28,39.
Moreover, the Gerlache Strait is affected by irregular intrusions of Circumpolar Deep Water (CDW; e.g., Refs.36,42,43,44) (Fig. 1b). CDW is a warm, salty, poorly oxygenated and carbon- and nutrient-rich water mass flowing eastward with the Antarctic Circumpolar Current at intermediate and deep levels around the continent43,45,46. CDW intrusions along the western shelf of the Antarctic Peninsula are often associated with upwelling, mainly caused by shallow bathymetry47 and predominant wind systems36. These intrusions are also affected by modes of climate variability that regulate the intensity of winds in the Southern Ocean, such as the El Niño Southern Oscillation (ENSO) and Southern Annular Mode (SAM)45,48,49. During the positive phases of the SAM, the westerly winds are intensified, and the frequency and intensity of episodic CDW intrusions increase45. Conversely, under extreme ENSO, winds are weakened and cooled48, probably reducing CDW intrusions on the western shelf of the Antarctic Peninsula. Under any of these conditions, the physical properties of CDW change when it is mixed with cooler and less saline surface waters, originating the modified CDW (mCDW) in the shelf and coastal domain.
At depths greater than 100 m, the Gerlache Strait is influenced by the mixing of water masses sourced from the Bellingshausen and Weddell seas. In addition to mCDW, the north of the strait is influenced by a modified variety of High Salinity Shelf Water (HSSW), which is cooler and more oxygenated than CDW45,50. HSSW is formed on the northwestern Weddell Sea continental shelf and is advected towards and along the Bransfield Strait by the Antarctic Coastal Current50,51. Signs of its presence at deep levels of the Gerlache Strait are an important aspect of the NAP because HSSW is younger than CDW, and the biogeochemical impact of mixing between the modified varieties of these waters is not yet completely understood21,22,40. However, a consequence of HSSW is the intrusion of anthropogenic carbon in deep levels of the strait25,26, which can intensify the ocean acidification process in the region.
Hydrographic properties and the carbonate system
Negative sea surface temperatures were recorded from April to November (Fig. 2a), and the lowest values in summer were observed in the northernmost part of the strait, where the highest salinities were recorded (Figure S4). The opposite temperature distribution pattern occurred during spring, when the lowest temperatures were recorded at the southern end of the strait. At the connection between the central basin of the Gerlache Strait and the Bellingshausen Sea (i.e., Schollaert Channel), higher temperatures were associated with lower salinity (Figure S4). On the other hand, the spatial distributions of temperature and salinity in autumn and winter were more homogeneous than those in summer and spring. The carbonate system properties also demonstrated distinct spatial distribution patterns among seasons (Figures S5–S8). The seasonal variabilities of total alkalinity (AT) and total dissolved inorganic carbon (CT) followed that of seawater CO2 partial pressure (pCO2sw) and were inverse to those of pH and the calcite and aragonite saturation states (ΩCa and ΩAr, respectively) throughout the year. AT was higher than CT from December to March and was lower than CT during the rest of the year (Fig. 2d). This seasonal pattern was also observed for CO2 saturation relative to the atmosphere; i.e., the difference (∆pCO2) between pCO2sw and the CO2 partial pressure in the atmosphere (pCO2atm) was positive from April to November and negative from December to March (Fig. 2b). Minimum pH values (total scale) of 7.99 ± 0.02 were observed in winter, while in the other seasons, they were equal to or greater than 8.00 (Fig. 2c). Undersaturated carbonate calcium conditions (i.e., Ω less than 1) were not observed for either species during the seasonal cycle (Fig. 2c), although the lowest surface values of ΩCa and ΩAr were recorded in winter, on average.
In summer, virtually all processes exerted some influence on the surface CO2 system, as shown by the wide dispersion of the salinity-normalized AT and CT (nAT and nCT, respectively; Fig. 3a). In general, carbonate dissolution seems to exert a greater influence in autumn and winter than in spring and summer, although sea ice growth also acts to control AT and CT in winter. Carbonate dissolution/calcification processes were observed to play a role in changing the AT and CT surface distributions in spring, although sea ice growth and melting processes are also expected to exert an influence, mainly during October and November, in association with low temperatures (Fig. 3d) and high pCO2sw. On the other hand, high temperatures (> 0 °C) in spring were associated with an increased influence of photosynthesis on the AT and CT (Fig. 3d).
Drivers of pCO2 sw seasonal changes
CT had the dominant effect on changes in pCO2sw throughout the year. AT and temperature were secondary drivers of these changes, while salinity had a minor influence on surface pCO2sw (Fig. 4). In summer and spring, there was a considerable decrease in pCO2sw, mainly due to the CT drawdown. This decrease was compensated by the increasing effect on pCO2sw of the reduction in AT and the increase in temperature. In winter and autumn, the considerable increase in pCO2sw was driven by the increase in CT and partially compensated for by the increase in AT and decrease in temperature.
Net sea-air CO2 fluxes (FCO2)
FCO2 exhibited distinct seasonality throughout the year, with the region swinging from a strong CO2 sink (FCO2 < − 12 mmol m–2 day–1) in summer to a strong CO2 source (FCO2 > 12 mmol m–2 day–1) in winter (Fig. 5). During autumn and spring, the behaviour of the region oscillated between the major situations normally observed during winter and summer, resulting in a moderate FCO2. Despite this well-marked seasonality, the region was an annual weak CO2 source from 2002 to 2017, with an average estimated FCO2 of 1.24 ± 4.33 mmol m–2 day–1. Notably, with high spatial and temporal variability, this net near-equilibrium condition was achieved because the region switched from a moderate to strong CO2 ocean sink from December to March to a moderate to strong CO2 source to the atmosphere throughout the rest of the year (Fig. 5). Months with the most intense CO2 uptake levels (< − 12 mmol m–2 day–1) have occurred more frequently since 2011, with the peak in January and February of 2016. On the other hand, months with the maximum CO2 outgassing (> 12 mmol m–2 day–1) seem to have become less frequent since 2009 (Fig. 5).
Considering all seasons between 2002 and 2017, high seasonal variability in FCO2 magnitude was identified (Fig. 6). However, the behaviour of the Gerlache Strait as a CO2 sink or source remained almost consistent within each season, as observed in summer (Fig. 6b) and winter (Fig. 6d). Only two particular exceptions occurred in the autumns of 2011 and 2014, when the region was a weak CO2 sink (Fig. 6c). Exceptions were also identified in spring, when the region behaved as a strong CO2 source in 2008 and a particularly strong CO2 sink in 2010 (Fig. 6e). Although the specific episodes in autumn did not appear to influence the average annual FCO2, the unusual spring FCO2 magnitudes coincided with increases in the average annual FCO2 in the respective years (Fig. 6a). The Gerlache Strait acted as an absolute annual CO2 source of 4.4 ± 2.8 mmol m–2 day–1 from 2002 to 2009 and has become predominantly a net annual CO2 sink of − 2.0 ± 3.0 mmol m–2 day–1 since 2010 (Fig. 6a).
A seasonal pattern in the spatial distribution of FCO2 along the Gerlache Strait was also identified. This pattern was characterized by a more homogeneous spatial distribution in autumn and winter (Fig. 7b,c) than in summer and spring (Fig. 7a,d). Moreover, the northernmost part of the strait, north of 64°S, had a higher annual FCO2 (3 ± 8 mmol m–2 day–1) than the southernmost part of the strait, south of 65°S. In the southernmost part, there was an annual CO2 uptake of − 7 ± 16 mmol m–2 day–1.
Seasonal changes in sea-air CO2 fluxes
In late spring and summer, the Gerlache Strait is a CO2 sink, with rates ranging from − 13 ± 12 mmol m–2 day–1 in January to − 5 ± 9 mmol m–2 day–1 in March (Fig. 5). This strong CO2 uptake is driven by an increase in biological activity coupled with meltwater input (Fig. 8a)14,15,20,52,53,54 from December until late summer (Fig. 5), when sea ice formation becomes gradually more intense9,10. This is revealed by the substantial CT drawdown (Fig. 4), which characterizes the influence of photosynthesis on the surface water3,55,56, associated with a slight decrease in AT as a result of further respiration (Fig. 3b). Phytoplankton growth is favoured by the increased stability of the nutrient-rich shallower mixed layer in summer and late spring (Fig. 8a), mainly due to meltwater input14, 46,53,54,57. This is more evident in the southernmost part of the strait, where intrusions of warmer mCDW would likely lead to sea ice melting36 and the higher percentage of meteoric water (Figure S9) than in the northernmost region, which is comparatively ice-free (Figure S9). Hence, this could potentially account for the greater CO2 uptake in the southern region than in the northern region (Fig. 7). Nevertheless, the spatial variability of the carbonate system parameters is clearly greater in spring and summer than in autumn and winter. Therefore, it is likely that other oceanographic processes simultaneously have roles in changing the surface nAT and nCT.
In fact, during early spring, the carbonate dissolution/precipitation and sea ice growth/melt associated with low temperatures (Fig. 3d) seem to influence the carbonate system due to the increase in CT that is rejected through the sea ice brine. However, the impact of each of these processes, and even the presence of other involved processes, is not yet well understood. The dominant processes in spring (i.e., carbonate dissolution/precipitation or photosynthesis/respiration), as well as during other seasons, can also exhibit interannual variability. For example, during summer, there is variability in CO2 uptake oscillating between 2 and 4 years, by which FCO2 in the region alternates between strong CO2 sink and near-equilibrium conditions15. This variability is associated with both intense biological activity and the intrusion of local upwelled CO2-rich waters (e.g., mCDW). In addition, it is linked to the influence of modes of climate variability, such as ENSO, which decreases the wind intensity, leading to favourable conditions for phytoplankton blooms14. This explains why the most intense CO2 uptake was recorded in 2016 (Fig. 5), as this was the year with the most extreme ENSO since 199858, which was associated with biogeochemical changes along the water column41. Therefore, the same mechanism underlying the shift in the dominant physical processes may occur in other seasons of the year. This would likely explain why the region was an exceptionally strong CO2 source in spring 2008 but a strong CO2 sink in spring 2010 (Fig. 6e).
In autumn, the region becomes a moderate CO2 source to the atmosphere, with the maximum magnitude in August (14 ± 7 mmol m–2 day–1). Such behaviour is due to a significant increase in CT, which leads to an increase in pCO2sw. This is further partially offset by the effect that the increase in AT has on pCO2sw (Fig. 4), implicating the upwelling process as a likely cause. In fact, more intense short-term irregular intrusions of mCDW44,59,60 coupled to the deeper mixed layer, which lead to intensified vertical mixing in the winter61, are likely to carry CO2-rich waters to the surface layer of the strait (Fig. 8b). Indeed, this has been the process most observed in other Southern Ocean coastal regions8,11,24. On the western Antarctic Peninsula shelf, for example, there is no evidence of inorganic macronutrient regeneration in late summer, revealing that the increase in CT must be more associated with upwelling and/or advection processes18. Although these mCDW intrusions can occur throughout the year and through virtually all connections of the Gerlache Strait36,42,43, they are expected to be more intense in winter61 and at the southern end of the strait62. In addition, the rejection of CT through sea ice brine63,64 is an important process (Fig. 8b). Despite occurring more intensely in winter than in other seasons, this process should also contribute to CO2 release in autumn, as it was also dominant in controlling AT and CT (Fig. 3c). The increase in CT due to ice growth, first shown in a laboratory experiment63, occurs in both Arctic and Antarctic regions, where there is an intense sea ice dynamic64. Hence, the increase in CT leads to high pCO2sw values but is also related to decreases in ΩCa and ΩAr65. Thus, these conditions contribute to maintaining a relatively low pH (≤ 8.00) until mid-spring, when sea ice begins to melt and both CT and pCO2sw decrease towards the summer season.
Although the spatial distribution of FCO2 is more homogeneous in autumn and winter than in other seasons (Fig. 7), there is intense interannual variability in these fluxes (Fig. 6). It is not yet clear what drives this variability, but it has been linked to sea ice cover variability in other Antarctic regions8,13,66. This link makes sense due to the good correlation (r2 = 0.73; p = 0.0006; n = 12) of the FCO2 seasonal cycle with the sea ice cover seasonality in the Gerlache Strait, mainly in the months when it acts as a CO2 source (r2 = 0.93; p = 0.0136; n = 7) (Figure S10). Despite the strong CO2 outgassing during these periods, sea ice cover constrains sea-air CO2 exchanges8,26, leading to the conclusion that this CO2 outgassing could be even more intense under sea ice-free conditions, as observed in the Arctic Ocean67. Hence, the FCO2 dynamics in sea ice-covered periods may be more sensitive than previously thought.
Seasonality of the carbonate system and acidification process
The carbonate system parameters on the surface of the strait follow seasonal FCO2 dynamics, that is, sea ice dynamics. The lower pH, ΩCa and ΩAr values in winter than in other seasons, although expected, reinforce the biogeochemical sensitivity of this season. The low temperatures and the brine released by sea ice growth lead to the dissolution of calcium carbonate and decreases in ΩCa and ΩAr19. However, we did not find the calcium carbonate in the surface of the Gerlache Strait to be in a subsaturated state, even in winter when there was high pCO2sw; this was also the case in Ryder Bay18,19, a region located farther south on the western Antarctic Peninsula shelf, which is under dynamic conditions similar to those of the Gerlache Strait. In summer, carbonate mineral supersaturation is associated with regions where there is strong CO2 uptake, such as in the southernmost portion of the strait, where meteoric water input is most intense (Figure S9) and salinity is relatively low (Figures S4 and S7). This reveals that the intense pCO2sw drawdown caused by biological activity outweighs the increase in pCO2sw by the effect of carbonate precipitation18, and carbonate dissolution is minimized due to the biological uptake of CT. Nevertheless, the sensitivity of these parameters should be observed in more detail, as carbonate calcification and dissolution processes also seem to play an important role in controlling AT and CT (Fig. 3b,c). Furthermore, because we found minimum pH values in winter (7.92) lower than those at Ryder Bay in 1994 (8.11) and 2010 (8.00)7 as well as between 2011 and 2014 (7.95)19, these waters may be experiencing ocean acidification, although counterintuitive processes may be offsetting the effects in the studied region22. In fact, the waters of the Gerlache Strait have previously been reported to show signs of acidification in summer below the mixed layer20,22, with surface pH values lower than those found at Ryder Bay (8.21–8.4818).
The effects of intensified summer CO2 uptake on calcite and aragonite saturation in surface waters may emerge in the coming years. However, supersaturation of these carbonate species is associated with decreased pCO2sw values in summer15. This reveals that these feedback effects need to be further investigated, especially considering the residence time of these waters in coastal regions. As strong summer CO2 sink periods are extended, an inverse effect of sea surface acidification may occur, as observed in the southernmost portion of the Gerlache Strait. Nevertheless, the acidification process should occur in the deep layers of these strong CO2 sink regions and in adjacent deep waters due to horizontal advection. Indeed, this will likely be the case because the residence time of surface waters in this region was estimated to be less than 7 days, while the residence time in adjacent larger basins ranges between 13 and 40 days50. Therefore, assuming a steady increase in both atmospheric CO268 and temperature69, the Southern Ocean coastal regions may become intense hotspots of deep-ocean acidification, with some expected implications for organisms throughout the water column and the food web as a whole. For example, on the sea surface, there may be a restructuring of the food web due to a shift in the dominant groups of phytoplankton, such as from diatoms to smaller organisms [Refs.24,53 and references therein]. Such changes will potentially decrease the transfer of carbon, energy and nutrients through organisms such as diatoms to pelagic and benthic ecosystems, with complex feedbacks on ocean biogeochemistry and climate24. In this sense, these findings shed light on the importance of clarifying the real impacts of these changes throughout the water column. This is because, despite showing signs of acidification, most studies provide only snapshots, and coupled ocean–land–ice processes can mask the real ocean acidification state of Southern Ocean coastal regions.
Annual budget of sea-air CO2 exchanges
We have identified the Gerlache Strait as a weak CO2 source from 2002 to 2017, with an annual budget of sea-air CO2 exchanges at near-equilibrium conditions. This contrasts with the expectations for other Antarctic coastal regions, which demonstrate annual CO2 sink behaviour5,13,25, such as in summer and spring11,14,33. The studied region acts as a moderate CO2 source in autumn and a strong CO2 source in winter. The CO2 outgassing that occurs during 8 months of the year (i.e., from April to November) is almost fully compensated for in only 4 months (i.e., from December to March), when the region acts as a moderate to strong CO2 sink. Although this behaviour is not considered typical for Antarctic coastal regions, the Gerlache Strait lies at approximately 64°S, where Takahashi et al.70 verified an approximately neutral annual sea-air CO2 flux. Nevertheless, here, we hypothesize that this scenario is more common to coastal regions of the Southern Ocean than previously thought because incipient signs of this behaviour have already been identified in other Antarctic coastal regions. For example, Bakker et al.26 found strong supersaturation of seawater CO2 relative to atmospheric CO2 in autumn and winter in the Weddell Sea but suggested that the region was an annual CO2 sink. These contrasting summer/winter behaviours, with an annual CO2 sink budget, also extend to other Southern Ocean coastal regions, such as the western Antarctic Peninsula5,7,8,11, the Ross Sea13, the Indian Antarctic sector6,71 and even the Antarctic Zone south of 62°S as a whole72. However, the relatively low monthly and interannual coverage in most of these studies may have biased the integrated FCO2 budget throughout the year. This is particularly true if we take into account recent estimates of FCO2 from long-term climatology for global coastal regions4. In this climatology, the NAP, as well as the Weddell Sea and much of the Atlantic and Indian sectors of the Southern Ocean, was a net CO2 source between 1998 and 2015. Despite this, the CO2 uptake by CO2 sink regions was so intense that the annual FCO2 budget for this period was approximately − 17 Tg C year–14.
Expected scenarios for the future of sea-air CO2 exchanges
The recent changes observed in the NAP, mainly related to the intensification of the westerly winds49, rising temperatures73 and the prolongation of ice-free water periods74,75, are expected to persist in the coming years24,28. In this sense, two future scenarios for net sea-air CO2 fluxes can be projected. First, with longer ice-free water periods, these coastal regions could release CO2 that would otherwise remain in the seawater isolated by sea ice, intensifying the annual CO2 source. This release may be enhanced by intensified mCDW intrusion into the western Antarctic Peninsula shelf that have been projected24,45, although little is known about its periodicity and variability. On the other hand, nutrient-rich mCDW intrusions coupled with the delayed sea ice cover period and rising temperatures should lead to prolonged phytoplankton growth75. Thus, strong CO2 sink periods should also extend beyond late summer. As CO2 uptake has intensified in the summer14,15 and proved to nearly counteract annual CO2 evasion, this region could become an annual CO2 sink in future years, particularly assuming that the Southern Ocean is becoming greener75. Actually, this second scenario seems likely to occur, as the magnitude and frequency of FCO2 in months when the region is a strong CO2 sink are increasing and in months when the region is a strong CO2 source have been less frequent (Fig. 5), leading to intensified annual CO2 uptake since 2010 (Fig. 6a).
These scenarios become more complex when we take into account the influence of the modes of climate variability. For example, the positive phase of SAM has been associated with more intense CO2 outgassing due to the deepening of the mixed layer76. Conversely, it was also associated with higher CO2 uptake due to the intensification of upwelling, which supplies iron and nutrients to the sea surface and hence increases phytoplankton growth77. This reveals the sensitivity of sea-air CO2 exchanges to these feedback mechanisms and the urgent need to broaden investigations for a coupled analysis of ocean-climate systems. Nevertheless, signs of intensifying summer CO2 sink behaviour14,15 suggest that the influence of SAM should be reversing the flux to encourage annual net CO2 uptake in Antarctic coastal regions.
Dataset and carbonate system properties
We used the data available from Surface Ocean CO2 Atlas version 6 (SOCATv6)78 to compile a temporal series spanning 2002 to 2017 (Figure S2) of the sea surface (up to a depth of 5 m) temperature (SST), salinity (SSS) and seawater CO2 partial pressure (pCO2sw) of the Gerlache Strait. Here, we evaluated the seasonal variability of the net sea-air CO2 flux (FCO2) and hydrographic and carbonate system parameters. Therefore, the seasons were defined as (1) summer: January to March; (2) autumn: April to June; (3) winter: July to September; and (4) spring: October to December. We analysed the months in which the data covered the majority of the Gerlache Strait in all seasons (Figure S3).
The pCO2sw data extracted from SOCATv6 were directly measured using air–water equilibrators and an infrared analyser for CO2 quantification78. However, SOCATv6 provides surface pCO2sw data with only corresponding SST and SSS values. Hence, we used total alkalinity (AT) from the High Latitude Oceanography Group (GOAL)79 and the World Data Center PANGAEA80 to estimate AT from SSS using Eq. 1 (r2 = 0.98, RMSE = 4.4, n = 140).
These data were sampled in the austral summers of 1995/96 (PANGAEA; https://doi.pangaea.de/10.1594/PANGAEA.825645;81) and 2015–2019 (GOAL; Table S1;15,22). Equation 1 was developed using the curve fitting toolbox of MATLAB, with the least absolute residual mode and first-order polynomial adjustment. This option considered all the data important, minimized the residuals, and can be used when data series have few nonconfigurable values82. Using the estimated AT and pCO2sw from SOCATv6, we calculated the total dissolved inorganic carbon (CT), pH and saturation states of calcite (ΩCa) and aragonite (ΩAr) with CO2SYS version 2.183,84. This program determines these parameters from the thermodynamic equilibrium relation between the carbonate species using carbonate dissociation constants. Because of the good response obtained in high-latitude regions14, 15,20,85,86, we used the constants K1 and K2 proposed by Goyet and Poisson87 and the sulphate and borate constants proposed by Dickson88 and Uppström89, respectively.
Drivers of pCO2 sw changes
The pCO2sw drivers throughout the seasons were calculated based on the difference between the values of the parameters in each season and their respective averages in previous seasons (ΔpCO2drv; Table 1). Then, the ΔpCO2drv values were separated into categories representing the contributions of differences in CT, AT, SST and SSS. The relative contributions of the drivers changing pCO2sw were assessed by converting their relative changes into pCO2sw units (μatm) following Lenton et al.55 as in Eq. 2:
where ΔCT, ΔAT, ΔSST and ΔSSS are the differences between the values of the parameters and their respective averages in previous seasons. This analysis was conducted in each year, and the results were averaged to represent an average year. The partial derivatives were calculated using Eqs. 3 to 6 (see details in Takahashi et al.3). These approximations have been widely used in the Southern Ocean12,21,51 to evaluate pCO2sw drivers, both seasonally and spatially. Here, we used the average Revelle and Alkalinity factors of 14 and − 13, respectively.
Net sea-air CO2 flux (FCO2)
where ∆pCO2 is the difference between pCO2sw and atmospheric pCO2 (pCO2air); Kt is the gas transfer velocity, depending on wind speed91; Ks is the CO2 solubility coefficient, as a function of both SST and SSS92; and Ice is a dimensionless coefficient corresponding to the fraction of the air–water interface (between 0 and 1) covered by sea ice. We used monthly averages of pCO2air and wind speed (m s–1) data from the U.S. Palmer Station, located in the southern part of the Gerlache Strait. The station continuously measures meteorological parameters throughout the year68. We calculated pCO2air from the monthly averages of the atmospheric molar fraction of CO2 (xCO2air) and atmospheric pressure (both from the Palmer Station), which was corrected by the water vapour pressure estimated from SST and SSS by the widely used equations of Weiss and Price93. Sea ice cover was obtained from the monthly mean of the 0.25° daily satellite products by Reynolds et al.94, which cover the entire length of the Gerlache Strait (Figure S9e–h).
Spatial distributions of properties
All spatial distribution maps for the properties in this study were interpolated using Data-Interpolating Variational Analysis (DIVA) gridding95. We used a length scale value of 15‰ for both the X and Y axes to ensure optimal preservation of data structure and smoothness. The averaging and all other calculations performed in this study were based only on the observed or reconstructed data and not on the interpolated data. Map interpolations were made to provide reader-friendly visualization of the results.
Limitations and uncertainties
We estimated the propagated uncertainty from the partial derivatives of all calculated parameters (Table 2) in relation to each variable involved in the calculation as follows:
where the derived functions \(f(x)\) are the calculated parameters (i.e., FCO2, CT, Ω and pH) and σ is the uncertainty associated with each variable involved in calculation of the parameter. Because SSS uncertainties are expected to be low enough to be negligible (i.e., < 0.001, according to the GOAL and PANGAEA datasets), they were not considered here. Hence, the propagated uncertainties in CT, Ω and pH fundamentally represented the errors associated with the estimated AT (± 4.4 μmol kg–1), SST (± 0.05 °C) and measured pCO2sw. We used pCO2sw data from SOCATv6 with uncertainties < 2 µatm (55% of total) and < 5 µatm (45%). We calculated the propagated uncertainties for all carbonate system properties with the CO2SYS error tool96. For FCO2, uncertainty was related to the standard error of the averaged wind speed for each season, the measured pCO2sw and xCO2air, and sea ice cover. The analytical error for xCO2air measurements from the U.S. Palmer Station was estimated to be ± 0.07 µmol/mol for the studied period68. Sea ice concentrations were computed to a precision of 1% coverage94,97.
Finally, we used a first-order polynomial relationship between AT and SSS to estimate AT and calculate the other parameters of the carbonate system based on summertime data. We assumed this relationship for all seasons because the summer was the only period with available AT data for the study region. However, the summer is characterized by greater AT variability than other seasons, implying that the ranges of AT and SSS may represent the annual range (i.e., AT: 2200–2320 μmol kg−1; SSS: 32–34.5). Such limitations are mainly due to the scarcity of data in periods other than summer and highlight the need for additional efforts to better understand the dynamics of the carbonate system parameters in coastal regions of the Southern Ocean.
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This study contributes to the activities of the Brazilian Ocean Acidification Network (BrOA; www.broa.furg.br) and the Brazilian High Latitude Oceanography Group (GOAL; www.goal.furg.br), which is part of the Brazilian Antarctic Program (PROANTAR). GOAL has been funded by and/or has received logistical support from the Brazilian Ministry of the Environment (MMA), the Brazilian Ministry of Science, Technology, and Innovation (MCTI), the Brazilian Navy, the Secretariat of the Interministerial Commission for the Resources of the Sea (SECIRM), and the Council for Research and Scientific Development of Brazil (CNPq) through grants from the Brazilian National Institute of Science and Technology of Cryosphere (INCT-CRIOSFERA; CNPq Grants Nos. 573720/2008-8 and 465680/2014-3; FAPERGS Grant no. 17/2551-0000518-0), NAUTILUS, INTERBIOTA, PROVOCCAR and ECOPELAGOS projects (CNPq Grants Nos. 405869/2013-4, 407889/2013-2, 442628/2018-8 and 442637/2018-7, respectively), and Higher Education Personnel Improvement Coordination (CAPES Grant No. 23038.001421/2014-30). T.M. received financial support from PhD Grant No. 88887.360799/2019-00 from CAPES. R.K. received financial support from researcher Grant No. 304937/2018-5 from CNPq and 888881.195000/2018-01 from CAPES. We are thankful for the resources provided by CAPES to support the Graduate Program in Oceanology. We appreciate the availability of high-quality data from the SOCATv6, PANGAEA and Palmer Station datasets. Special thanks to the scientists (Taro Takahashi, Colm Sweeney, David Munro, Stu Sutherland, Timothy Newberger, Steven van Heuven, Mario Hoppema, Vassilis Kitidis and Ian Brown) onboard the RV Lawrence M. Gould, Nathaniel B. Palmer, Polarstern and James Clark Ross, who provided the surface ocean pCO2 measurements publicly available via the SOCAT dataset. We thank all researchers and students from LEOC/FURG and other GOAL groups for their contributions to cruise planning, sampling, and analyses. We also thank the Brazilian Navy, especially the crew onboard the RV Almirante Maximiano, for providing logistical and sampling support during the NAUTILUS and INTERBIOTA cruises.
The authors declare no competing interests.
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Monteiro, T., Kerr, R. & Machado, E.d. Seasonal variability of net sea-air CO2 fluxes in a coastal region of the northern Antarctic Peninsula. Sci Rep 10, 14875 (2020). https://doi.org/10.1038/s41598-020-71814-0