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The annual cycle of surface CO2 and O2 in the Ross Sea: A model for gas exchange on the continental shelves of Antarctica Colm Sweeney1 1Lamont Doherty Earth Observatory, Palisades, NY 10964. Running Head: Annual cycle of surface CO2 and O2 in the Ross Sea Draft: 10/15/01 Submitted to: Special volume on the Ross Sea of the Antarctic Research Series Abstract The annual cycle of NO3 + NO2 + NH4, CO2 and O2 in the surface waters of the southwestern Ross Sea along 76.5oS is presented in this study. From the surface data and sea ice concentrations annual sea-air fluxes of CO2 (-1.5±1.5 mol C m-2) and O2 (-3.7±3.0 mol C m-2) are calculated and confirmed by a mass balance approach which accounts for the total flux of CO2 (0.16±0.13) and O2 (-5.2±0.2 mol C m-2) entering the Ross Sea from off the shelf. The mass balance approach assumes that a negligible amount of carbon and oxygen accumulates in the sediments and that all of the gas that ventilates to the atmosphere must be replaced by fresher waters entering the Ross Sea. Based on this study, a combination of winter sea ice cover and summer primary productivity prevent any significant change in the CO2 inventory due to gas exchange despite the high partial pressure of CO2 surface waters (425 atm) during the winter. Oxygen inventories in the Ross Sea, on the other hand, are significantly increased as a result of gas exchange with the atmosphere due to low O2 concentrations in the Ross Sea which are 90 mol kg-1 below saturation at sea surface temperatures of –1.89 C. The high flux associated with large sea surface gradient in O2 is the source of high PO4* found in deep waters formed along the Antarctic continental shelf. Based on stability of wintertime CO2 concentrations and the “ice rectification” hypothesis introduced by Yager et al. (1995), it is projected that with increases in atmospheric pCO2 and greater seasonal ice cover, the Ross Sea will become a greater CO2 sink with time. This analysis also supports the hypothesis that winter ice cover and summer primary productivity at the polar front may have been an important factor in the decrease in CO2 during the last glacial maximum. Introduction In the last decade the Ross Sea region has been extensively studied which has lead to a rapid increase in our understanding of the annual variability of inorganic carbon and nutrients (Gordon et al., 2000; Sweeney et al., 2000a; Sweeney et al., 2000b). In particular, the Ross Sea has been noted for the extreme rates of carbon and nutrient uptake through primary productivity of diatoms and Phaeocystis Antarctica (Smith and Gordon, 1997; Arrigo et al., 1999; DiTullio et al., 2000; Smith et al., 2000b). Despite this excessive biological uptake and export of nutrients and inorganic carbon at depths greater than 200 m, there has been little effort to understand what the implications of the high biological uptake and export are to the net air-sea exchange of CO2 and O2 in the Ross Sea. This study will show the annual cycle of CO2 and O2 in the surface of the Ross Sea and the implied air-sea gas exchange that is derived from the observed saturation level of CO2 and O2 in the surface waters and wind speed. In this analysis it is clear that the effect of ice coverage on gas exchange in the Ross Sea is significant and can only be constrained through a careful balance of the carbon and oxygen budgets in the Ross Sea. To estimate of the carbon and oxygen that is entering and exiting the Ross Sea from off the shelf, the balance of salt based on 18O of seawater measurements and an analysis of the hydrological cycle in the Ross Sea made by Jacobs and Fairbanks (Jacobs et al., 1985) will be used. By combining the above estimates with estimates of the annual burial rates of organic matter in the sediments of the Ross Sea, the carbon and oxygen budget can be closed in the Ross Sea. Methods 3.1 Oceanographic cruises The seasonal trends outlined in this study summarize observations made on oceanographic cruises in the Ross Sea during 1996 and 1997 on the R.V.I. B Nathaniel B. Palmer as part of the U.S. Southern Ocean Joint Global Ocean Flux Study (JGOFS/AESOPS, or Antarctic Environment Southern Ocean Process Study, Smith et al., 2000a). The first cruise (NBP96-04A) was designed to observe the early spring prebloom conditions and document the factors controlling the initiation of the bloom. The second cruise (NBP97-01) was intended to investigate the CO2 and nutrient dynamics during the austral summer, while the third cruise (NBP97-03), during autumn, was intended to observe the heterotrophic portion of the seasonal cycle when surface water nutrient and CO2 return to wintertime values. The fourth cruise (NBP97-08) was conducted during the subsequent austral growing season (late spring) between the periods bracketed by the first and second cruise and observed the progression of the bloom through the peak of primary productivity and phytoplankton biomass accumulation. The seasonal trends are based on only those measurements taken from a series stations centered around 76o 30’S. In order to identify major water masses in the Ross Sea, a larger dataset was used which not only included data from the AESOPS cruises but also those from Research on Ocean – Atmospheric Variability and Ecosystem Response in the Ross Sea (ROAVERRS – NBP98-01) (Figure 1). To calculate the pre-phytoplankton bloom carbon and nutrient concentrations of water masses off of the continental shelf, data from the Winter Southern Ocean World Ocean Circulation Experiment (WOCE S-4P, NBP94-05) was used. 3.2 Analytical Methods 3.2.1 Nutrients and Oxygen In general, the methods employed for the bottle salinity, dissolved oxygen, and nutrient analyses (PO43-, NO3-, NO2-, NH4+ and SiO(OH)3-) were similar to those described in the JGOFS protocols (JGOFS, 1996; http://usjgofs.whoi.edu/protocols.html). Minor differences in procedure are described in Gordon et al. (2000) and in the files that accompany the archived data (http//usjgofs.whoi.edu). Particulars concerning nutrient analysis during the NBP94-05 cruise are described in (Rubin et al., 1998) and do not differ significantly from procedures used during the JGOFS cruises. 3.2.2 Carbonate System Carbonate system measurements made on the JGOFS expeditions have been described fully in Sweeney et al. (2000a). Briefly, total CO2 (TCO2) was measured by coulometry in all cruises to precisions less than ±1.4 mol kg-1. All TCO2 values reported in this study have been corrected using Certified Reference Material (http://wwwmpl.ucsd.edu/people/adickson/), whose values were determined manometrically by C.D. Keeling. The partial pressure of CO2 (pCO2) exerted by 500 ml seawater samples during the NBP94-05, NBP97-01 and NBP97-08 cruise was measured by a fully automated equilibrator-gas chromatograph system (Chipman et al., 1993). This system equilibrates 500 ml samples of seawater with a head space of gas of known volume, pressure, temperature and initial concentration of gas. Once the head space has been fully equilibrated with the CO2 gas in the seawater sample a fixed volume of gas was than passed through a gas chromatograph using a hydrogen gas carrier. The hydrogen gas carrier also enabled the catalytic conversion of the CO2 to methane and quantification of the CO2 concentration (mole fraction – ppm) with a flame ionization detector. The CO2 concentration was calibrated using three CO2-air gas mixtures calibrated against the World Meteorological Organization (WMO) standards (Scripps Institution of Oceanography, unpublished data, 1994) whose values bracketed values observed in the water samples. Because the samples were not dried, the partial pressure of CO2 was calculated in the following way: pCO2 @ 4.0 C meas ( ppm) Total pressure of equilibrat ion (atm) (1) where pCO2 @ 4.0 is the partial pressure of CO2 of a seawater sample measured in a constant temperature bath of 4.00 C. The pCO2 was then converted to insitu temperatures using (Chipman et al., 1993): T 0.0423 4.0 pCO2 @T insitu pCO2 @ 4.0 o e insitu (2) where pCO2 @ Tinsitu is the pCO2 corrected to insitu temperatures measured by a conductivity temperature detector (CTD). Based on duplicate measurements, the precision of our measurements was ±0.2 atm. On two cruises (NBP96-04B and NBP97-03) alkalinity measurements were made instead of pCO2 measurements. The alkalinity measurements (Millero et al., 1993) were made with a precision of ±2.0 mol kg-1. From the alkalinity, TCO2, temperature, salinity and nutrient measurements, the partial pressure of CO2 was calculated using formulations of Roy et al. (1993). As described in Sweeney et al. (2000a), a comparison with other methods and constants indicate that the calculated deep water alkalinities from the Roy et al. (1993) formulation are closest to those measured in the deep water of the Ross Sea. 3.1.3 Wind and ice data Sea ice concentrations presented in this study are derived from multi-channel passive microwave SSM/I (1996-present) satellite data. This data is available from the EOS Distributed Active Archive Center (DAAC) at the National Snow and Ice Data Center (NSIDC), University of Colorado in Boulder, Colorado (http://nsidc.org). NSIDC provides sea-ice concentrations derived from both the Goddard Space Flight Center (GSFC) NASA Team (Cavalieri et al., 1991; Cavalieri et al., 1997; Gloersen et al., 1992) and Bootstrap (Comiso, 1995) algorithms. The two algorithms use different channel combinations, reference brightness temperatures (i.e., tie-points) and weather filters, so they therefore have different sensitivities and biases (Comiso, 1997). The data used in this study has been derived using the Bootstrap algorithm. 3.1.4 The annual climatology It is clear that the annual variability physical, biological and chemical is extreme in the Ross Sea (Jacobs and Giulivi, 1998; Orsi et al., 2001). However, in an effort to put together a climatological average for the Ross Sea. it is necessary to merge data from a few different years together. In particular, this paper will merge the four JGOFS cruises into one year requiring data collected November and December of 1997 to fall between data collected in late October of 1996 and data collected from January and February of 1997. Admittedly, other physical, chemical and biological data indicate that the conditions of the November/December cruise made in 1997 differ significantly from the previous year. One of the most significant differences is ice cover. To adjust for this discrepancy, the ice coverage for both years will be shown to indicate how a major physical constraint on the biological draw down or production of CO2 and O2 may have affected the seasonal cycle. In the end, it should be pointed out that the relative timing of the onset of the bloom makes little difference to the overall flux of CO2 and O2 in the Ross Sea. Results 4.1 Seasonal cycle of physical parameters in the Ross Sea The seasonal cycle of temperature and salinity in Ross Sea is unique compared to many other areas of the world oceans because while ice melting and freezing drive dramatic changes in surface salinity, surface temperature does not vary more than 2 C throughout the whole season cycle (Figure 2a-b). The combination of small seasonal changes in temperature and large seasonal changes in salinity makes salinity changes and, by inference, ice melt and freezing, the primary drivers of seasonal stratification in the Ross Sea. Figure 2c shows a rapid increase in the mixed layer depth along 76.5oS in the southwestern Ross Sea from late winter values of ~400 m (depth representing a 0.05 kg m-3 increase in density from the surface, http://usjgofs.whoi.edu/) with the decrease in ice concentration. By mid-January the mixed layer depths along 76.5oS are 40 m. With the onset of ice in late March the pycnocline at the surface has been eroded concurrently with an increase in salinity and sea ice concentration to depths of ~200 m. 4.2 Annual cycle of surface CO2, O2 and nutrients in the Ross Sea 4.2.1 Annual nitrogen and carbon cycle From deep water measurements of pCO2 made in the late austral winter of the 1996, it is estimated that the surface pCO2 is 425 atm at temperatures of -1.89 C before the phytoplankton bloom has started in the southwestern Ross Sea (Figure 3a). By the end of October, a decrease in pCO2 of almost 25 atm and little change in temperature indicate a draw down in CO2 through primary production despite heavy sea ice cover. This draw down in CO2 accelerates as the sea ice concentration decreases. At the time of the maximum draw down in CO2 in late January, pCO2 values are as low as 130 atm along 76.5oS. Low values in pCO2 in the upper 20 m of the water column correspond to TCO2 values of ~2075 mol kg-1 which are ~150 mol kg-1 below the pre- phytoplankton bloom values of 2233 mol kg-1 (Figure 3b). By the time winter sea ice concentration have reached a winter average of 80%, the pCO2 and TCO2 concentrations appear to be returning to winter values. Measurements in late March indicate that mean TCO2 and pCO2 in the upper 20 m of the water column were 2218 mol kg-1 and 377 mol, respectively which is still below pre-phytoplankton bloom levels. Similarly, the total inorganic nitrogen (NO3 + NO2 + NH4, TIN) decreases rapidly due to the onset of a phytoplankton bloom starting at the end of October. This draw down in TIN from values of 30 mol kg-1 continues through late January resulting in TIN values as low as 5 mol kg-1 in the upper 20 m of the water column by the end of January. As with the pCO2 and TCO2, surface TIN, values do not return to prephytoplankton bloom values by late March despite the fact that phytoplankton growth has stopped (Smith et al., 2000b) and the mixed layer extends to depths of 200 m (Figure 3c) – implying significant overturning of deep CO2 saturated waters. To illustrate how the surface concentration of TCO2 would evolve from prephytoplankton bloom levels without gas exchange, the change in TIN and the Redfield ratio based on Takahashi et al. (1985) are used (solid lines in Figure 3b). Using the trend line from Figure 3c and the Redfield ratio for TCO2: TIN derived along deep ocean isopycnals (116/16, Takahashi et al., 1985) an estimated concentration of TCO2 without the effect of gas exchange (TCO2NOGAS) in the surface waters along 76.5oS is derived using the following: TCO2NOGAS=TIN(116/7)+TCO2DW (3) where TCO2DW pre-phytoplankton bloom value of TCO2 (2233 mol kg-1) and TIN is the change in surface TIN concentration from pre-phytoplankton bloom conditions. This estimate does not include the effects of gas exchange and assumes: 1) that the biological uptake and remineralization of inorganic carbon and nitrogen occur at a constant ratio and 2) that the ratio of TIN and TCO2 below the mixed layer stays constant. By the end of March, when the mixed layer depths are ~200 m, the difference in measured TCO2 and the TCO2NOGAS is 6.4 mol kg-1 indicating a net flux of less than 1.3 mol C m-2 into the Ross Sea for the period beginning in early October to the beginning of March (Table 1). 4.2.2 The annual oxygen cycle Concurrent with the dramatic draw down in CO2 and TIN, the surface oxygen increases from pre-phytoplankton levels far below saturation (~280 mol kg-1, 100 mol kg-1 below saturation) to values greater than 400 mol kg-1 through the middle of December when there is a large data gap. Because of the small inventory of O2 in the mixed layer and the large variability in sea-air flux in the Ross Sea, it is difficult to estimate how supersaturated O2 concentrations became as a result of the biological production in the period when no measurements have been made. In the same way that the change in TCO2 concentration with no gas exchange is estimated over the growing season, the change in oxygen concentration in the surface waters can be estimated. The change in oxygen concentration with no gas exchange (O2NOGAS) is estimated using the change in the TIN concentration and the Redfield ratio for O2:TIN ratio of 170/16 (Anderson and Sarmiento, 1994): O2NOGAS=TIN(170/16)+O2DW (4) where O2DW pre-phytoplankton bloom value of O2 (280 mol kg-1). From the change in TIN concentrations it is clear that without gas exchange O2 values could be as high as 150 mmol kg-1 over saturation in late December (solid line Figure 3d). With gas exchange and moderate gas exchange fluxes, it is likely that the oxygen concentration continues to rise with the increases in chlorophyll concentrations which are observed in late December (indicating increases in primary productivity, Arrigo et al., 2000). Based on the relative saturation of oxygen in the surface waters and the low average monthly wind speeds in late December and early January, it is likely that the O2 values will reach 450 mol kg-1. The peak in O2 rapidly lowers with decreases in primary productivity, and increases in wind speed – effectively shutting down the source of new O2 and decreasing the residence time of O2 in the mixed layer, respectively. Although there is another data gap between the middle of February and late March, there is a significant downward trend in oxygen indicating that oxygen fell below saturation by the end of February due to remineralization of organic matter and overturning of deep oxygen depleted waters in the Ross Sea. 4.2.3 The significance of 76.5oS in southwestern Ross Sea It is clear from other studies of the Ross Sea that the biological draw down of CO2 and TIN and production of oxygen observed along the 76.5oS is not necessarily representative of the average in the Ross Sea. Indeed, Sweeney et al. (2000a) point out that the areal average net community production (NCP) over the whole Ross Sea (defined by the area inside of 1000 m isopleth) is ~65% of the average NCP along the 76.5oS (7.5 mol CO2 m-2) by the end of January. Because sea ice is slow to disappear in other areas of the Ross Sea, the draw down in nutrients and measured primary productivity is significantly delayed and reduced due to the shorter interval of sea ice-free conditions throughout most of the Ross Sea (Arrigo et al., 2000). Thus, while the seasonal trends in the surface concentrations of nutrients, carbon and oxygen along 76.5oS are useful for illustrating the relationship between ice concentration and chemical composition of the surface waters, the nutrient and carbon draw down at this location should be considered an end-member in the Ross Sea. 4.3 Annual air-sea fluxes of CO2 and O2 While fluxes of TCO2 and O2 can be estimated by using TIN over the bloom period, these estimates makes many assumptions about the biological uptake and remineralization ratios as well as the pre-phytoplankton bloom ratios of TCO2, O2 and TIN in water masses that may move into the study area over the course of the bloom. It is important, therefore, to look at other methods for estimating gas exchange fluxes. One such method is the direct calculation of the gas transfer coefficient across the sea surface using the relative saturation of CO2 and O2. The net sea-air flux of CO2 and O2 is calculated using: F = kC w - sC a (5) where s is the inverse of Henry’s Law Constant (the ratio of concentration of gas in air to the concentration of gas in water) or the solubility coefficient of the gas in water and Cw and Ca are the concentration of gas in seawater and the overlying air, respectively. The solubility for CO2 and O2 were calculated as a function of temperature and salinity (Weiss, 1970;Weiss, 1974), k (cm hr-1) is gas transfer velocity which is taken to be a function of wind speed (Wanninkhof, 1992). Local wind speeds have been compiled by National Center for Environmental Prediction – National Center for Atmospheric Research (NCEP-NCAR) (Lamont Climate Group Library – http://rainbow.ldeo.columbia.edu). To calculate the gas transfer coefficient for average monthly wind speeds (uav) the following is used: k = 0.39 uav2 (Sc/660)-0.5 (6) where k (cm hr-1) is the gas transfer velocity and Sc is the Schmidt number, which is a dimensionless function of temperature and salinity. Although this relationship has been found to be consistent with the direct measurements obtained during the recent Gas Ex-98 field study using a eddy-correlation method (Wanninkhof and McGillis, 1999), errors resulting from the non-linear relationship between wind speed and gas transfer velocity can lead to underestimates of average transfer velocities in regions with highly variable wind speeds. Because of highly variable wind speeds in both space and time, the transfer velocity represented by Eq. (6) in the Southern Ocean may be underestimated by as much as 30% (Boutin and Etcheto, 1991). Table 1. Sea-air flux along the 76.5oS in the Southwestern Ross Sea. Fluxes are calculated assuming no sea ice cover (without ice), with sea ice (with ice) and based on the difference in measured and estimated oxygen and CO2 using the change in TIN (TIN and equation 3 and 4). Flux is expressed as mol m-2 for the time interval indicated and positive values represent a flux out of the Ross Sea. Gas Annual Flux CO2 (without ice) CO2 (with ice) CO2 (TIN) O2 (without ice) O2 (with ice) O2 (TIN) -0.45±1.0 -1.5±1.0 -47.3±3.0 -3.7±3.0 Bloom period flux (Mid Oct. –Mar.) -2.0±0.45 -1.8±0.45 -1.3±0.8 -3.4±1.5 4.6±1.5 2.7±1.0 Winter Gas flux (Mar. –Mid Oct.) 1.55±0.7 0.1±0.6 -44±1.5 -8.3±1.5 4.2.1 CO2 sea-air fluxes For CO2 the large difference between atmospheric and surface water pCO2 (pCO2) results in a large flux of CO2 into the Ross Sea (1.8 mol m-2) from Mid October to Late March when the Ross Sea is open (Figure 3a and 4a). This large flux into the Ross Sea is driven by the biological draw down in CO2 from late October to the middle of February. While it is unclear how sea ice will effect gas exchange, assuming that the gas exchange is linearly proportional to surface concentration of sea ice would result in a dramatic reduction of gas exchange after the beginning of March until the middle of October. Because of the heavy sea ice cover, it is unlikely that the CO2 supersaturated surface waters in the Ross Sea are well ventilated in the winter. Yager et al. (1995) refer to the reduction in the sea-air exchange of CO2 during winter due to sea ice as a “seasonal rectification”. In their model they suggest that sea ice not only impedes gas exchange during the winter but also provides a habitat for ice-algae to grow at the end of the winter. The ice algae and phytoplankton which take advantage of the shallow mixed layers left by melting ice both act to significantly draw down CO2(aq) concentrations in the water through photosynthesis. Thus, further inhibiting ventilation of the CO2 rich winter waters as the sea-ice melts. Because the sea-air flux of CO2 is small (average of 0-25 mmol m-2 day-1) compared to the large deficit (~6000 mmol m-2, assuming TCO2 concentration are 150 mmol kg-1 below saturation and 40 m mixed layer depths), the period with no sea-ice is not long enough for the gas flux to return the CO2 concentrations back to equilibrium with the atmospheric CO2 concentrations without the additional help of overturning of the deep waters. In this way the biological draw down and sea ice act to suppress ventilation of highly super-saturated waters with respect to CO2. 4.2. O2 sea-air fluxes A similar cycle is seen in the annual flux of oxygen (Figure 4b). Because of the highly super saturated surface waters in the early part of the bloom period (Figure 3d), there is a large flux of O2 out of the Ross Sea. This degassing of O2 from the surface waters continues through the middle of February when the mixed layer depth decrease indicates that overturning and primary productivity have reached their minimums (Gordon et al., 2000; Smith et al., 2000b). Accounting for sea ice in the daily O2 fluxes reduced the annual sea-air flux from –47 to –4 mol m-2. It is also evident from the quick rise in oxygen above saturation levels (Figure 3d) that biological production of oxygen prevented the ventilation of O2 depleted waters as sea ice concentration decreased in the early austral spring. Unlike CO2 the sea-air flux of oxygen is large (0-200 mmol m-2) while the deficit of oxygen is small (~3000 mmol m-2, assuming the O2 concentration is 75 mmol kg-1 above saturation and 40 m mixed layer depths). Thus, while daily flux of CO2 into the Ross Sea is too small to bring the CO2 back to equilibrium in the time lag between the heavy net community production and the onset of sea ice at the end of the austral summer, the daily flux of O2 is sufficient. With a large flux of O2 out of the Ross Sea and deepening mixed layers, the O2 concentrations quickly become under-saturated and provide a gradient for a strong flux of O2 into the Ross Sea both before and after the onset sea ice cover in the Ross Sea. In this way the oxygen cycle is similar to the CO2 cycle in the Ross Sea because the sea ice “rectifies” the winter flux of oxygen into the Ross Sea; however, biological productivity is not as effective at preventing ventilation of O2 under-saturated deep waters. It is likely that the impact of primary production on the sea-air flux of oxygen is even less pronounced throughout the rest of the Ross Sea where primary production is reduced significantly due to a possible lack of micro-nutrients and persistent sea-ice cover (Martin et al., 1990; Arrigo et al., 1998; Fitzwater et al., 2000). The rapid equilibration time of O2 and the highly under-saturated waters observed in the late winter (~80 mol kg-1 below saturation) at the surface are essential mechanisms for providing excess oxygen to the deep waters formed on the shelf regions of the Antarctic. Broecker et al. (1986) exhibits this phenomena in the distribution of PO4* in the world oceans. PO4* illustrates the ratios of oxygen concentration ([O2]) to phosphate ion concentration ([PO4]) in the following relationship: PO4*=[PO4] + [O2]/175 - 1.95 (7) The distribution of PO4* indicates that deep water in the North Atlantic may have values as low as 0.73 mol kg-1 while deep water formed around the shelves of the Antarctic have values as high as 1.95 mol kg-1. Assuming that 175 moles of O2 are used up for every phosphate ion produced in biological remineralization (and the reverse for biological production), variations in PO4* precludes the effect biology on the oxygen to phosphate ratios. For this reason waters with a high PO4* found on the continental shelves of the Antarctic are waters where O2 has been added through non – biological process such as sea-air gas exchange. 4.4 Estimates of CO2 and O2 due to deep water formation While estimates of the sea-air fluxes of CO2 and O2 based on direct measurements of surface water concentrations and wind speed provide an initial estimate of the sea-air flux, the high meso-scale variability and temporal gaps in data collection add large amount of uncertainty to the estimates. To confirm the estimates made from surface measurements in the southwestern Ross Sea, an attempt to approach the problem from the bottom up is made by estimating the sea-air flux based on the difference in CO2 and O2 being buried and exported on and off the shelf. This problem has been somewhat simplified by a 14C analysis done which shows negligible accumulation of organic carbon (0.012 mol C m-2 yr-1) in sediment cores west of 175 W in the Ross Sea (DeMaster et al., 1996). This would imply that if there is a flux of O2 or CO2 into or out of the Ross Sea through sea-air gas exchange it would be transported off the shelf to insure a constant annual mean concentration of both gases. Table 2 Average values of physical and chemical properties for water masses found in the Ross Sea. Temperature, salinity and 18O are taken from Jacobs et al. (1985). Nutrient and CO2 data for High Salinity Shelf Water (HSSW, S>34.6 and T<1.5C), Low Salinity Shelf Water (LSSW, S<34.6, T>-1.89C and T<-1.5C), Deep Ice Shelf Water (DISW, S>34.6 and T<-1.89C), Shallow Ice Shelf Water (SISW, DISW nutrients have been normalized by salinity) and Modified Circumpolar Deep Water (MCDW, T>-1.5C, SiO4>78 mol kg-1) taken from JGOFS/AESOPS data during October, 1996; February, 1997; April, 1997 and NovemberDecember, 1997. Nutrient and CO2 data for Circumpolar Deep Water (CDW, Maximum temperatures below 150 m), Winter Water (Tmin, Minimum T in upper 100 m) and Antarctic Surface Water (AASW, values based on salinity verses concentrations trend), taken during the austral winter (September-October) of 1994 in the Ross Gyre between 175oW and 140 oW (NBP94-5). Water Mass CDW AASW WW HSSW LSSW MCDW SISW DISW Temp (C) 1.17±0.25 -0.96±0.57 -1.64±0.18 -1.91±0.02 -1.56±0.21 -0.84±0.33 -2.04±0.04 -2.03±0.08 Salinity 34.70±0.02 34.11±0.18 34.30±0.05 34.84±0.05 34.53±0.04 34.54±0.02 34.36±0.02 34.68±0.04 18 O TCO2 TIN (o%) (mol kg-1) (mol kg-1) -0.07±0.05 2255±1 32.3±0.1 -0.31±0.08 2193±2 27.7±0.7 -0.44±0.15 2218±2 30.5±0.7 -0.42±0.05 2256±1 30.8±0.1 -0.45±0.04 2232±1 30.0±0.1 -0.34±0.09 2240±1 31.2±0.1 -0.58±0.04 2227±1 30.6±0.1 -0.54±0.06 2247±1 30.9±0.1 PO4 SiO4 Oxygen (mol kg-1) (mol kg-1) (mol kg-1) 2.22±0.01 93.5±1.2 183±1 1.96±0.05 55.5±5.2 300±6 2.09±0.05 73.0±5.3 255±6 2.16±0.01 78.2±0.2 285±1 2.10±0.01 76.4±0.2 283±1 2.18±0.01 86.2±1.0 247±3 2.15±0.01 77.1±0.1 281±1 2.17±0.01 77.8±0.1 284±1 4.4.1 Background In the most simplistic picture, the Ross Sea may be defined as a region which has a total area of ~940,000 km2 bounded by the 1000 m isopleth to the northeast (~73°S) between Cape Adare (170°E) and Cape Colbeck (158°W) (Figure 1). Almost 500,000 km-2 of the Ross Sea is covered by the Ross Ice Shelf which extends to a depth of greater than 200 m and covers the regions to south of 78°S. To the north and east of the shelf slope break is an area called the Ross Gyre. The Ross Gyre extends north to the Antarctic Circumpolar current (ACC) from 160°E to 140°W. In this sector of the Southern Ocean the southern limit of the ACC lies between 65°S and 60°S (Orsi et al., 1995). The waters of the Ross Gyre are contained between the ACC and the Ross Sea and flow clockwise (cyclonic) driven by westward winds located south of the ACC. At the southern extreme of the Ross Gyre the clockwise circulation translates into a westward flow. A portion of this westward flowing water moves onto the continental shelf of the Ross Sea while the bulk of it moves along the continental slope (Gill, 1973; Ainley and Jacobs, 1981) and mixes with HSSW, LSSW and ISW coming off the shelf at depths greater than 500 m. From this simplified picture other investigators have assumed that only half of the AABW formed on the continental slope of the Ross Sea is HSSW, LSSW and ISW (Jacobs et al., 1985). The rest of the water making up AABW is Lower Circumpolar Deep Water (LCDW) which originates to the north at a depth below 2000 m in the ACC but reaches 200 m depth as it flows poleward (Locarnini, 1994). Because it is partially formed from warmer intermediate waters to the north of the ACC, the LCDW plays an important role supplying the heat needed to maintain the polynyas at the shelf break of the Ross Sea through most of the winter (Jacobs and Comiso, 1989). Once the LCDW has moved onto the shelf it is observed to have temperatures and salinities lower than those observed off the shelf due to mixing with fresher and colder surface waters and was first distinguished as Modified Circumpolar Deep Water (MCDW, Jacobs et al., 1970, Figure 5a and 6, Table 2). It is the LCDW and colder Antarctic Surface Waters (AASW) and Winter Water (also known as temperature minimum water, Tmin) which replace the colder and more saline HSSW, LSSW and ISW water leaving the Ross Sea. To keep this circulation going, it is important to not only extract heat but also add salt to the waters going off the shelf. While heat can easily be extracted by the relatively high winds, weak pycnoclines and deep mixed layers, the addition of salinity requires a more complicated process. One of the primary mechanisms suggested for generating the salinity needed to create HSSW, LSSW and ISW in the Ross Sea is through brine rejection (Gill, 1973; Killworth, 1974; Jacobs et al., 1985; Zwally et al., 1985; Broecker et al., 1986; Locarnini, 1994; Toggweiler and Samuels, 1995). Through this mechanism AASW in the Ross Sea are frozen and pushed northwest off the shelf by prevailing currents and winds (Jacobs and Comiso, 1989). The brine left behind by the exported sea ice is added to the water of the Ross Sea to form LSSW and HSSW. From the relatively high salinity, low 18O and supercooled temperature of ISW (Table 2) it is likely Deep Ice Shelf Water (DISW) is formed from HSSW that has been subducted under the Ross Ice Shelf to a depth sufficient to allow the temperatures to decrease below the surface freezing point due to basal melting of the Ross Ice Shelf. 4.4.2 The Ross Sea salinity balance Using a mass balance approach and estimates of salinity, temperature and 18O specified by Jacobs et al., (Jacobs et al., 1985) (Figure 5a-b, 6 and Table 2) a net flux of 45 cm yr-1 of ice are exported off the shelf which translates into the formation of 1.4 Sof deep water on the continental shelf defining the Ross Sea. This calculation is based on the following assumptions made by Jacobs et al. (1985) including proportional mixture of waters flowing on and off the shelf (Table 3): Assumption #1: The average 18O of water in Ross Sea stays constant (at steady state) despite a large input of 18O depleted melt water and precipitation. Based on Jacobs et al. (1985), glacial melt water, with a 18O of -36o% is added to the average depth of the Ross Sea at the rate of about 0.36 m yr-1 thus decreasing the 18O by 0.025o% yr-1. In addition, the estimated precipitation and the freezing of sea ice will decrease the 18O by 0.005o% yr-1 and 0.002o% yr-1, respectively. The cumulative decrease in the 18O (0.0332o% yr-1 *3.2 x 105 km3) will be countered by an equivalent increase in the 18O due to the difference in the 18O coming on and going off the shelf (0.24o%, Figure 5b, 6 and Table 2). Thus, Annual 18O decrease (precip., ice melt, etc.) = (0.0332 o%)(3.2 x 1014 m3) =1.06 x 1013 o% m3 yr-1 18O flux increase from deep water formation = (0.24 o%)(Deep water formation rate) Assuming no inter annual variability in 18O (steady state): 18O flux increase from deep water formation =Annual 18O decrease (precip., ice melt, etc.) Deep water formation rate = 4.39 1013 m3 yr-1 (or 1.4 S) Table 3 Average values of water flowing onto the continental shelf of the Ross Sea based on water mass recipes from (Jacobs et al., 1985). Temp (C) Inflow Water* -0.065 Salinity 34.453 18 O TCO2 TIN PO4 SiO4 Oxygen (o%) (mol kg-1) (mol kg-1) (mol kg-1) (mol kg-1) (mol kg-1) -0.2225 2230±1 30.7±0.2 2.12±0.02 78.8±1.9 230±2 34.54 -0.42 2232±1 30.3±0.2 2.12±0.01 76.5±1.1 276±2 Average Shelf -1.45 Water** -1.689 34.5876 -0.465 2237±1 30.2±0.1 2.12±0.00 76.8±0.2 283±1 Outflow Water*** *Water coming onto shelf=50% CDW + 25% AASW + 25%WW **Average Shelf water = 15% AASW +20% MCDW +35% LSSW + 20% HSSW + 5% DISW+ 5% SISW ***Average going off = 70% LSSW + 10% HSSW + 20% DISW Assumption #2: Ice contains ~4100 g salt m-3 (Jacobs et al., 1985) which is about 10% of normal seawater. Using this assumption, the quantity of ice that is be exported off the shelf can be calculated based on the salinity difference between water coming onto and off of the shelf (0.135) given the formation rate of deep water. Salt flux onto the shelf = Salt flux off the shelf Salt flux off of the shelf = (134.6 g m-3)(4.39 1013 m3 yr-1) = 5.91 x 1015 g salt yr-1 Salt flux onto the shelf = (Depth of net ice export)(Area of RS)(Salt released by ice) Depth of net ice export = 5.91 x 1015 g salt yr-1/30000 g salt m-3/4.41 x 1011 m2 = 0.45 m yr-1 Assumption #3: Using a mass balance approach Jacobs et al. (1985) suggest that precipitation and glacial melt add 0.52 m yr-1 of freshwater to Ross Sea per year and only half of the ice formed is exported off the continental shelf. From this, the total amount of ice formed each year can be calculated. Salt flux to balance fresh water input = (Salt content of Ross Sea)(Depth of freshwater) 1.8 x 104 g salt m-2 yr-1 = (34540 g salt m-3)(.52 m yr-1) Ice export to balance fresh water = (Salt flux to balance fresh water input)/(Salt released by ice) 0.60 m yr-1 = 1.8 x 104 g salt m-2 yr-1/(34110 g salt m-3-4100 g salt m-3) Annual ice accumulation = 2[(Net ice export) + (Ice export to balance fresh water)] = 2(0.45 m yr-1 + 0.60 m yr-1) = 2.10 m yr-1 Assumption #4: Along with salt rejection there will also be an enrichment in nutrients and CO2 due to the brine left behind as a result of exported ice. Thus, the total flux of CO2, nutrients and oxygen onto the shelf can be calculated as sum of net flux, incoming minus outgoing flux of nutrients, and the flux of nutrients derived from brine left by the sea ice exported off the shelf (brine flux). Table 4: Fluxes of Nutrients and CO2 coming into the Ross Sea. The brine flux into the Ross Sea is calculated assuming that the source of ice is AASW and that the same fraction of nutrient and CO2 will be removed from the AASW as salt (the salinity of the ice is assumed to be 4.1). The net flux into the Ross Sea is based on the difference in nutrient and CO2 flux coming into and going out of the Ross Sea (Table 1.2). Uncertainties reflect the propagation of errors from estimating average nutrient and CO2 concentrations of incoming and outgoing water. Brine Flux: Nutrient (109 . mol yr-1) TCO2 386.5±0.2 NO3+ NO2+NH4 5.2±0.0 PO4 0.37±0.00 SiO4 13.3±0.2 O2 47.9±0.3 Net Flux: (109 . mol yr-1) -315.2±58.6 19.9±8.7 0.05±0.83 88.1±83.4 -2325±82 Total Flux Total Flux (109 . mol yr-1) (mol m-2 yr-1) 71.3±58.6 0.16±0.13 25.1±8.7 0.06±0.02 0.001±0.002 0.42±0.83 101.4±83.4 0.2±0.2 -2276.9±81.8 -5.2±0.2 Figure 7a-c shows the salinity normalized concentrations of TCO2, O2 and SiO4 as a function of salinity. By normalizing the each water mass concentration to the mean salinity of the Ross Sea one can see the effect of ice melt and precipitation or freezing and evaporation have on each water masses. While not as rigorous as the calculations described above it helps to illustrate difference between the concentrations of all the water masses in addition to accounting for concentration enrichment due to brine rejection. It is clear from the error bars that while oxygen in the waters leaving the Ross Sea are enriched by 50 mol kg-1 and accounts for a total flux off the Ross Sea shelf of 5.2 mol O2 m-2 yr-1, the total CO2 and silicate in the waters leaving the Ross Sea is not significantly depleted. The fact that only 0.2±0.2 mol of SiO4 m-2 is added to the Ross Sea annually is an important confirmation of the recipes for incoming and outgoing waters suggested by Jacobs et al. (1985) because it confirms estimates which suggested that 0.11 mol SiO4 m-2 yr-1 accumulates on the shelf every year (DeMaster et al., 1996). If the amount of CDW entering the Ross Sea was 60% of incoming water masses instead of 50% as Jacobs et al. (1985) suggest the accumulation SiO4 would increase to 0.5±0.2 mol m-2yr-1 – an estimate significantly different from DeMaster et al. (1996). The salinity balance and the recipes of incoming and outgoing water masses of Jacobs et al. (1985) confirms that there is a significant sea-air flux of O2 into the Ross Sea but does not confirm the air-sea flux of CO2 into the Ross Sea calculated from the annual climatology of sea surface pCO2. The lack of convergence in estimates may be explained in two ways. First, it is important to acknowledge that in addition to the many assumption made to for the salinity balance approach no accounting has been done of particulate matter that may be exported out of the highly productive Ross Sea. This is especially relevant in light of the disparity between estimates of exported particulate carbon in the Ross Sea. Sweeney et al. (2000b) suggested that 3.8 mol m-2 of organic carbon was exported past 200 m based on the difference between NCP and total organic carbon in the upper 200 meters while only 0.29 mol C m-2 was caught in the sediment traps at 200 m (Collier et al., 2000) during that same period. If lateral advection of this material were responsible for some of the disparity in export estimates, accounting for particulate organic matter might significantly decrease the net flux of carbon into the Ross Sea from waters off the shelf. If enough organic matter was exported off the shelf the deficit in the mean annual total CO2 concentration which would have to be made up with flux of atmospheric CO2 into the Ross Sea. Presumably an export of organic material would also imply a greater flux of O2 through gas exchange into the Ross Sea as well. It is clear, based on the need to maintain a net flux of nitrate and phosphate into the Ross Sea near zero (assuming negligible sedimentary accumulation), that the full 3.5 mol C m-2 discrepancy between estimates of Sweeney et al. (2000b) and Collier et al. (2000) can be accounted for. However, if 1 mol C m-2 yr-1 was exported off the continental shelf of the Ross Sea as particulate organic matter this would also imply a net export 0.14 mol N m-2 yr-1 and 0.0086 mol P m-2 yr-1 as organic matter using Redfield ratio (Anderson and Sarmiento, 1994). The second reason for the disparity between the two estimates of the CO2 sea-air flux is the anomalously high productivity found in the southwestern Ross Sea along 76.5oS. While it is clear that phytoplankton growth does occur throughout the Ross Sea, Sweeney et al., (2000a) show that even in late January during the height of the phytoplankton bloom that some areas of the Ross Sea surface CO2(aq) are at equilibrium with atmospheric CO2. This would imply that while the phytoplankton bloom observed along 76.5oS in the southwestern Ross Sea provided a gradient which causes a net flux of CO2 into the Ross Sea, the phytoplankton bloom did not draw down CO2 to the same extend throughout the Ross Sea. As pointed out previously, Sweeney et al. (2000a) indicate that the mean NCP along 76.5oS was almost 35% higher than the mean for the entire Ross Sea. It is, therefore, likely that the estimated sea-air flux base on surface measurements along 76.5oS is bias by the excessive biological draw down in CO2 that was observed in that region. Discussion Although the Ross Sea may be considered somewhat anomalous because of the high primary productivity, it may provide a very good model for understanding the major mechanisms that control gas exchange in high latitudes. 5.1 Implications for gas exchange on the continental shelves of Antarctic It is clear from both the analysis of surface water measurements and analysis of incoming and outgoing water masses from the Ross Sea that sea ice plays a major role in the prevention of gas exchange as observed by Yager et al. (1995) and Gibson and Trull (Gibson and Trull, 1999). The major piece of evidence for the lack of gas flux during wintertime when the sea ice cover is extensive can be found in the oxygen concentrations throughout the winter in the Ross Sea (Figure 3d). Despite the large daily fluxes of oxygen that are estimated during the austral winter without ice cover (Figure 4), there is no evidence from the analysis of water masses moving onto or off of the shelf that would support O2 fluxes as high as 47 mol m-2 yr-1 which is estimated in conditions with no sea ice. Gibson and Trull (Gibson and Trull, 1999) have made similar observation in Prydz Bay, East Antarctica where oxygen remained under-saturated throughout the winter. Despite the presences of winter sea ice and high biological production in the Ross Sea (Smith and Gordon, 1997; Smith et al., 2000b) and elsewhere in the Antarctic shelf regions, there is a large flux of oxygen into waters on the continental shelves due to the contribution of CDW which contains waters that are extremely under-saturated in O2 coming onto the shelf. As discussed earlier, it is this large flux of O2 into the Antarctic surface waters that provides the high end-member PO4* in the deep waters that is formed on the shelves of Antarctica. 5.2 Implications for gas exchange in the past and future From the interaction of sea ice and primary production and the resulting gas exchange that is observed in the Ross Sea, it is possible to confirm “rectification” hypothesis suggested by Yager et al. (1995). Specifically, this theory points out the importance of the phytoplankton bloom both before the sea ice breaks up and after it has disappeared. Because there is very little gas exchange during the winter, the CO2 saturated waters are never able to degas. It is only after CO2 has been depleted in the surface waters by primary productivity that the sea ice retreats providing a large sink, not source, for atmospheric CO2. Yager et al. (1995) suggest that with increased warming due to increases in atmospheric CO2 levels and consequential increase in seasonal ice coverage that there may be a negative feedback provided by the interaction between sea ice and primary production. While primary production plays a significant role in creating a sea-air gradient for CO2 gas exchange, so does the concentration of CO2 in the atmosphere. If the rate of increase in atmospheric CO2 were to stay constant, the atmospheric pCO2 will be equal to that of the pre-phytoplankton bloom pCO2 of 425 atm in less than 40 years. This increase in atmospheric pCO2 as a result of anthropogenic inputs may also provide an important negative feedback for gas exchange in the future as the air-sea gradient increases. Because the unventilated lower CDW is the largest source of water on the continental shelves of Antarctic, the wintertime concentrations of TCO2 on the continental shelves of Antarctica are unlikely to change much over the next 40 years. However, as the atmospheric CO2 increases over the next 40 years, the sea-air gradient will become increasingly negative and provide a greater flux of CO2 into the waters on the continental margins of Antarctica. It has also been suggested that the rectification hypothesis explains the large decrease in atmospheric CO2 during glacial time (Stephens and Keeling, 2000). Stephens and Keeling (2000) hypothesis that with the large decreases in temperature suggested in the high latitudes during the last glacial maximum (Petit et al., 1999) that winter sea ice coverage extended beyond the present day polar front (Crosta et al., 1998) and prevented exchange between atmosphere and deep CO2 saturated waters. In addition, they suggested that when the ice melted, it left well stratified and biologically productive waters which prevented further exchange with the atmosphere. While CO2 was not well ventilated, Stephens and Keeling (2000) found that O2 was quicker to equilibrate and was less affected by primary productivity as it has been pointed out in this study. Summary The annual change in the surface concentrations of CO2 and O2 are estimated to be more than ~150 mol kg-1 and ~160 mol kg-1, respectively, along 76.5oS in southwestern Ross Sea. The large changes in CO2 and O2 are also accompanied by ~25 mol kg-1 changes in TIN. These changes in nutrients, CO2 and O2 are primarily driven by a large phytoplankton bloom centered in this area of the Ross Sea polynya where sea ice concentrations decrease quickly in the late austral winter. The large amplitude in the annual cycle of both CO2 and O2 surface concentrations along 76.5oS in the southwestern Ross Sea creates large sea-air gradients which in regions without sea ice would be responsible for both gas fluxes into and out of ocean depending on the season. Based on estimates using a linear relationship between sea ice concentration and gas flux, the CO2 flux increases by 1.0 mol m-2 yr-1 and the O2 flux decreases by 44 mol m-2 yr-1 into the Ross Sea when sea ice concentrations are taken into account. The annual flux of CO2 (-1.5±1.5 mol C m-2) and O2 (-3.7±3.0 mol C m-2) calculated from measurements of surface concentrations through one annual cycle are confirmed by a mass balance approach which accounts for the total flux of CO2 (0.16±0.13) and O2 (-5.2±0.2 mol C m-2) entering the Ross Sea from off the shelf. In order to compare results, it is assumed that a negligible amount of carbon and oxygen accumulate in the sediments and that all of the gas that ventilates to the atmosphere must be supplied from fresh waters entering the Ross Sea. In comparing the two methods it is important to realize that the mass balance approach does not take into account possible exchange of particle matter with areas off the shelf. It also must be pointed out that data collected along 76.5oS from which sea-air gas exchange fluxes were calculated may over estimate the impact of biological draw down of CO2 and production O2 by as much as 35%. The role of sea ice and primary productivity in the annual cycle of gas exchange in the Ross Sea strongly supports the “rectification” hypothesis (Yager et al., 1995) and provides a working model for scenarios hypothesized by Stephens and Keeling (1999). In this scenario they suggest that a large portion of the decrease in atmospheric CO2 measured in ice cores can be accounted for by increases in sea ice coverage during the last glacial maximum. In addition, this study supprts Yager et al. (1995) who suggest that an increase in seasonal sea ice coverage in areas like the Ross Sea with global warming may promote a larger draw down in CO2 during the summer months and, hence, a greater sink for CO2 with global warming. References Ainley, D. and Jacobs, S.S., 1981. 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Isotopic versus micrometeorologic ocean CO fluxes: a serious conflict. Journal of Geophysical Research, 91: 10,517-10,527. 2 Cavalieri, D.J. et al., 1991. Aircraft active and passive microwave validation of sea ice concentration from the Defense Meteorological Satellite Program Special Sensor Microwave Imager. Journal of Geophysical Research, 96(C12): 21989-22008. Cavalieri, D.J., Parkinson, C.L., Gloersen, P. and Zwally, H.J., 1997. Arctic and Antarctic Sea Ice Concentrations from Multichannel Passive-Microwave Satellite Data Sets: October 1978-September 1995, Goddard Space Flight Center, Greenbelt, MD. Chipman, D.W., Marra, J. and Takahashi, T., 1993. Primary production at 47oN and 20oW in the North Atlantic Ocean: a comparison between the 14C incubation method and the mixed layer carbon budget. Deep-Sea Research II, 40: 151-169. Collier, R. et al., 2000. The vertical flux of biogenic and lithogenic material in the Ross Sea: Moored sediment trap observations 1996-1998. Deep-Sea Research Part IiTopical Studies in Oceanography, 47(15-16): 3491-3520. Comiso, J.C., 1995. SSM/I sea ice concentrations using the Bootstrap algorithm, National Aeronautics and Space Administration, Washington, D. C. Comiso, J.C., D. Cavalieri, C. Parkinson, and P. Gloersen, , Rem Sens Envir, 60 (3), 357 384, 1997., 1997. Passive microwave algorithms for sea ice concentration - a comparison of two techniques. Remote Sensing of Environment, 60(3): 357-384. Crosta, X., Pichon, J.J. and Burckle, L.H., 1998. Reappraisal of Antarctic seasonal seaice at the Last Glacial Maximum. Geophysical Research Letters, 25(14): 27032706. DeMaster, D.J., Ragueneau, O. and Nittrouer, C.A., 1996. Preservation efficiencies and accumulation for biogenic silica and organic C, N, and P in the high-latitude sediments: The Ross Sea. Journal of Geophysical Research, 101: 18501- 18518. DiTullio, G.R. et al., 2000. Rapid and early export of Phaeocystis antarctica blooms in the Ross Sea, Antarctica. 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Jacobs, S.S., Amos, A.F. and Bruchhausen, P.M., 1970. Ross Sea oceanography and Antarctic Bottom Water formation. Deep-Sea Research, 17: 935-962. Jacobs, S.S. and Comiso, J.C., 1989. Sea ice and oceanic processes on the Ross Sea continental shelf. Journal of Geophysical Research, 94: 18195-18211. Jacobs, S.S., Fairbanks, R.G. and Horibe, Y., 1985. Origin and evolution of water masses near the Antarctic continental margin: Evidence from H218O/ H216O ratios in seawater. In: S.S. Jacobs (Editor), Oceanology of the Antarctic Continental Shelf. Antarctic Research Series. American Geological Union, Washington, D. C., pp. 59-85. Jacobs, S.S. and Giulivi, C.F., 1998. Interannual ocean and sea ice variability in the Ross Sea. Antarctic Research Series, 75: 135-150. Killworth, P.D., 1974. A baroclinic model of motions on Antarctic continental shelves. Deep-Sea Research, 21: 815-837. Locarnini, R.A., 1994. Water Masses and Circulation in the Ross Sea Gyre Environs. Ph. D. 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Rubin, S.I., Takahashi, T., Chipman, D.W. and Goddard, J.G., 1998. Primary productivity and nutrient utilization ratios in the pacific sector of the southern ocean based on seasonal changes in seawater chemistry. Deep-Sea Research I, 45: 1211-1234. Smith, W.O., Anderson, R.F., Moore, J.K., Codispoti, L.A. and Morrison, J.M., 2000a. The US Southern Ocean Joint Global Ocean Flux Study: an introduction to AESOPS. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 47(1516): 3073-3093. Smith, W.O. and Gordon, L.I., 1997. Hyperproductivity of the Ross Sea (Antarctica) polynya during austral spring. Geophysical Research Letters, 24(3): 233-236. Smith, W.O., Marra, J., Hiscock, M.R. and Barber, R.T., 2000b. The seasonal cycle of phytoplankton biomass and primary productivity in the Ross Sea, Antarctica. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 47(15-16): 31193140. Stephens, B.B. and Keeling, R.F., 2000. The influence of Antarctic sea ice on glacialinterglacial CO2 variations. Nature, 404(6774): 171-174. Sweeney, C. et al., 2000a. Biogeochemical regimes, net community production and carbon export in the Ross Sea, Antarctica. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 47(15-16): 3369-3394. Sweeney, C. et al., 2000b. Nutrient and carbon removal ratios and fluxes in the Ross Sea, Antarctica. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 47(1516): 3395-3421. Takahashi, T., Broecker, W.S. and Langer, S., 1985. Redfield ratio based on chemical data from isopycnal surfaces. Journal Geophysical Research, 90: 6907-6924. Toggweiler, J.R. and Samuels, B., 1995. Effect of sea ice on the salinity of Antarctic bottom waters. Journal of Physical Oceanography, 25(9): 1980-1997. Wanninkhof, R., 1992. Relationship between Wind-Speed and Gas-Exchange over the Ocean. Journal of Geophysical Research-Oceans, 97(C5): 7373-7382. Wanninkhof, R. and McGillis, W.R., 1999. A cubic relationship between air-sea CO2 exchange and wind speed. Geophysical Research Letters, 26(13): 1889-1892. Weiss, R.F., 1970. Solubility of Nitrogen, Oxygen and Argon in Water and Seawater. Deep-Sea Research, 17(4): 721-&. Weiss, R.F., 1974. Carbon dioxide in seawater: The solubility of an ideal gas. Marine Chemistry, 2: 203-215. Zwally, H.J., Comiso, J.C. and Gordon, A.L., 1985. Antarctic offshore leads and polynyas and oceanographic effects. In: S.S. Jacobs (Editor), Oceanology of the Antarctic Continental Shelf. Antarctic Research Series. American Geological Union, Washington, D.C., pp. 203-226. Figure 1. Station locations. Hydrographic station location for cruises on the R/V Nathaniel B. Palmer. Black dots represent cruises done for the Antarctic Environment Southern Ocean Process Study (AESOPS – NBP96-04B, NBP97-01, NBP97-03 and NBP97-08) and (ROAVERRS – NBP98-01). The white dots represent data from the World Ocean Circulation Experiment (WOCE – NBP94-05). a) b) c) Figure 2. The seasonal cycle of a) temperature (C), b) salinity and c) mixed layer depth (m) in the Ross Sea at 76.5oS between 170oW and 180o. Average values were measured in the upper 20 m of the water column (●), a smoothed average of the measurements (--). The light gray background line refers to the % ice coverage (right axis) for the 1996-1997 season (solid line) and 1997-1998 season (dashed line). a) b) c) d) Figure 3. The seasonal cycle of surface a) partial pressure of CO2 (pCO2), b) total CO2 (TCO2), c) total inorganic nitrogen (TIN) and d) oxygen in the Ross Sea at 76.5oS between 170oW and 180o. Average values were measured in the upper 20 m of the water column (●), a smoothed average of the measurements (--). Solid line represents estimates of surface TCO2 and O2 concentrations based on changes in surface TIN using Redfield ratios of 116/7 and 175/7, respectively. The light gray background line refers to the % ice coverage (right axis) for the 1996-1997 (solid line) and 1997-1998 (dashed line) seasons. a) b) Figure 4. The daily sea-air flux of a) CO2 and b) oxygen in the Ross Sea at 76.5oS between 170oW and 180o. Daily flux of gas based on the average sea ice concentration (-) and no sea ice conditions (--) assuming the flux is proportional to the concentration of sea ice, wind speed and sea-air gradient. The fraction of sea ice coverage used was for the 1996-1997 season. a) b) Figure 5. Temperature/Salinity and 18O/Salinity relationship between water masses on (o) and off (●) of the Ross Shelf. Incoming water (x) is 50% CDW, 25% AASW and 25%Tmin. Outgoing water (●) is 70% LSSW + 10% HSSW + 20% DISW. Error bars represent the standard error of the mean. Figure 6 18O and salt budget of the Ross Sea according to Jacobs et al. (1985). Based on Jacobs et al. (1985), water masses coming into the Ross Sea (Circumpolar Deep Water (CDW), Antarctic Surface Water (AASW) and Winter Water (WW)) have a 18O of 0.2225 and salinity of 34.453 while waters moving off of the continental shelf that defines the Ross Sea have a 18O of 0.465 and salinity of 34.588. a) b) c) Figure 7. Salinity verses a) total CO2 (TCO2) b) oxygen and c) Silicate. Each value represents the mean concentration of dissolved inorganic carbon, silicate and oxygen normalized to the average salinity of the Ross Sea (34.54, =[C]*salinity/34.54). Water masses on (o) and off (●) of the Ross Shelf have been seperated. Incoming water (x) is 50% CDW, 25% AASW and 25%Tmin. Outgoing water (●) is 70% LSSW + 10% HSSW + 20% DISW. Error bars represent the standard error of the mean.