Coulometric total carbon dioxide analysis for marine studies: Automation and calibration

An automated instrument for the coulometric detection of total carbon dioxide (TCO₂) was developed from the manual prototype of Johnson et al. Pure CO₂ was used to calibrate the detector, the whole analytical procedure was controlled by a microcomputer, and the unit was compact enough for field and shipboard use. Some 67 samples from the Askö field station on the Baltic Sea (salinity = 6; TCO₂ ranging from 1224.3 to 1276.1 μmol l⁻¹ with a mean of 1245.6 μmol l⁻¹) and 31 samples from Swedish lakes (TCO₂ ranging from 19.5 to 252.3 μmol l⁻¹ with a mean of 72.9 μmol l⁻¹) were analyzed. The pooled standard deviation of these analyses was ± 1.0 μmol l⁻¹ (% CV of 0.08 and 1.3%, respectively). Precisions of < 0.1% were routine for waters exceeding 1000 μmol l⁻¹ TCO₂. At Askö on the Baltic Sea, the mean absolute difference between coulometric and pH-alkalinity determinations of TCO₂ on 22 parallel samples was 6.7 μmol kg⁻¹ or 0.5% of the mean. Community metabolism studies gave maximum rates of net production (TCO₂ uptake) and respiration (TCO₂ production) of 0.9-1.2 and 0.3-0.5 μmol l⁻¹ b⁻¹, respectively. The results of this study provide solutions to the problems observed with the earlier manual prototype.     

Rates of calcium carbonate dissolution and organic carbon decomposition in the North Pacific ocean

Recent carbonate data collected in the North Pacific were combined with the data in the literature in order to understand more clearly the carbonate chemistry in the North Pacific. Our analyses show that inorganic CaCO₃ dissolution contributes about 26% of the total inorganic CO₂ increase of deep water, after leaving the Southern Ocean. The calcium and alkalinity data indicate a CaCO₃ dissolution rate of 0.060±0.010 and 0.053±0.005 µ mol kg^–1 yr^–1 respectively, for waters deeper than 2,000 m in reference to the Weddell Sea Deep Water. The organic carbon decomposition rate is 0.107±0.012 µ mol kg^–1 yr^–1 while the oxygen consumption rate is 0.13±0.002 µ mol kg^–1 yr^–1. These results which are based on the direct comparison of two water masses agree well with other estimates which are based on methods such as the one-dimensional-diffusion-advection model. Comparison of data along the two sections at 165°E and 150°W shows no significant difference in the ratio of the CaCO₃ dissolution rate and the organic carbon decomposition rate. The eastern section, however, has a higher TCO₂ input than the western section because of the older age of the deep water along the eastern section.     

Development and assessment of an analytical system for the accurate and continual measurement of total dissolved inorganic carbon

An automated coulometric titration system based on that described by Johnson, Sieburth, Williams and Brandstrom (1987, Mar. Chem., 21: 117–133) has been evolved for the accurate and continual measurement of total dissolved inorganic carbon (TCO₂). The instrument achieves an analytical precision (1 SD) of ±0.5–1.0 μmol kg⁻¹ (0.025–0.05%). The accuracy of the system has been examined by a limited comparison with other coulometric-based titrators and with a manometric-based system; agreement was to 1 μmol kg⁻¹. The capability for automatic continual analysis allows surface mapping of TCO₂; a sample rate of 10 analyses h⁻¹ gives a mapping resolution of 1–2 km. Provision for frequent standardization with a liquid substandard has been included in the development. The ability to achieve high-density analyses while maintaining interlaboratory consistency and standardization constitutes a vital contribution to surveys of ocean carbon chemistry (e.g. Joint Global Ocean Flux Study, World Ocean Circulation Experiment).     

Oxygen Utilization and Organic Carbon Remineralization in the Upper Water Column of the Pacific Ocean

As a part of the JGOFS synthesis and modeling project, researchers have been working to synthesize the WOCE/JGOFS/DOE/NOAA global CO₂ survey data to better understand carbon cycling processes in the oceans. Working with international investigators we have compiled a Pacific Ocean data set with over 35,000 unique samples analyzed for at least two carbon species, oxygen, nutrients, chlorofluorocarbon (CFC) tracers, and hydrographic parameters. We use these data here to estimate in-situ oxygen utilization rates (OUR) and organic carbon remineralization rates within the upper water column of the Pacific Ocean. OURs are derived from the observed apparent oxygen utilization (AOU) and the water age estimates based on CFCs in the upper water and natural radiocarbon in deep waters. The rates are generally highest just below the euphotic zone and decrease with depth to values that are much lower and nearly constant in water deeper than 1200 m. OURs ranged from about 0.02–10 μmol kg⁻¹yr⁻¹ in the upper water masses from about 100–1000 m, and averaged = 0.10 μmol kg⁻¹yr⁻¹ in deep waters below 1200 m. The OUR data can be used to directly estimate organic carbon remineralization rates using the C:O Redfield ratio given in Anderson and Sarmiento (1994). When these rates are integrated we obtain an estimate of 5.3 ± 1 Pg C yr⁻¹ for the remineralization of organic carbon in the upper water column of the Pacific Ocean. This revised version was published online in July 2006 with corrections to the Cover Date.     

Increase of carbon dioxide in the bottom water of the Weddell Sea, Antarctica

High precision total CO₂ (TCO₂) data are presented from the NW Weddell Sea obtained during two cruises which were 3 years apart. A TCO₂ increase from 1993 to 1996 was observed in the newly formed bottom water, whereas no TCO₂ increase was found in the surrounding water masses. Accompanying this TCO₂ increase in the bottom water was an oxygen decrease. Obviously, bottom water with variable characteristics is produced along the margins of the Weddell Sea. Examination of possible causes leads to the conclusion that the bottom water variability is largely due to varying amounts of Warm Deep Water intruding onto the shelves of the Weddell Sea, thus changing the shelf water end-member of bottom water formation. Analysis of the data, using the observed differences of oxygen to perform a correction, suggested that some part of the TCO₂ increase of the bottom water is due to the increased level of anthropogenic CO₂. The TCO₂ increase of the bottom water is commensurate to a tentative annual increase of about 1 μmol kg⁻¹ in the surface water source of this bottom water. This would agree fairly well with the increase of the partial pressure of CO₂ in the atmosphere.     

The behaviour of dissolved Cd, Co, Zn, and Pb in North Atlantic near-surface waters (30°N/60°W–60°N/2°W)

In September 1993 (M26) and June/July 1996 (M36), a total of 239 surface samples (7 m depth) were collected on two transects across the open Atlantic Ocean (224 samples) and northwest European shelf edge area. We present an overview of the horizontal variability of dissolved Cd, Co, Zn, and Pb in between the northwest and northeast Atlantic Ocean in relation to salinity and the nutrients. Our data show a preferential incorporation of Cd relative to P in the particulate material of the surface ocean when related to previously published parallel measurements on suspended particulate matter from the same cruise. There is a good agreement with results recently estimated from a model by Elderfield and Rickaby (Nature 405 (2000) 305), who predict for the North Atlantic Ocean a best fit for α_Cd/P=[Cd/P]_POM/[Cd/P]_SW of 2.5, whereas the approach of our transect shows a α_Cd/P value of 2.6. The Co concentrations of our transects varied from <5 to 131 pmol kg⁻¹, with the lowest values in the subtropical gyre. There were pronounced elevations in the low-salinity ranges of the northwest Atlantic and towards the European shelf. The Co data are decoupled from the Mn distribution and support the hypothesis of marginal inputs as the dominant source. Zinc varied from a minimum of <0.07 nmol kg⁻¹ to a maximum of 1.2 and 4.8 nmol kg⁻¹ in regions influenced by Labrador shelf or European coastal waters, respectively. In subtropical and northeast Atlantic waters, the average Zn concentration was 0.16 nmol kg⁻¹. Zinc concentrations at nearly three quarters of the stations between 40°N and 60°N were <0.1 nmol kg⁻¹. This suggests that biological factors control Zn concentrations in large areas of the North Atlantic surface waters. The Pb data indicated that significant differences in concentration between the northwest and northeast Atlantic surface waters presently (1996) do not exist for this metal. The transects in 1993 and 1996 exhibited Pb concentrations in the northeast Atlantic surface waters of 30 to 40 pmol kg⁻¹, about a fifth to a quarter of the concentrations observed in 1981. This decline is supported by our particle flux measurements in deep waters of the same region.     

Persistently declining oxygen levels in the interior waters of the eastern subarctic Pacific

Fifty years of measurements at Ocean Station Papa (OSP, 50°N, 145°W) show trends in the interior waters of the subarctic Pacific that are both impacted by short term (few years to bi-decadal) atmospheric or ocean circulation oscillations and by persistent climate trends. Between 1956 and 2006, waters below the ocean mixed layer to a depth of at least 1000 m have been warming and losing oxygen. On density surfaces found in the depth range 100-400 m (σ_θ = 26.3-27.0), the ocean is warming at 0.005-0.012 °C y⁻¹, whereas oxygen is declining at 0.39-0.70 μmol kg⁻¹ y⁻¹ or at an integrated rate of 123 mmol m⁻² y⁻¹ (decrease of 22% over 50 years). During this time, the hypoxic boundary (defined as 60 μmol O₂ kg⁻¹) has shoaled from ∼400 to 300 m. In the Alaska Gyre, the 26.2 isopycnal occasionally ventilates, whereas at OSP 26.0σ_θ has not been seen at the ocean surface since 1971 as the upper ocean continues to stratify. To interpret the 50 year record at OSP, the isopycnal transport of oxygenated waters within the interior of the subarctic Pacific is assessed by using a slightly modified “NO” parameter [Broecker, W., 1974. “NO” a conservative water-mass tracer. Earth and Planetary Science Letters 23, 100-107]. The highest nitrate-oxygen signature in interior waters of the North Pacific is found in the Bering Sea Gyre, Western Subarctic Gyre and East Kamchatka Current region as a consequence of winter mixing to the ∼26.6 isopycnal. By mixing with low NO waters found in the subtropics and Okhotsk Sea, this signature is diluted as waters flow eastward across the Pacific. Evidence of low NO waters flowing north from California is seen along the coasts of British Columbia and SE Alaska. Oxygen in the subsurface waters of the Alaskan Gyre was supplied ∼60% by subarctic and 40% by subtropical waters during WOCE surveys, whereas such estimates are shown to periodically vary by 20% at OSP. Other features discernable in the OSP data include periods of increased ventilation of deeper isopycnals on an ∼18 year cycle and strong, short term (few month) variability caused by passing mesoscale eddies. The potential impacts of declining oxygen on coastal ecosystems are discussed.     

Alkalinity changes in the Sargasso Sea: geochemical evidence of calcification?

Strong seasonal patterns in upper ocean total carbon dioxide (TCO₂), alkalinity (TA) and calculated pCO₂ were observed in a time series of water column measurements collected at the US Joint Global Ocean Flux Study (JGOFS) BATS site (31 °50′N, 64 °10′W) in the Sargasso Sea. TA distribution was a conservative function of salinity. However, in February 1992, a non-conservative decrease in TA was observed, with maximum depletion of 25–30 μmoles kg⁻¹ occuring in the surface layer and at the depth of the chlorophyll maximum (˜ 80–100 m). Mixed-layer TCO₂ also decreased, while surface pCO₂ increased by 25–30 μatm. We suggest these changes in carbon dioxide species resulted from open-ocean calcification by carbonate-secreting organisms rather than physical processes. Coccolithophore calcification is the most likely cause of this event although calcification by foraminifera or pteropods cannot be ruled out. Due to the transient increase in surface pCO₂, the net annual transfer of CO₂ into the ocean at BATS was reduced. These observations demonstrate the potential importance of open-ocean calcification and biological community structure in the biogeochemical cycling of carbon.     

Increase in anthropogenic CO2 in the Atlantic Ocean in the last two decades

Data from the first systematic survey of inorganic carbon parameters on a global scale, the GEOSECS program, are compared with those collected during WOCE/JGOFS to study the changes in carbon and other geochemical properties, and anthropogenic CO₂ increase in the Atlantic Ocean from the 1970s to the early 1990s. This first data-based estimate of CO₂ increase over this period was accomplished by adjusting the GEOSECS data set to be consistent with recent high-quality carbon data. Multiple Linear Regression (MLR) and extended Multiple Linear Regression (eMLR) analyses to these carbon data are applied by regressing DIC with potential temperature, salinity, AOU, silica, and PO₄ in three latitudinal regions for the western and eastern basins in the Atlantic Ocean. The results from MLR (and eMLR provided in parentheses) indicate that the mean anthropogenic CO₂ uptake rate in the western basin is 0.70 (0.53) mol m^?2 yr^?1 for the region north of 15°N; 0.53 (0.36) mol m^?2 yr^?1 for the equatorial region between 15°N and 15°S; and 0.83 (0.35) mol m^?2 yr^?1 in the South Atlantic south of 15°S. For the eastern basin an estimate of 0.57 (0.45) mol m^?2 yr^?1 is obtained for the equatorial region, and 0.28 (0.34) mol m^?2 yr^?1 for the South Atlantic south of 15°S. The results of using eMLR are systematically lower than those from MLR method in the western basin. The anthropogenic CO₂ increase is also estimated in the upper thermocline from salinity normalized DIC after correction for AOU along the isopycnal surfaces. For these depths the results are consistent with the CO₂ uptake rates derived from both MLR and eMLR methods.     

Intermediate Waters in the East/Japan Sea

Properties of the intermediate layer in the East/Japan Sea are examined by using CREAMS data taken mainly in summer of 1995. Vertical profiles of potential temperature, salinity and dissolved oxygen and relationships between these physical and chemical properties show that the dissolved oxygen concentration of 250 μmol/l, roughly corresponding to 0.6°C at the depth of about 400 db, makes a boundary between intermediate and deep waters. Water colder than 0.6°C has a very stable relationship between potential temperature and salinity while salinity of the water warmer than 0.6°C is lower in the western Japan Basin than that in the eastern Japan Basin. The low salinity water with high oxygen corresponds to the East Sea Intermediate Water (ESIW; <34.06 psu, >250 μmol/l and >1.0°C) which was previously identified by Kim and Chung (1984) and the high salinity water with high oxygen found in eastern Japan Basin is named as the High Salinity Intermediate Water (HSIW; >34.07 psu, >250 μmol/l and >0.6°C). Spatial distribution of salinity and acceleration potential on the surface of σ_ϑ = 27.2 kg/m³ shows that the ESIW prevailing in the western Japan Basin is transported eastward by a zonal flow along the polar front near 40°N and a cyclonic gyre in the eastern Japan Basin is closely related to the HSIW. This revised version was published online in August 2006 with corrections to the Cover Date.     

‘NO’ as a conservative tracer in the Weddell Sea

The salinity maximum of the Warm Deep Water advecting into the Weddell Sea lies about 200 m below the temperature maximum and an NO minimum. The NO minimum is horizontally as well as vertically resolved on two sections towards the eastern and southern coast of the Weddell Sea, one towards Cap Norvegia, the other towards the Filchner Ice Shelf, whereas the temperature and salinity maxima are horizontally resolved on the former section only. Thus NO is a valuable complementary tool in studying the boundary current along the coast of the Weddell Sea. The NO signal indicates a non-continuity within the boundary current, as the minimum in the downstream section (less than 480 μmol kg⁻¹ ) is deeper than the upstream one ( more than 490 μmol kg⁻¹). The temperature maximum as well as the NO minimum descend from a depth of about 400 m in the Cap Norvegia section to about 600 m in the Filchner Ice Shelf section, the salinity maximum being correspondingly lowered. A plot of NO vs. salinity shows a continuous mixing line between Warm Deep Water and the freshest part of the Winter Water interval, thus essentially displaying Winter Water as itself lying on a mixing line. This indicates that Warm Deep Water is being advected well into the winter surface layer.     

Coulometric TCO2 analyses for marine studies; an introduction

Progress in the introduction of coulometry for the analysis of total carbon dioxide (TCO₂) in marine waters is described. An extractor—stripper removes CO₂ that is measured coulometrically by the quantity of electricity (coulombs) used to electrogenerate OH^? ions for the titration of the acid formed by the reaction of CO₂ and ethanolamine. The equivalence point is detected photometrically with thymolphthalein as the indicator, and Faraday's Law relates coulombs to equivalents of titrant generated and CO₂ determined so that there are no standard curves needed or titrants to standardize or store. Accuracy was determined by adding gelatin capsules containing 100–1500 μg C of pure CaCO₃ into the stripper, and accuracies of better than ± 1 μg C were achieved. The best precision for natural seawater (± 1 standard error) of ± 0.5 μmol l^?1 was found for 17 samples of Bermuda coastal waters having a mean TCO₂ of 2007.2 μmol l^?1 (0.05% CV). Sources of error and precautions are discussed. This method, which has been used successfully at sea, can be used to study a variety of marine phenomena involving TCO₂.     

Recurrent Red-tides in the Southampton Water Estuary Caused by the Phototrophic CiliateMesodinium rubrum

In the Southampton Water estuary (southern England, U.K.), red-tides caused by the planktonic, phototrophic ciliateMesodinium rubrum(=Myrionecta rubra) occur during most summers and sometimes in autumn. These events were investigated in detail between 1985 and 1987 and were characterized by levels of chlorophylla(chl a) of over 100 μg l⁻¹, cell numbers ofM. rubrumof over 1×10³ ml⁻¹, oxygen saturations of around 150%, and depleted numbers of macrozooplankton. Initiation of red-water did not appear to be triggered by irradiance or nutrients, but coincided with an increase in temperature and water column stability. This enhanced stability was promoted by increased surface to bottom gradients of both temperature and salinity, and by reduced mixing during neap tides. Development of red-water was accompanied by removal of most of the dissolved NH⁺₄from the water column, whereas some NO⁻₃persisted, presumably maintained by freshwater input. NO⁻₃and NH⁺₄gradually returned to pre-bloom concentrations as the red-water declined in late summer. Maximal biomass ofM. rubrumappeared to be limited by irradiance, and self-shading probably imposed an upper limit of around 300 mg chl a m⁻²within the water column. At the observed levels of chl a, irradiance values within the population maximum between 1 and 3 m depth were only just of the order (≈15 μmol photons m⁻² s⁻¹) required to balance estimated respiratory demands. Oxygen concentration became undersaturated during the late bloom phase, with minimal values of 20–30% saturation recorded in deeper waters; however, despite this and reduced numbers of macrozooplankton, direct deleterious effects on other organisms were not observed.     

Seasonal variability of dissolved oxygen,percent oxygen saturation,and apparent oxygen utilization in the Atlantic and Pacific Oceans

Using objectively analyzed seasonal fields of dissolved oxygen content, percent oxygen saturation, and apparent oxygen utilization (AOU), we describe the large-scale seasonal variability of oxygen for the Atlantic and Pacific Oceans in the upper 400 m. The winter minus summer basin zonal averages of AOU reveal a two-layer feature in both the Atlantic and the Pacific, for both hemispheres. Biological activity and seasonal stratification in the summer give the upper 50–75 m of the water column in each basin a lower AOU in summer than winter. Greater mixing of upper ocean waters in winter gives the 75–400 m layer lower AOU values in that season. The basin integral seasonal volumes of oxygen for both the North Atlantic and the North Pacific mirror what is occurring in the atmosphere, indicating that there is a seasonal flux of oxygen across the air–sea interface. Winter total O₂ volume in the ocean is above the annual mean; the summer volume is below. Larger seasonal differences in the total O₂ content are observed in the North Atlantic Ocean than the North Pacific Ocean. A seasonal net outgassing (SNO) of 8.3×10¹⁴ moles O₂ is calculated from basin means, which is 25% higher than previous results.     

Oxygen minimum zones in the eastern tropical Atlantic and Pacific oceans

Within the eastern tropical oceans of the Atlantic and Pacific basin vast oxygen minimum zones (OMZ) exist in the depth range between 100 and 900 m. Minimum oxygen values are reached at 300–500 m depth which in the eastern Pacific become suboxic (dissolved oxygen content <4.5 μmol kg⁻¹) with dissolved oxygen concentration of less than 1 μmol kg⁻¹. The OMZ of the eastern Atlantic is not suboxic and has relatively high oxygen minimum values of about 17 μmol kg⁻¹ in the South Atlantic and more than 40 μmol kg⁻¹ in the North Atlantic. About 20 (40%) of the North Pacific volume is occupied by an OMZ when using 45 μmol kg⁻¹ (or 90 μmol kg⁻¹, respectively) as an upper bound for OMZ oxygen concentration for ocean densities lighter than σ_θ < 27.2 kg m⁻³. The relative volumes reduce to less than half for the South Pacific (7% and 13%, respectively). The abundance of OMZs are considerably smaller (1% and 7%) for the South Atlantic and only 0% and 5% for the North Atlantic. Thermal domes characterized by upward displacements of isotherms located in the northeastern Pacific and Atlantic and in the southeastern Atlantic are co-located with the centres of the OMZs. They seem not to be directly involved in the generation of the OMZs.OMZs are a consequence of a combination of weak ocean ventilation, which supplies oxygen, and respiration, which consumes oxygen. Oxygen consumption can be approximated by the apparent oxygen utilization (AOU). However, AOU scaled with an appropriate consumption rate (aOUR) gives a time, the oxygen age. Here we derive oxygen ages using climatological AOU data and an empirical estimate of aOUR. Averaging oxygen ages for main thermocline isopycnals of the Atlantic and Pacific Ocean exhibit an exponential increase with density without an obvious signature of the OMZs. Oxygen supply originates from a surface outcrop area and can also be approximated by the turn-over time, the ratio of ocean volume to ventilating flux. The turn-over time corresponds well to the average oxygen ages for the well ventilated waters. However, in the density ranges of the suboxic OMZs the turn-over time substantially increases. This indicates that reduced ventilation in the outcrop is directly related to the existence of suboxic OMZs, but they are not obviously related to enhanced consumption indicated by the oxygen ages. The turn-over time suggests that the lower thermocline of the North Atlantic would be suboxic but at present this is compensated by the import of water from the well ventilated South Atlantic. The turn-over time approach itself is independent of details of ocean transport pathways. Instead the geographical location of the OMZ is to first order determined by: (i) the patterns of upwelling, either through Ekman or equatorial divergence, (ii) the regions of general sluggish horizontal transport at the eastern boundaries, and (iii) to a lesser extent to regions with high productivity as indicated through ocean colour data.     

Increase in total carbonate in the western North Pacific water and a hypothesis on the missing sink of anthropogenic carbon

Sea water samples were collected from various depths in the North Pacific (40–21°N) along 165°E in 1991. Their total carbonate (total dissolved carbonate species) contents were determined with random errors less than 0.2% by a coulometric method. The preformed carbonate contents defined by Chen (1982) were calculated from the obtained data and other observed data including potential temperature, salinity, dissolved oxygen and total alkalinity. The same calculation was done for the GEOSECS data obtained in nearly the same region in 1973. The difference between the two data sets reveals that the preformed carbonate has increased by 180±41 gC/m² during the last 18 years. This value is comparable or somewhat larger than 150 gC/m² obtained in the case that the ocean uptakes 3 GtC/yr for 18 years and distributes it equally among the world oceans. Based on the results, a hypothesis on the missing sink for the anthropogenic carbon dioxide is presented, in that the missing sink is the intermediate waters formed in the northern North Pacific and the Southern Ocean besides the deep waters formed in the North Atlantic and the Southern Ocean.     

CO2 in the Weddell Gyre and Antarctic Circumpolar Current: austral autumn and early winter

Quasi-continuous fugacity of CO₂ (fCO₂) data were collected in the eastern Weddell Gyre and southern Antarctic Circumpolar Current (ACC) of the Southern Ocean during austral autumn 1996. Full depth Total CO₂ (TCO₂) sections are presented for austral autumn and winter (1992) cruises. Pronounced fCO₂ gradients were observed at the Southern Ocean fronts. In the Weddell Gyre, fCO₂ regimes appeared to coincide with surface and subsurface hydrographic regimes. The southern ACC was supersaturated with respect to CO₂, as was part of the northern Weddell Gyre. The southern Weddell Gyre was markedly undersaturated. The great potential of autumn cooling for generating undersaturation and CO₂ uptake from the atmosphere was demonstrated. In the northeastern Weddell Gyre, upwelling of CO₂- and salt-rich deep water was shown to play a role as the horizontal fCO₂ distribution closely resembled that of the surface salinity. The total uptake of atmospheric CO₂ by the Weddell Gyre in autumn (45 days) was calculated to be 7·10¹² g C. The deep TCO₂ distribution noticeably reflected the different water masses in the region. A new deep TCO₂ maximum was detected in the ACC, which apparently characterizes the boundary between the equatorward flowing Antarctic Bottom Water (AABW) and the Circumpolar Deep Water (CDW). East of the Weddell Gyre, the AABW stratum is much thicker (>2000 m) than more to the west, on the prime meridian (<300 m).     

Oxygen dynamics in the North Atlantic subtropical gyre

Dissolved oxygen (DO) in the ocean is a tracer for most ocean biogeochemical processes including net community production and remineralization of organic matter which in turn constrains the biological carbon pump. Knowledge of oxygen dynamics in the North Atlantic Ocean is mainly derived from observations at the Bermuda Atlantic Time-series Study (BATS) site located in the western subtropical gyre which may skew our view of the biogeochemistry of the subtropical North Atlantic. This study presents and compares a 15 yr record of DO observations from ESTOC (European Station for Time-Series in the Ocean, Canary Islands) in the eastern subtropical North Atlantic with the 20 yr record at BATS. Our estimate for net community production of oxygen was 2.3±0.4 mol O₂ m⁻² yr⁻¹ and of oxygen consumption was −2.3±0.5 mol O₂ m⁻² yr⁻¹ at ESTOC, and 4 mol O₂ m⁻² yr⁻¹ and −4.4±1 mol m⁻² yr⁻¹ at BATS, respectively. These values were determined by analyzing the time-series using the Discrete Wavelet Transform (DWT) method. These flux values agree with similar estimates from in-situ observational studies but are higher than those from modeling studies. The difference in net oxygen production rates supports previous observations of a lower carbon export in the eastern compared to the western subtropical Atlantic. The inter-annual analysis showed clear annual cycles at BATS whereas longer cycles of nearly 4 years were apparent at ESTOC. The DWT analysis showed trends in DO anomalies dominated by long-term perturbations at a basin scale for the consumption zones at both sites, whereas yearly cycles dominated the production zone at BATS. The long-term perturbations found are likely associated with ventilation of the main thermocline, affecting the consumption and production zones at ESTOC.     

The reliability of the thermodynamic constants for the dissociation of carbonic acid in seawater

Laboratory measurements of all four CO₂ parameters [f_CO2 ( = fugacity of CO₂), pH, TCO₂ ( = total dissolved inorganic carbon), and TA ( = total alkalinity)] were made on the same sample of Gulf Stream seawater (S = 35) as a function of temperature (5–35 °C) and the ratio of TA/TCO₂ (X) (1.0–1.2). Overall the measurements were consistent to ±8 μ atm in f_CO2, ± 0.004 in pH, ± 3 μ mol kg⁻¹ in TCO₂, and ± 3 μ mol kg⁻¹ in TA with the thermodynamic constants of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). Deviations between the measured pH, TCO₂, TA and those calculated from various input combinations increase with increasing X when the same constants are used. This trend in the deviations indicates that the uncertainties in pK₂ become important with increasing X (surface waters), but are negligible for samples with the lower X (deep waters). This trend is < 5 μ mol kg⁻¹ when the pK₂ values of Lee and Millero (1995) are used.The overall probable error of the calculated f_CO2 due to uncertainties in the accuracy of the parameters (pH, TCO₂, TA, pK₀, pk₁, and pK₂) is ± 1.2%, which is similar to the differences between the measured values and those calculated using the thermodynamic constants of Millero (1995).The calculated values of pK₁, (from f_CO2-TCO₂-TA) agree to within ± 0.004 compared to the results of Dickson and Millero (1987), Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995) over the same experimental conditions. The calculated values of pK₂ (from pH-TCO₂-TA) are in good agreement (± 0.004) with the results of Lee and Millero (1995) and also in reasonable agreement (± 0.008) with the results of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). The salinity dependence of our derived values of pK₁ and pK₂, (S = 35) can be estimated using the equations determined by Millero (1995).