The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

The ‘International Intercomparison Exercise of fCO₂ Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO₂) systems, one discrete fCO₂ system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO₂ measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO₂, temperature measurements) and a common procedure for calculation of final fCO₂ were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO₂ in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO₂ measurements can be made in good agreement (±3 μatm) with underway fCO₂ data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO₂ system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO₂ results. Calculation of fCO₂ from high-quality total dissolved inorganic carbon (C_T) and total alkalinity (A_T) measurements does not yield results comparable in accuracy and precision to fCO₂ measurements.     

The carbon dioxide system in the northwestern Indian Ocean during south–west monsoon

Data on the carbonate system of the Northwestern Indian Ocean obtained on a cruise of F.S. Meteor during SW monsoon in July/August 1995 were compared with those of George et al. [George, M.D., Kumar, M.D., Naqvi, S.W.A., Banerjee, S., Narvekar, P.V., de Sousa, S.N., Jayakumar, D.A., 1994. A study of the carbon dioxide system in the northern Indian Ocean during premonsoon. Mar. Chem. 47, 243–254] collected during intermonsoon. In general, deep water values agreed well between the two expeditions. Surface waters, however, showed a substantial increase in dissolved inorganic carbon (C_T) in the coastal regions due to strong upwelling in the SW monsoon. This was also accompanied by very high CO₂ partial pressures in surface waters. The north–south gradients in vertical profiles of the measured parameters in the Arabian Sea are discussed by comparing profiles from the oligotrophic equatorial region with those from the highly productive central Arabian Sea. The effect of denitrification on regenerated C_T and A_T is minor, with contributions of <9 and <8 μmol kg⁻¹, respectively, to the total amount regenerated also utilizing oxygen. The dissolution of biogenic carbonates is discussed; different approaches to define the depth, where the dissolution starts (lysocline(s), carbonate critical depth (CCrD)), are compared together with the calculation of saturation depth from carbonate concentrations. It is shown, that small differences in measured C_T and A_T (found between our data and those measured during GEOSECS) and different calculation approaches to the CO₂ system (different dissociation constants for species involved and taking into account phosphate and silicate concentrations) can produce pronounced differences in the calculated saturation depths. However, C_T and A_T data suggest substantial dissolution of biogenic carbonate in the water column even above the calcite lysocline, irrespective of the procedures followed to calculate this horizon.     

A high accuracy method for determining nitrogen, argon and oxygen in seawater

An improved gas chromatographic system was constructed to analyze oceanic dissolved N₂, Ar and O₂ with a higher accuracy and shorter analytical time. To obtain a higher accuracy of N₂, Ar and O₂ measurements, the following was added to the system: (I) an air trapping system; (II) a N₂–CO₂ trapping system after the operation of the air trapping system; (III) an active carbon column system for separating N₂ and CO₂ completely and (IV) the introduction of automatic valves controlling most of the system. Compared to previous studies, the precision of the measurements of N₂, Ar and O₂ concentrations was higher at 0.04%, 0.05% and 0.02%, respectively, and our analytical time was shorter at 600 s. Using the improved analytical technique, concentrations of N₂ (C_N2, 561.69–611.81 μmol/kg) and Ar (C_Ar, 15.126–16.238 μmol/kg), saturation states of N₂ (ΔN₂, − 5.1–0.9%) and Ar (ΔAr, − 7.0 to − 1.1%) from 0 m to 3000 m depth in the western North Pacific were observed during March 2005. Based on these data, we propose a new concept for estimating the amount of bubble injection (B). The total error in calculating B was estimated to be about 20%. We estimated B from 12 to 43 μmol/kg in this region using the observational values of N₂ and Ar. As each water mass had a significantly different value of B even with an error of 20%, it is possible to use it as an index of sea surface state for when each water mass is produced in the sea surface mixed layer. Moreover, based on our values of B, we estimated preformed dissolved oxygen (DO) (C_preDO, 309–332 μmol/kg) and the saturation state of C_preDO (ΔpreDO, − 7.0 to − 1.2%) in this region. Thus, the difference between C_preDO and DO content in the ocean interior may be a more useful index for biogenic organic decomposition in the ocean field compared to Apparent Oxygen Utilization (AOU). Until now, the estimation of oceanic uptake of anthropogenic CO₂ has used AOU as a major parameter. Therefore, it may be necessary to re-evaluate the oceanic uptake of anthropogenic CO₂ based on our new concept of B.     

Accumulation of total CO2 during stagnation in the Baltic Sea deep water and its relationship to nutrient and oxygen concentrations

Accumulation of total CO₂ (C_T) was investigated in the sub-halocline deep water of the Gotland Sea (Baltic Sea) during a period of stagnation from 1995 to 1999. Depth profiles for C_T, nitrate, phosphate, and oxygen were measured during seven cruises in a grid consisting of 26 stations. The mean C_T increased by more than 60 μmol/kg from October 1995 to July 1999 corresponding to a mean accumulation rate of 1.1 mol/m² year. Taking into account vertical mixing, the vertical distribution of the C_T accumulation was used to determine mineralization rates at different depths. High rates immediately below the halocline indicated the existence of a fraction of organic matter, which is rapidly mineralized during sinking through the water column. A second fraction is more refractive and accumulates at the sediment surface in the deep center of the basin where it is slowly mineralized and partly buried. Phosphate release rates in anoxic waters and especially at the redoxcline were substantially higher than those estimated on the basis of the carbon mineralization and the Redfield C/P ratio. This is attributed to non-Redfield mineralization ratios and the dissolution of iron oxide/phosphate associates. The formation of nitrate by mineralization under oxic conditions was almost completely compensated by denitrification. Using the carbon mineralization rates and a C/N ratio of 8.4, a denitrification rate of 280 mmol/m² year was obtained, which approximately balances the input of nitrate/ammonia into the surface water. Relating the apparent oxygen utilization (AOU) to the C_T fraction that was generated by mineralization yielded a carbon mineralization/O₂ consumption ratio of 0.83.     

Alkalinity titration in seawater: How accurately can the data be fitted by an equilibrium model?

Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg⁻¹. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E₀, total alkalinity A_t, total carbonate C_t, and first acidity constant of carbon dioxide pK₁ are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. C_x=20 μmol kg⁻¹, pK_x=6.2) produces a deviation approaching 20 μmol kg⁻¹ at constant C_t; however, adjustment of C_t by about −18 μmol kg⁻¹ to produce a good fit leaves only ± 1.5 μmol kg⁻¹ residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l⁻¹) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in C_t in the pH range 5–6, as a result of CO₂ gas loss from the titration vessel. Attempts to compensate for this by adjustment of A_t, C_t, or pK₁ produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H⁺ scale (for which [HSO₄⁻] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H⁺]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO₄⁻] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na⁺ as well as H⁺ can be adequately compensated to pH 9.5 by a linear selectivity expression.     

Time-series of surface water CO2 and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): Seasonality of uptake and release

High resolution measurements of carbon dioxide and oxygen were made in surface waters of the central Arkona Sea (Baltic Sea) from May 2003 to September 2004. Sensors for CO₂ partial pressure (pCO₂^w) and oxygen (O₂) concentration were mounted in 7 m depth on a moored platform which is used for hydrographic and meteorological monitoring. The pCO₂^w data were obtained in half hour intervals and O₂ was measured each hour as an average of a 10 min measurement. To check the performance of the sensors, pCO₂^w and O₂ were determined by shipboard measurements on a research vessel which visited the site in 1–2 month intervals. In addition, pCO₂^w was measured on a “volunteer observing ship” (VOS) passing the platform each second day at a distance of about 25 km. Minima of 220 to 250 μatm of pCO₂^w were observed at the time of the spring bloom and a cyanobacteria bloom in mid-summer. During winter the pCO₂^w was mostly close to equilibrium with the atmosphere but maxima of 430 to 530 μatm were also observed. The seasonality of oxygen and pCO₂^w showed an opposing pattern. From a multiple regression analysis, we concluded that two processes primarily controlled pCO₂^w during our study: biological turnover and mixing. A parameterization, based on apparent oxygen utilisation (AOU) and salinity (S) only (pCO₂^w = 1.23 AOU + 43 S), reproduced the seasonality of pCO₂^w in surface water reasonably well. Based on our pCO₂, salinity, and temperature data set, we attempted to separate processes changing total inorganic carbon concentrations (C_T) by using an alkalinity–salinity relation for the area. The contribution of CO₂ gas exchange and mixing were calculated and from this the biological turnover was deduced to reveal the calculated C_T changes.The net annual uptake of CO₂ in the central Arkona Sea was estimated to be about 1.5 Tg (1.5·10¹² g) which was approximately balanced by a net oxygen release considering the uncertainties of the flux calculations. Near-coast CO₂ emission due to episodic upwelling partly compensated the uptake of the central part of the Arkona Sea reducing the overall magnitude of the CO₂ uptake.     

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.     

Time series of carbonate system variables off Otaru coast in Hokkaido, Japan

We report several biogeochemical parameters (dissolved inorganic carbon (DIC), total alkalinity (TA), dissolved oxygen (DO), phosphate (PO₄), nitrate + nitrite (NO₃ + NO₂), silicate (Si(OH)₄)) in a region off Otaru coast in Hokkaido, Japan on a “weekly” basis during the period of April 2002–May 2003. To better understand the long-term temporal variations of the main factors affecting CO₂ flux in this coastal region and its role as a sink/source of atmospheric CO₂, we constructed an algorithm of DIC and TA using other hydrographic properties. We estimated the CO₂ flux across the air–sea interface by using the classical bulk method. During 1998–2003 in our study region, the estimated fCO_2sea ranged about 185–335 μatm. The maximum of fCO_2sea in the summer was primarily due to the change of water temperature. The minimum of fCO_2sea in the early spring can be explained not only by the change of water temperature but also the change of nutrients and chlorophyll-a. To clarify the factors affecting fCO_2sea (water temperature, salinity, and biological activity), we carried out a sensitivity analysis of these effects on the variation of fCO_2sea. In spring, the biological effect had the largest effect for the minimum of fCO_2sea (40%). In summer, the water temperature effect had the largest effect for the maximum of fCO_2sea (25%). In fall, the water temperature effect had the largest effect for the minimum of fCO_2sea (53%). In winter, the biological effect had the largest effect for the minimum of fCO_2sea (35%).We found that our study region was a sink region of CO₂ throughout a year (−0.78 mol/m²/yr). Furthermore, we estimated that the increase of fCO_2sea was about 0.56 μatm/yr under equilibrium with the atmospheric CO₂ content for the period 1998–2003, with the temporal changes in the variables (T, S, PO₄) on fCO_2sea, thus as the maximum trend of each variable on fCO_2sea was 0.22 μatm/yr, and the trend of residual fCO₂ including gas exchange was 0.34 μatm/yr. This result suggests that interaction among variables would affect gas exchange between air and sea effects on fCO_2sea. We conclude that this study region as a representative coastal region of marginal seas of the North Pacific is special because it was measured, but there is no particular significance in comparison to any other area.     

A seasonal carbon budget for the sub-Antarctic Ocean, South of Australia

Changes from winter (July) to summer (February) in mixed layer carbon tracers and nutrients measured in the sub-Antarctic zone (SAZ), south of Australia, were used to derive a seasonal carbon budget. The region showed a strong winter to summer decrease in dissolved inorganic carbon (DIC;  45 µmol/kg) and fugacity of carbon dioxide (fCO₂;  25 µatm), and an increase in stable carbon isotopic composition of DIC (δ¹³C_DIC;  0.5‰), based on data collected between November 1997 and July 1999.The observed mixed layer changes are due to a combination of ocean mixing, air–sea exchange of CO₂, and biological carbon production and export. After correction for mixing, we find that DIC decreases by up to 42 ± 3 µmol/kg from winter (July) to summer (February), with δ¹³C_DIC enriched by up to 0.45 ± 0.05‰ for the same period. The enrichment of δ¹³C_DIC between winter and summer is due to the preferential uptake of ¹²CO₂ by marine phytoplankton during photosynthesis. Biological processes dominate the seasonal carbon budget (≈ 80%), while air–sea exchange of CO₂ (≈ 10%) and mixing (≈ 10%) have smaller effects. We found the seasonal amplitude of fCO₂ to be about half that of a study undertaken during 1991–1995 [Metzl, N., Tilbrook, B. and Poisson, A., 1999. The annual fCO₂ cycle and the air–sea CO₂ flux in the sub-Antarctic Ocean. Tellus Series B—Chemical and Physical Meteorology, 51(4): 849–861.] for the same region, indicating that SAZ may undergo significant inter-annual variations in surface fCO₂. The seasonal DIC depletion implies a minimum biological carbon export of 3400 mmol C/ m² from July to February. A comparison with nutrient changes indicates that organic carbon export occurs close to Redfield values (ΔP:ΔN:ΔC = 1:16:119). Extrapolating our estimates to the circumpolar sub-Antarctic Ocean implies a minimum organic carbon export of 0.65 GtC from the July to February period, about 5–7% of estimates of global export flux. Our estimate for biological carbon export is an order of magnitude greater than anthropogenic CO₂ uptake in the same region and suggests that changes in biological export in the region may have large implications for future CO₂ uptake by the ocean.     

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO₂ evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1–5 μmol of carbon and has an associated blank of 0.1–0.2 μmol of carbon.Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO₂ as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3.. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The δ¹³C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC.The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average δ¹³C = −12.4.). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and δ¹³C of pore-water DOC was nearly 8. lighter at 1.5–2.0-cm depth than in the mat surface layer (0–0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and δ¹³C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.     

Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements

Appropriate conditions have been achieved for the accurate, rapid, and highly precise shipboard simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation. A nitrogen-specific Antek 705D chemiluminescence detector and a CO₂-specific LiCor Li6252 IRGA have been coupled in-series with a Shimadzu TOC-5000 organic carbon analyser. Precision of both simultaneous measurements is ≤1.5%, i.e. ±1 μmol C l⁻¹ and ±0.3 μmol N l⁻¹, respectively. Quality of analysis is not compromised by vibrations associated with ocean going research vessels.     

Intercomparison of shipboard and moored CARIOCA buoy seawater fCO2 measurements in the Sargasso Sea

The ocean is an important sink for carbon and heat, yet high-resolution measurements of biogeochemical properties relevant to global climate change are being made only sporadically in the ocean at present. There is a growing need for automated, real-time, long-term measurements of CO₂ in the ocean using a network of sensors, strategically placed on ships, moorings, free-drifting buoys and autonomous remotely operated vehicles. The ground-truthing of new sensor technologies is a vital component of present and future efforts to monitor changes in the ocean carbon cycle and air–sea exchange of CO₂.A comparison of a moored Carbon Interface Ocean Atmosphere (CARIOCA) buoy and shipboard fugacity of CO₂ (fCO₂) measurements was conducted in the western North Atlantic during two extended periods (>1 month) in 1997. The CARIOCA buoy was deployed on the Bermuda Testbed Mooring (BTM), which is located 5 km north of the site of the US Joint Global Ocean Flux Study (JGOFS) Bermuda Atlantic Time-series Study (BATS). The high frequency of sampling revealed that temperature and fCO₂ responded to physical forcing by the atmosphere on timescales from diurnal to 4–8 days. Concurrent with the deployments of the CARIOCA buoy, frequent measurements of surface fCO₂ were made from the R/V Weatherbird II during opportunistic visits to the BTM and BATS sites, providing a direct calibration of the CARIOCA buoy fCO₂ data. Although, the in situ ground-truthing of the CARIOCA buoy was complicated by diurnal processes, sub-mesoscale and fine-scale variability, the CARIOCA buoy fCO₂ data was accurate within 3±6 μatm of shipboard fCO₂ data for periods up to 50 days. Longer-term assessments were not possible due to the CARIOCA buoy breaking free of the BTM and drifting into waters with different fCO₂-temperature properties. Strategies are put forward for future calibration of other in situ sensors.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

The influence of island generated eddies on the carbon dioxide system, south of the Canary Islands

Measurements of surface partial pressure of CO₂ and water column alkalinity, pH_T, nutrients, oxygen, fluorescence and hydrography were carried out, south of the Canary Islands during September 1998. Cyclonic and anticyclonic eddies were alternatively observed from the northwestern area to the central area of the Canary Islands. Nutrient pumping and vertical uplifting of the deep chlorophyll maximum by cyclonic eddies were also ascertained by upward displacement of dissolved inorganic carbon. A model was applied to determine the net inorganic carbon balance in the cyclonic eddy. The fluxes were determined considering both the diffusive and convective contributions from the upward pumping and the corresponding horizontal transport of water outside the area. An increase in the total inorganic carbon concentration in the upper layers inside the eddy field of 133 mmol C m^− 2 d^− 1 was determined. The upward flux of inorganic carbon decreased the effect of the increased primary production on the carbon dioxide chemistry. The reduced fCO₂ inside the cyclonic eddy, 15 μatm lower than that observed in non-affected surface water, was explained by thermodynamic aspects, biological activity, eddy upward pumping and diffusion and air–sea water exchange effects.     

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).     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

Temperature dependence of CO2 fugacity in seawater

Ideally, the correction of the measured CO₂ fugacity (fCO₂) at temperature T_m to fCO₂ at the in-situ temperature T_in should be made by using at least 2 known parameters (pH-A_T, C_T-A_T,…) and the reliable constants for carbonic acid. In practice however, a measured CO₂ property pair is not always available. When fCO₂ is measured alone, one must make an estimate of the effect of temperature on seawater fCO₂ from the accurate knowledge of seawater salinity and temperature and the approximate knowledge of the carbonate parameters. In this paper we present an empirical relationship that can be used to estimate the effect of temperature on fCO₂. The equation is of the form:

ƒCO_2[t] − ƒCO_2[20]=A + Bt + Ct² + Dt³ + Et⁴

where fCO_2[t] and fCO_2[20] represent fCO₂ at temperatures t°C and 20°C, respectively; the parameters A, B, etc. are functions of the ratio X = C_T/A_T:

E = e₀ + e₁X + e₂X²ln(X) + e₃exp(X) + e₄/ln(X)

where the parameters a_i, b_i, etc. are functions of salinity.The 25-parameter equation is fitted by the values of fCO₂ calculated using the constants of Goyet and Poisson (1989), when X varies from 0.8 to 1.0, t varies from −1dgC to 40°C, and S varies from 30 to 40. For T_m - T_in within ± 10°C, direct measurements of fCO₂ as a function of the temperature (from −I to 30°C verify this equation within less than ±5 μatm.     

Annual cycle of fCO2 under sea-ice and in open water in Prydz Bay, East Antarctica

The annual cycle of dissolved nutrients and the fugacity of CO₂ (fCO₂), calculated from the concentration of dissolved inorganic carbon (DIC) and pH, was studied over a 14-month long period (December 1993 to February 1995) at a site in Prydz Bay near Davis Station, Vestfold Hills, East Antarctica. Significant spring decreases in fCO₂ began under the sea-ice in mid-October, when both water column and sea-ice algal activity resulted in the removal of nutrients and DIC and increased pH. Minimum fCO₂ (<100 μatm) and lowest nutrient and DIC concentrations occurred in December and January. The low summer fCO₂ values were clearly the result of biological activity. The seasonal depletion of dissolved nitrate reached 85% in mid-summer when chlorophyll-a concentrations exceeded 15 mg m⁻³. Oceanic uptake of carbon dioxide from the atmosphere, calculated from the fugacity difference and daily wind speeds, averaged more than 30 mmol m⁻² day⁻¹ during the summer ice-free period. This exchange replaced approximately half of the DIC consumed by biological activity. Apparent nutrient utilisation ratios (C/N/P) were close to Redfield values. In autumn fCO₂ began to rise, continuing slowly well into winter, and reaching a maximum close to modern atmospheric values between July and September. This increase can be attributed to a combination of local remineralisation of organic carbon in the water column and the steady increase in the mixing depth of the water column. At first glance, this suggests that air–sea equilibration occurred in winter despite the sea-ice cover, perhaps by horizontal circulation from regions outside the pack ice, or through openings in the ice. However, the persistent 15 to 20% undersaturation of dissolved oxygen throughout the winter suggests an alternate explanation. The late winter fCO₂ level may represent a characteristic established by global circulation, so that as a result of increasing atmospheric CO₂ concentrations, these Antarctic waters are in transition from being a winter-time source of CO₂ to the atmosphere to becoming a sink. Our fCO₂ observations emphasize the need to address seasonal variations in assessing Antarctic contributions to the oceanic control of atmospheric CO₂.     

Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy

A new deep-sea laser Raman spectrometer (DORISS—Deep Ocean Raman In Situ Spectrometer) is used to observe the preferential dissolution of CO₂ into seawater from a 50%–50% CO₂–N₂ gas mixture in a set of experiments that test a proposed method of CO₂ sequestration in the deep ocean. In a first set of experiments performed at 300 m depth, an open-bottomed 1000 cm³ cube was used to contain the gas mixture; and in a second set of experiments a 2.5 cm³ funnel was used to hold a bubble of the gas mixture in front of the sampling optic. By observing the changing ratios of the CO₂ and N₂ Raman bands we were able to determine the gas flux and the mass transfer coefficient at 300 m depth and compare them to theoretical calculations for air–sea gas exchange. Although each experiment had a different configuration, comparable results were obtained. As expected, the ratio of CO₂ to N₂ drops off at an exponential rate as CO₂ is preferentially dissolved in seawater. In fitting the data with theoretical gas flux calculations, the boundary layer thickness was determined to be  42 μm for the gas cube, and  165 μm for the gas funnel reflecting different boundary layer turbulence. The mass transfer coefficients for CO₂ are k_L = 2.82 × 10^− 5 m/s for the gas cube experiment, and k_L = 7.98 × 10^− 6 m/s for the gas funnel experiment.