The effect of analytical error on the evaluation of the components of the aquatic carbon-dioxide system

A study has been made of the effect of error in the measurement of the determinable parameters of the marine CO₂ system on the calculation of the remaining parameters from equations such as those of Park (1969). This approach can be used either to assess and compare experimental data, or to aid in the choice of suitable combinations of determinable parameters for solving any particular problem. Now that the total alkalinity and total inorganic carbon (C_T) can be determined extremely accurately by titration, a combination of carbonate alkalinity and C_T is the most satisfactory combination for the majority of applications. If, however, P_CO2 is required it should be measured directly.     

Improved Method for Calculating Anthropogenic CO2 in the Upper Layer of the North Pacific Subtropical Gyre along 175°E

Seawater samples were collected in the North Pacific along 175°E during a cruise of the Northwest Pacific Carbon Cycle Study (NOPACCS) program in 1994. Many properties related to the carbonate system were analyzed. By using well-known ratios to correct for chemical changes in seawater, the CO₂ concentration at a given depth was back calculated to its initial concentration at the time when the water left the surface in winter. We estimated sea-surface CO₂ and titration alkalinity (TA) in present-day winter, from which we evaluated the degree of air-sea CO₂ disequilibrium in winter was. Using a correction factor for air-sea CO₂ disequilibrium in winter, we reconstructed sea-surface CO₂ in pre-industrial times. The difference between the back-calculated initial CO₂ and sea-surface CO₂ in pre-industrial times should correspond to anthropgenic CO₂ input. Although the mixing of different water masses may cause systematic error in the calculation, we found that the nonlinear effect induced by the mixing of different water masses was negligible in the upper layer of the North Pacific subtropical gyre along 175°E. The results of our improved method of assessing the distribution of anthropogenic CO₂ in that region show marked differences from those obtained using the previous back-calculation method.     

Calibration and evaluation of a carbonate microsensor for studies of the marine inorganic carbon system

Accurate and rapid determination of inorganic carbon constituents in ocean environments is important for understanding the carbon cycle, especially in the context of ocean-acidification research. A microsensor capable of directly measuring carbonate ion (CO₃ ^2–) concentrations would be desirable. In this study, a carbonate microsensor with a polymeric liquid membrane was fabricated, and two calibration methods were used to evaluate its performance. The first method was based on continuous titration. Small increments of HCl were added to seawater or Na₂CO₃ solution to adjust the total alkalinity and pH values and thus obtain a series of carbonate concentrations. The second method used a series of discrete standards. Varying amounts of HCl or NaOH were added to separate seawater aliquots, and the CO₃ ^2– concentration of each standard was calculated from the resulting total alkalinity and total dissolved inorganic carbon. Both methods were found to be adequate for achieving accurate calibration of the CO₃ ^2– sensor, and both are suitable for field work. The discrete standards method, however, is more convenient and may provide a better linear range at low CO₃ ^2– concentrations (detection range: 2–300 μmol/kg) than the continuous titration method in seawater (detection range: 10–250 μmol/kg). This CO₃ ^2– microsensor can be used for 5–7 d and detects changes in carbonate concentration as low as 2 μmol/kg in the inorganic carbon constituents of the environments where marine calcareous organisms grow. The CO₃ ^2– microelectrode was further assessed by applying it to the measurement of pore-water CO₃ ^2– concentration profiles in a marine sediment core.     

Comparison of the results of determination of the carbonate system and the total alkalinity of seawater according to the data obtained by using different analytic methods

On the basis of the data of hydrochemical investigations of waters of the Sevastopol Bay, we discuss the results of the analysis of the carbonate system and the total alkalinity of seawater obtained by using two methods. By using the linear method of least squares, we compare the results of the analysis of the carbonate system according to pH values and the total alkalinity and according to pH values and dissolved inorganic carbon. It is shown that, within the investigated range of pH values, Alk, and TCO₂, the mean relative deviations of values of the fugacity of CO₂ and the concentrations of dissolved CO₂ and CO₃²⁻ ions computed by using different input parameters are equal to 3.0, 1.0, and 9.6%, respectively.     

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.     

Diurnal and seasonal variation in physico-chemical conditions within intertidal rock pools

A study of the diurnal and seasonal variation in the physico-chemical conditions within intertidal rock pools on the West coast of Scotland was undertaken to provide data on the environmental conditions experienced by animals inhabiting these pools. The temperature, pH, partial pressure of oxygen (P_O2) and salinity were measured every hour for 24 h and the total alkalinity, partial pressure of carbon dioxide (P_CO2) and carbon dioxide content (C_CO2) calculated. This sampling regime was carried out once a month for 12 months to determine the extent of seasonal variation in conditions within temperate pools.Large diurnal variations were recorded in nearly all the physico-chemical parameters measured. The greatest variation was recorded in the temperature and P_O2 of the water but significant changes in pH and P_CO2 were also recorded. Total alkalinity varied little during any 24 h period but carbonate alkalinity, which was always lower than total alkalinity, showed slightly greater variation. There was also considerable variation in the magnitude of these diurnal changes between pools at different heights on the shore.Diurnal variation in the physico-chemical conditions within the pools were observed throughout the year although the magnitude of these changes varied seasonally. Detailed studies on individual pools demonstrated that appreciable local variation existed in the physico-chemical conditions within each pool.     

Determination of alkalinities of estuarine waters by a two-point potentiometric titration

Gran plots of titrations of seawater with acid are straight lines after protonation of all weak acids when ion-pairing is taken into account. This property is used to calibrate the pH electrode and to determine the endpoint of what is essentially a two-point alkalinity titration of the sample. First the initial sample pH is measured; then a standard addition of acid is made giving a pH near 3.2 (pH₁); a further acid addition is made giving a pH near 2 (pH₂). The slope of the electrode response and the total alkalinity are calculated from pH₂ and pH₁. The advantages of this method are that no separate calibrations are necessary: no corrections for variations in activity coefficients are needed because pH values are obtained on the seawater pH scale; and the instruments used for the determinations are very simple. The standard deviation of the alkalinity determination of seawater by the proposed technique was − 0.10%.     

Assessments of anthropogenic CO2 distribution in the tropical Atlantic Ocean

With a limited number of properties (salinity, temperature, total dissolved inorganic carbon, total alkalinity, and oxygen) from a recent cruise in the tropical Atlantic Ocean, we use the simple and recent approach TrOCA (Tracer combining Oxygen, inorganic Carbon, and total Alkalinity) to estimate the distribution of anthropogenic CO₂ along three latitudinal sections. In order to assess the quality of the anthropogenic CO₂ distribution, results from the method are compared to the CFC-11 measurements. We discuss the large-scale distribution of the main water masses of the tropical Atlantic Ocean in the light of the anthropogenic CO₂ and the CFC-11 distributions. Keeping in mind that the anthropogenic CO₂ emission began 60 years earlier than that of CFC-11, the former provides new insight on the local circulation and efficiency of the tropical waters to store the atmospheric carbon.     

A preliminary study of carbon system in the East China Sea

In the central part of the East China Sea, the activity of CO₂ in the surface water and total carbonate, pH and alkalinity in the water column were determined in winter and autumn of 1993. The activity of CO₂ in the continental shelf water was about 50 ppm lower than that of surface air. This decrease corresponds to the absorption of about 40 gC/m²/yr of atmospheric CO₂ in the coastal zone or 1 GtC/yr in the global continental shelf, if this rate is applicable to entire coastal seas. The normalized total carbonate contents were higher in the water near the coast and near the bottom. This increase toward the bottom may be due to the organic matter deposited on the bottom. This conclusion is supported by the distribution of pH. The normalized alkalinity distribution also showed higher values in the near-coast water, but in the surface water, indicating the supply of bicarbonate from river water. The residence time of the East China Sea water, including the Yellow Sea water, has been calculated to be about 0.8 yr from the excess alkalinity and the alkalinity input. Using this residence time and the excess carbonate, we can estimate that the amount of dissolved carbonate transported from the coastal zone to the oceanic basin is about 70 gC/m²/yr or 2 GtC/yr/area-of-global-continental-shelf. This also means that the rivers transport carbon to the oceans at a rate of 30 gC/m²/yr of the coastal sea or 0.8 GtC/yr/ area-of-global shelf, the carbon consisting of dissolved inorganic carbonate and terrestrial organic carbon decomposed on the continental shelf.     

Recent increase in surface fCO<Subscript>2</Subscript> in the western subtropical North Pacific

We observed unusually high levels (> 440 μatm) of carbon dioxide fugacity (fCO₂) in surface seawater in the western subtropical North Pacific, the area where Subtropical Mode Water is formed, during summer 2015. The NOAA Kuroshio Extension Observatory moored buoy located in this region also measured high CO₂ values, up to 500 μatm during this period. These high sea surface fCO₂ (fCO_2SW) values are explained by much higher normalized total dissolved inorganic carbon and slightly higher normalized total alkalinity concentrations in this region compared to the equatorial Pacific. Moreover, these values are much higher than the climatological CO₂ values, even considering increasing atmospheric CO₂, indicating a recent large increase in sea surface CO₂ concentrations. A large seasonal change in sea surface temperature contributed to higher surface fCO_2SW in the summer of 2015.     

Decadal evolution of anthropogenic CO2 in the northwestern Mediterranean Sea from the mid-1990s to the mid-2000s

Monthly observations accumulated over more than a decade at the DYFAMED time-series station allow us to estimate the temporal evolution of anthropogenic CO₂ in the western Mediterranean Sea. This objective is reached by using recognized interpolation procedures to reconstruct the incomplete distributions of measured total dissolved inorganic carbon and total alkalinity. These reconstructed fields, associated with those available for dissolved oxygen and temperature, are used to estimate the distribution of anthropogenic CO₂. This is done with the recently developed Tracer combining Oxygen, inorganic Carbon, and total alkalinity (TrOCA) approach. The main results indicate that (1) the concentrations of anthropogenic CO₂ are much higher than those found in the Atlantic Ocean (the minimum concentration at the DYFAMED site is 50 μmol kg⁻¹), and (2) the temporal trend for anthropogenic CO₂ is decreasing, especially in the intermediate and the deep layers of the water column at the DYFAMED site. This decrease in anthropogenic CO₂ is significantly correlated with a decrease in the dissolved oxygen and with an increase in both salinity and temperature. These trends are discussed in the light of recent published works that propose explanations for the observed increases in salinity and temperature that occurred in the western basin since the 1950s. We conclude that the decrease in anthropogenic CO₂ probably resulted from an invasion of old water masses. Different hypotheses on the origin of these water masses are considered and several arguments indicate that the eastern Mediterranean transient (EMT) could have played an important role in the observed decrease in anthropogenic CO₂ concentrations at the DYFAMED site.     

Total inorganic carbon in sea ice

The method proposed for determining the total inorganic carbon (TC) concentrations in sea ice (Arctic region, North Pole-35 expedition) based on the measurement of the total alkalinity (TA) and the pH in the melt waters without the CO₂ exchange with the atmosphere is considered. It is shown that the TC/Sal and TA/TC values through the entire ice section remain similar to these parameters in the subice water. The surface snow and the uppermost ice layers are characterized by elevated TA/TC values, which indicate the reaction Ca²⁺ + 2HCO₃⁻ = ↓CaCO₃ + ↑CO₂ + H₂O. The release of CO₂ to the atmosphere due to the decomposition of calcium hydrocarbonate is as high as ∼20 mmol/m². The meltwater of the examined ice is undersaturated with CO₂, which may result in a sink of atmospheric CO₂ (∼30 mmol/m²).     

Intraannual and long-term variations of the carbonate system of the aerobic zone in the black sea

We provide an expert quality assessment of the data for 1932–1993 and used these data to perform the numerical analysis of the carbonate system of the aerobic zone in the Black Sea. The intraannual and long-term variations of the carbonate system are studied in the abyssal part of the sea for 1960–1993. We propose explanations of the intraannual variations of the analyzed system for various layers of the aerobic zone and reveal long-term variations of the pH values, total alkalinity, and the ratios of the components of the carbonate system. We discover and explain the observed increase in the concentrations of TCO₂ and CO₂ and the partial pressure of carbon dioxide pCO₂, as well as a decrease in pH values and the concentration of CO₃²⁻ in waters of the aerobic zone of the Black Sea.     

Surface water carbon dioxide in the southwest Indian sector of the Southern Ocean: a highly variable CO2 source/sink region in summer

Measurements of partial pressure of carbon dioxide (pCO₂), total dissolved inorganic carbon (TCO₂), total alkalinity (TA) and chlorophyll a (Chl a) have been made in surface water in the southwestern Indian sector of the Southern Ocean (20–85°E) in the austral summer (INDIVAT V cruise, January-February 1987). Between Antarctica and Africa, pCO₂ distribution was linked to the oceanic frontal zones and Chi a variations. The pCO₂ spatial structure was very close to that explored in summer 1967 in the same region but the pCO₂ differences between the ocean and the atmosphere were smaller in 1987 than 20 years ago. At all latitudes we found strongly contrasting surface pCO₂ characteristics between eastern (around 80°E) and western (around 25°E) regions; C02 sources were mainly in the west and CO₂ sinks in the east. South of 60°S, the contrast could be due to biological activity. Between 60°S and the Antarctic Polar Front, intensification of upwelling might be responsible for the higher _pCO₂ values in the west.     

Seasonal Changes in Oceanic pCO2 in the Oyashio Region from Winter to Spring

We observed the partial pressure of oceanic CO₂, pCO₂ ^sea, and related surface properties in the westernmost region of the subarctic North Pacific, seasonally from 1998 to 2001. The pCO₂ ^sea in the Oyashio region showed a large decrease from winter to spring. In winter, pCO₂ ^sea was higher than 400 μatm in the Oyashio region and this region was a source of atmospheric CO₂. In spring, pCO₂ ^sea decreased to extremely low values, less than 200 μatm (minimum, 139 μatm in 2001), around the Oyashio region with low surface salinity and this region turned out to be a strong sink. The spatial variations of pCO₂ ^sea were especially large in spring in this region. The typical Oyashio water with minimal mixing with subtropical warm water was extracted based on the criterion of potential alkalinity. The contribution of main oceanic processes to the changes in pCO₂ ^sea from winter to spring was estimated from the changes in the concentrations of dissolved inorganic carbon and nutrients, total alkalinity, temperature and salinity observed in surface waters in respective years. These quantifications indicated that photosynthesis made the largest contribution to the observed pCO₂ ^sea decreases in all years and its magnitude was variable year by year. These year-to-year differences in spring biological contribution could be linked to those in the development of the density stratification due to the decrease in surface salinity. Thus, the changes in the surface physical structure could induce those in pCO₂ ^sea in the Oyashio region in spring. Furthermore, it is suggested that the direction and magnitude of the air-sea CO₂ flux during this season could be controlled significantly by the onset time of the spring bloom. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbonate chemistry and projected future changes in pH and CaCO3 saturation state of the South China Sea

To study the dissolved carbonate system in the South China Sea (SCS) and to understand the water mass exchange between the SCS and the West Philippine Sea (WPS), pH, total alkalinity and total CO₂ were measured aboard the R/V Ocean Researcher 1. Because of the sill that separates these two seas in the Luzon Strait with a maximum depth of 2200 m, the SCS Deep Water has characteristics similar to those of water at about 2200 m in the WPS. The minimum pH and the maxima of normalized alkalinity and total CO₂ commonly found in the open oceans at mid-depth also prevail in the WPS but are, however, very weak in the SCS. Rivers and inflows from Kuroshio Surface and Deep Waters through the Luzon Strait as well as those through the Mindoro Strait transport carbon to the SCS year-round. Meanwhile, the outflowing Taiwan Strait water as well as the SCS Surface and Intermediate Waters of the Luzon Strait transports carbon out of the SCS year-round. The Sunda Shelf is also a channel for carbon transport into the SCS in the wet season and out of the SCS in the dry season.fCO₂ data and mass balance calculations indicate that the SCS is a weak CO₂ source in the wet season but an even weaker CO₂ sink in the dry season. With these facts taken together, the SCS is likely a very weak CO₂ source. Anthropogenic CO₂ penetrates to about 1500 m in depth in the SCS, and the entire SCS contains 0.60 ± 0.15 × 10¹⁵ g of excess carbon. Typical profiles of pH as well as the degree of saturation of each of calcite and aragonite in 1850 and 1997 are presented, and those for 2050 AD are projected. The maximum decrease in pH is estimated to be 0.16 pH units in the surface layer when the amount of CO₂ is doubled. It is anticipated that aragonite in the upper continental slope will likely start to dissolve, thereby neutralizing excess CO₂ by around 2050 AD. This paper is unique in that it presents the results of the first attempt ever to estimate the past, present and future physico-chemical properties of the world's largest marginal sea.     

Anthropogenic CO2 fluxes in the Otranto Strait (E. Mediterranean) in February 1995

This study presents the distribution and fluxes of dissolved inorganic carbon (C_T), total alkalinity (A_T) and anthropogenic carbon (C_ant) along the Otranto strait, during February 1995. Based on a limited number of properties (temperature, dissolved oxygen, total alkalinity and dissolved inorganic carbon), the composite tracer TrOCA was used to estimate the concentration of anthropogenic CO₂ in the Otranto strait.Total alkalinity exhibits high values and weak variability throughout the water column of the strait, probably associated with the dense water formation processes in the Adriatic basin that induce a rapid transport of the coastal alkalinity to the deep waters. Elevated C_ant concentrations and high anthropogenic pH variations are observed in the bottom layer of the strait, associated with the presence of Adriatic Deep Water (ADW). The study shows that large amounts of C_ant have penetrated the highly alkaline Eastern Mediterranean waters, thereby causing a significant pH reduction since the pre-industrial era.Estimates of the transports of C_T and C_ant through the strait indicate that during February 1995, the Adriatic Sea imports through the Otranto strait natural and anthropogenic carbon and acts as a net sink of carbon for the Ionian Sea. The anthropogenic carbon that is imported to the Adriatic Sea represents less than 1% of the net C_T inflow. The Levantine Intermediate Water (LIW) contributes to about one-third of the total C_T and C_ant inflow. Although the amounts of C_ant annually transported by LIW and ADW are almost equal, the contribution of C_ant to the C_T transported by each water mass is slightly higher in ADW (3.1%) than in LIW (2.6%), as a result of its higher mean C_ant concentration. The ADW, despite its weak contribution to the total outflow of C_ant, has a vital role for the sequestration and storage of the anthropogenic carbon, as this water mass is the main component of the Eastern Mediterranean Deep Waters and, thus, the anthropogenic CO₂ is transferred in the deep horizons of the Eastern Mediterranean, where it remains isolated for many years.     

The role of pHT measurements in marine CO2-system characterizations

Spectrophotometric pH_T measurements can routinely be obtained with an imprecision on the order of ±0.0005 pH_T units. This level of imprecision is equivalent to an imprecision in total hydrogen ion concentration of ±0.1% (where pH_T=−log[H⁺]_T and [H⁺]_T≅[H⁺]+[HSO₄⁻]). At this level of precision, pH_T measurements provide an important tool in quality control assessments of other CO₂-system parameters (CO₂ fugacity, total inorganic carbon, total alkalinity). CO₂ fugacities and total alkalinities calculated using measured pH_T and total inorganic carbon, for the large data set considered in this work, have relative precisions on the order of 0.15 and 0.1%, respectively. The precision of total inorganic carbon calculated via pH_T and salinity-normalized-alkalinity is on the order of 0.02% or better. In this work, using the NOAA 1992 boreal autumn Equatorial Pacific (EqPac) dataset, it is shown that CO₂-system variables calculated via pH_T can be used to enhance both the precision and accuracy of directly measured parameters. Through the procedures described in this work significant problems were revealed in the initial version of the 1992 NOAA dataset, and the dataset was greatly improved. Additionally, in this work, we revisit CO₂-system thermodynamic consistency issues in view of changes in the pH_T values assigned to tris seawater buffers and consequential changes in the calibration of sulfonephthalein pH_T indicators. As the principal result of a +0.0047 increase in the pK of meta cresol purple, CO₂ fugacity calculations and measurements are in very good agreement for the NOAA 1992 boreal autumn EqPac dataset. We note, as well, that due to a reassignment of the titrant acid concentration used in the NOAA 1992 boreal autumn dataset, measured total alkalinities are in good agreement with total alkalinities calculated from total carbon and pH_T.     

Alkalinity of sea ice in the high-latitudinal arctic according to the surveys performed at north pole drifting station 34 and characterization of the role of the arctic ice in the CO<Subscript>2</Subscript> exchange

The variability of the total alkalinity in the sea ice of the high-latitudinal Arctic from November 2005 to May 2006 is considered. For the bulk of the one- and two-year sea ice, the alkalinity dependence on the salinity is described as TA = k × Sal, where k is the salinity: alkalinity ratio in the under-ice water. The given relationship is valid within a wide salinity range from 0.1 psu in the desalinated fraction of two-year ice to 36 psu in the snow on the young ice surface. Geochemically significant deviations from the relationship noted were observed exclusively in the snow and the upper layer of one-year ice. In the upper layer of one-year ice, an alkalinity deficiency is observed (ΔTA ～ ?0.07 mequiv/kg, or ?15%). In the snow on the surface of the one-year ice, an alkalinity excess is formed under the desalination (ΔTA is as high as 1.3 mequiv/kg, 380%). The deviations registered are caused by the possibility of carbonate precipitation in the form of CaCO₃ · 6H₂O under the seawater freezing. It is shown that the ice formation and the following melting might cause a loss of the atmospheric CO₂ of up to 3 × 10¹² g C/year.     

白令海BR断面海-气CO2通量及其参数特征

通过对2008年夏季白令海大气和海水pCO2连续观测资料,结合BR断面上站位水体垂直采样测量,对白令海不同海区pCO2的分布特征及其与理化参数的关系进行了初步研究,结果表明,将白令海划分为4个具有不同CO2吸收能力的海区,其中陆坡流区碳通量高达-18.72 mmol/(m2·d),是海盆北区的近2倍,比海盆南区高一个量...