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1.
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.  相似文献   

2.
A preliminary study of carbon system in the East China Sea   总被引：1，自引：0，他引：1  
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.  相似文献   

3.
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.  相似文献   

4.
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5.
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.  相似文献   

6.
In the Mediterranean Sea the carbon chemistry is poorly known. However, the impact of the regional and large-scale anthropogenic pressures on this fragile environment rapidly modifies the distribution of the carbonate system key properties like CT (total dissolved inorganic carbon), AT (total alkalinity), CANT (anthropogenic CO2), and pH. This leads inexorably to the acidification of its waters. In order to improve our knowledge, we first develop interpolation procedures to estimate CT and AT from oxygen, salinity, and temperature data using all available data from the EU/MEDAR/MEDATLAS II database. The acceptable levels of precision obtained for these estimates (6.11 ??mol-kg−1 for CT and 6.08 ??mol kg−1 for AT) allow us to draw the distribution of CANT (with an uncertainty of 6.75 ??mol kg−1) using the Tracer combining Oxygen, inorganic Carbon, and total Alkalinity (TrOCA) approach. The results indicate that: 1) all Mediterranean water bodies are contaminated by anthropogenic carbon; 2) the lowest concentration of CANT is 37.5 ??mol kg−1; and 3) the western basin is more contaminated than the Eastern basin. After reconstructing the distribution of key properties (CT, AT, CANT) for four periods of time (between 1986 and 2001) along a west-east section throughout the whole Mediterranean Sea, we analyze the impact of the Eastern Mediterranean Transient (EMT). Not only has the concentration of CANT increased (especially in the intermediate and the bottom layers of the eastern basin, during and after the EMT), but also the distribution of all properties has been considerably perturbed. This is discussed in detail. For the first time, the level of acidification is estimated for the Mediterranean Sea. Our results indicate that for the year 2001 all waters (even the deepest) have been acidified by values ranging from −0.14 to −0.05 pH unit since the beginning of the industrial era, which is clearly higher than elsewhere in the open ocean. Given that the pH of seawater may affect a very large number of chemical and biological processes, our results stress the necessity to develop new programs of research to understand and then predict the evolution of the carbonate system properties in the Mediterranean Sea.  相似文献   

7.
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 At, total carbonate Ct, 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. Cx=20 μmol kg−1, pKx=6.2) produces a deviation approaching 20 μmol kg−1 at constant Ct; however, adjustment of Ct 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 Ct 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 At, Ct, 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.  相似文献   

8.
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 (CT) and total alkalinity (AT) measurements does not yield results comparable in accuracy and precision to fCO2 measurements.  相似文献   

9.
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.  相似文献   

10.
彭鹏飞  马媛  史荣君  王迪  许欣  颜彬 《海洋科学》2022,46(10):140-149
根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的pH、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(PP)、表层海水CO2分压[p(CO2)]和海-气界面CO2交换通量(FCO2),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chla、DIC、HCO3–和PP显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO3–、和CO32–显著大于养殖旺季,养殖旺季的p(CO2)和FCO2显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO2交换通量FCO2平均值分别是(42.04±9.56)、(276.14±52.55)、(–11.59±18.15)和(–13.02±6.71)mmol/(m2·d),冬季各站位FCO2值离散度较大,其中位数是–10.73mmol/(m2·d)。在全年尺度,表层海水p(CO2)及FCO2与水温呈显著正相关,与盐度呈显著负相关。在非养殖区,浮游植物光合作用可能对影响表层海水p(CO2)及FCO2起主导作用。养殖牡蛎钙化、呼吸作用等生理因素释放的CO2对表层海水p(CO2)及FCO2未产生显著影响。考洲洋养殖海域养殖旺季为CO2的源,养殖淡季整体为CO2的弱汇。  相似文献   

11.
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12.
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 (fCO2SW) 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 fCO2SW in the summer of 2015.  相似文献   

13.
A direct method involving a single iteration (a quadratic equation solved twice) is given for the calculation of carbonate ion concentration from total CO2 and titration alkalinity. The simplified calculation should allow wider use of existing total CO2 and titration alkalinity data.  相似文献   

14.
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).  相似文献   

15.
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.  相似文献   

16.
This study presents the distribution and fluxes of dissolved inorganic carbon (CT), total alkalinity (AT) and anthropogenic carbon (Cant) 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 Cant 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 Cant have penetrated the highly alkaline Eastern Mediterranean waters, thereby causing a significant pH reduction since the pre-industrial era.Estimates of the transports of CT and Cant 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 CT inflow. The Levantine Intermediate Water (LIW) contributes to about one-third of the total CT and Cant inflow. Although the amounts of Cant annually transported by LIW and ADW are almost equal, the contribution of Cant to the CT transported by each water mass is slightly higher in ADW (3.1%) than in LIW (2.6%), as a result of its higher mean Cant concentration. The ADW, despite its weak contribution to the total outflow of Cant, 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.  相似文献   

17.
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 (CT) can be determined extremely accurately by titration, a combination of carbonate alkalinity and CT is the most satisfactory combination for the majority of applications. If, however, PCO2 is required it should be measured directly.  相似文献   

18.
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 fCO2sea ranged about 185–335 μatm. The maximum of fCO2sea in the summer was primarily due to the change of water temperature. The minimum of fCO2sea 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 fCO2sea (water temperature, salinity, and biological activity), we carried out a sensitivity analysis of these effects on the variation of fCO2sea. In spring, the biological effect had the largest effect for the minimum of fCO2sea (40%). In summer, the water temperature effect had the largest effect for the maximum of fCO2sea (25%). In fall, the water temperature effect had the largest effect for the minimum of fCO2sea (53%). In winter, the biological effect had the largest effect for the minimum of fCO2sea (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 fCO2sea 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 fCO2sea, thus as the maximum trend of each variable on fCO2sea 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 fCO2sea. 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.  相似文献   

19.
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.  相似文献   

20.
云贵高原湖泊沉积物─水界面碱度扩散通量研究   总被引：4，自引：0，他引：4  
于１９９１－１９９５年间５次在云贵高原泸沽湖，洱海湖和贵州阿哈湖，百花湖的湖心采集沉积物柱芯，界面水和湖水样品，通过其ｐＨ值和ＨＣＯ３浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上不体碱度的影响程度，研究结果表明，云贵高原某些湖水寄宿时间对较长，湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一，湖水寄宿时间较短，深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不地。  相似文献   

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