Effects of CO<Subscript>2</Subscript> Enrichment on Marine Phytoplankton

Rising atmospheric CO₂ and deliberate CO₂ sequestration in the ocean change seawater carbonate chemistry in a similar way, lowering seawater pH, carbonate ion concentration and carbonate saturation state and increasing dissolved CO₂ concentration. These changes affect marine plankton in various ways. On the organismal level, a moderate increase in CO₂ facilitates photosynthetic carbon fixation of some phytoplankton groups. It also enhances the release of dissolved carbohydrates, most notably during the decline of nutrient-limited phytoplankton blooms. A decrease in the carbonate saturation state represses biogenic calcification of the predominant marine calcifying organisms, foraminifera and coccolithophorids. On the ecosystem level these responses influence phytoplankton species composition and succession, favouring algal species which predominantly rely on CO₂ utilization. Increased phytoplankton exudation promotes particle aggregation and marine snow formation, enhancing the vertical flux of biogenic material. A decrease in calcification may affect the competitive advantage of calcifying organisms, with possible impacts on their distribution and abundance. On the biogeochemical level, biological responses to CO₂ enrichment and the related changes in carbonate chemistry can strongly alter the cycling of carbon and other bio-active elements in the ocean. Both decreasing calcification and enhanced carbon overproduction due to release of extracellular carbohydrates have the potential to increase the CO₂ storage capacity of the ocean. Although the significance of such biological responses to CO₂ enrichment becomes increasingly evident, our ability to make reliable predictions of their future developments and to quantify their potential ecological and biogeochemical impacts is still in its infancy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbonate dissolution in the South Atlantic Ocean: evidence from ultrastructure breakdown in Globigerina bulloides

Ultrastructure dissolution susceptibility of the planktic foraminifer Globigerina bulloides, carbonate ion content of the water column, calcium carbonate content of the sediment surface, and carbonate/carbon weight percentage ratio derived from sediment surface samples were investigated in order to reconstruct the position of the calcite saturation horizon, the sedimentary calcite lysocline, and the calcium carbonate compensation depth (CCD) in the modern South Atlantic Ocean. Carbonate ion data from the water column refer to the GEOSECS locations 48, 103, and 109 and calcium carbonate data come from 19 GeoB sediment surface samples of 4 transects into the Brazil, the Guinea, and the Cape Basins. We present a new (paleo-) oceanographic tool, namely the Globigerina bulloides dissolution index (BDX). Further, we give evidence (a) for progressive G. bulloides ultrastructural breakdown with increasing carbonate dissolution even above the lysocline; (b) for a sharp BDX increase at the sedimentary lysocline; and (c) for the total absence of this species at the CCD. BDX puts us in the position to distinguish the upper open ocean and the upwelling influenced continental margin above from the deep ocean below the sedimentary lysocline. Carbonate ion data from water column samples, calcite weight percentage data from surface sediment samples, and carbonate/carbon weight percentage ratio appear to be good proxies to confirm BDX. As shown by BDX both the calcite saturation horizon (in the water column) and the sedimentary lysocline (at the sediment–water interface) mark the boundary between the carbonate ion undersaturated and highly corrosive Antarctic Bottom Water and the carbonate ion saturated North Atlantic Deep Water (NADW) of the modern South Atlantic.     

Perspectives on Biological Research for CO<Subscript>2</Subscript> Ocean Sequestration

Feasibility studies recently suggest that sequestration of anthropogenic CO₂ in the deep ocean could help reduce the atmospheric CO₂ concentration. However, implementation of this strategy could have a significant environmental impact on marine organisms. This has highlighted the urgent need of further studies concerning the biological impact of CO₂ ocean sequestration. In this paper we summarize the recent literature reporting on the biological impact of CO₂ and discuss the research work required for the future. Although fundamental research of the effect of CO₂ on marine organisms before the practical consideration of CO₂ ocean sequestration was limited, laboratory and field studies concerning biological impacts have been increasing after the first international workshop in 1991 discussing CO₂ ocean sequestration. Acute impacts of CO₂ ocean sequestration could be determined by laboratory and field experiments and assessed by simulation models as described by the following papers in this section. On the other hand, chronic effects of CO₂ ocean sequestration, those directly related to the marine ecosystem, would be difficult to verify by means of experiments and to assess using ecosystem models. One of the practical solutions for this issue implies field experiments starting with controlled small scale and eventually to a large scale of CO₂ injection intended to determine ecosystem alteration. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interstitial water chemistry of Jamaican reef sediment: sulfate reduction and submarine cementation

Chemical and isotopic analyses of pore waters from Jamaican reef sediment suggest the importance of microbial sulfate reduction as a major control upon the origin, distribution, and composition of submarine cements in this fringing reef setting. Fore-reef sediment pore waters exhibit active sulfate reduction and enrichment in ¹⁸O which is consistent with associated active magnesian calcite cementation, alkalinity consumption, and cement enrichment in ¹⁸O. Conversely, lack of widespread submarine cementation in the back-reef corresponds to the diminished resupply of sulfate coupled with input of CO₂-charged meteoric water from a nearby unconfined aquifer into the more stagnant pore waters which lower pore-water magnesian calcite saturation states and preclude active submarine cementation.     

Features of coastal upwelling regions that determine net air-sea CO<Subscript>2</Subscript> flux

The influence of the coastal ocean on global net annual air-sea CO₂ fluxes remains uncertain. However, it is well known that air-sea pCO₂ disequilibria can be large (ocean pCO₂ ranging from ∼400 μatm above atmospheric saturation to ∼250 μatm below) in eastern boundary currents, and it has been hypothesized that these regions may be an appreciable net carbon sink. In addition it has been shown that the high productivity in these regions (responsible for the exceptionally low surface pCO₂) can cause nutrients and inorganic carbon to become more concentrated in the lower layer of the water column over the shelf relative to adjacent open ocean waters of the same density. This paper explores the potential role of the winter season in determining the net annual CO₂ flux in temperate zone eastern boundary currents, using the results from a box model. The model is parameterized and forced to represent the northernmost part of the upwelling region on the North American Pacific coast. Model results are compared to the few summer data that exist in that region. The model is also used to determine the effect that upwelling and downwelling strength have on the net annual CO₂ flux. Results show that downwelling may play an important role in limiting the amount of CO₂ outgassing that occurs during winter. Finally data from three distinct regions on the Pacific coast are compared to highlight the importance of upwelling and downwelling strength in determining carbon fluxes in eastern boundary currents and to suggest that other features, such as shelf width, are likely to be important.     

Sub-Lethal Effects of Elevated Concentration of CO<Subscript>2</Subscript> on Planktonic Copepods and Sea Urchins

Data concerning the effects of high CO₂ concentrations on marine organisms are essential for both predicting future impacts of the increasing atmospheric CO₂ concentration and assessing the effects of deep-sea CO₂sequestration. Here we review our recent studies evaluating the effects of elevated CO₂ concentrations in seawater on the mortality and egg production of the marine planktonic copepod, Acartia steueri, and on the fertilization rate and larval morphology of sea urchin embryos, Hemicentrotus pulcherrimus and Echinometra mathaei. Under conditions of +10,000 ppm CO₂ in seawater (pH 6.8), the egg production rates of copepods decreased significantly. The survival rates of adult copepods were not affected when reared under increased CO₂ for 8 days, however longer exposure times could have revealed toxic effects of elevated CO₂ concentrations. The fertilization rate of sea urchin eggs of both species decreased with increasing CO₂ concentration. Furthermore, the size of pluteus larvae decreased with increasing CO₂ concentration and malformed skeletogenesis was observed in both larvae. This suggests that calcification is affected by elevated CO₂ in the seawater. From these results, we conclude that increased CO₂ concentration in seawater will chronically affect several marine organisms and we discuss the effects of increased CO₂ on the marine carbon cycle and marine ecosystem. This revised version was published online in July 2006 with corrections to the Cover Date.     

Benthic remineralization and burial of biogenic SiO2, CaCO3, organic carbon, and detrital material in the Southern Ocean along a transect at 170° West

We investigated the composition, recycling, and mass accumulation rates of sediments along a transect in the Southern Ocean located from 66°S to 57°S at 170°W. This transect also corresponds to the location of a sediment trap mooring line. The sediments at the seven sites studied range from largely terrigenous material to nearly pure (>90%) biogenic silica. CaCO₃ is a minor but persistent component at most sites. Mass accumulation rates have been determined on the basis of excess ²³⁰Th in the sediments, i.e., ²³⁰Th-normalized accumulation rates. The influence of redistribution of sediments on the sea floor has been estimated from ¹⁴C analyses. The recycling of material delivered to the sediments has been characterized on the basis of pore water studies that make extensive use of both in situ sampling and shipboard extractions. The influence of the highly variable rates of input of particulate matter that characterize much of the Southern Ocean upon pore water gradients and fluxes across the sediment water interface has been considered.We find only poor correspondence between BSiO₂ burial fraction (=burial/particulate flux), a quantifiable measure of preservation efficiency, and BSiO₂ particulate rain along the transect. However, preservation does appear to be closely linked to a combination of sedimentation rate and particulate rain.The burial fraction of BSiO₂ is small relative to benthic rain (5–19%). Despite the small fraction buried, burial flux normalized to (sedimentation rate)^1/2 appears to provide a very consistent means of predicting benthic particulate rain over a large range of rain rates, including data from a number of different studies and environments. At sites with BSiO₂ rain 250 mmol m⁻² yr⁻¹ the average difference between predicted and observed rain is 25–30%. Such rain rates occur in many marine areas, particularly the Southern Ocean, with the result that this relationship potentially provides a means of estimating BSiO₂ benthic rain over prolonged periods in the past on the basis of readily measured sediment parameters.At the southern-most deep ocean station, the particulate flux was characterized by an extremely high C_org/CaCO₃ ratio (>10), but this high ratio does not appear to have a substantial influence on CaCO₃ burial. CaCO₃ is preserved in the sediments at this site despite a particulate flux with a 10-fold excess of C_org above that required for complete dissolution in the sediments. The unexpectedly high preservation of CaCO₃ is due largely to the very steep C_org oxidation rate profile at this site. As a result, a large fraction of the organic matter oxidized in the sediments does so in close proximity to the sediment–water interface where most of the metabolic CO₂ is neutralized by CO₃²⁻ from the overlying water, rather than by the dissolution of sedimentary CaCO₃.Diagenetic modeling indicates that at several of the stations, the remineralization fluxes of carbonate species across the sediment–water interface may not have been at steady state as a result of the highly pulsed nature of particulate rain in this environment. We estimate that at the time of our sampling it is possible that near-interface fluxes could have been a factor of 1.6–2 times the annual average.At every site on the transect, the burial fluxes of detrital material are substantially greater than the detrital particulate rain measured in the sediment traps, by as much as a factor of 40. Detrital burial is bimodal, being greatest at the southern and northern extremes of the transect. We postulate that the excess of burial over particulate rain in the south reflects the contribution of ice rafted debris at these high latitudes. Increases in the supply at the northern stations must have a different source. We believe that the excess at these stations is material eroded from the sea floor to the west, possibly on the Campbell Plateau, and advected by currents to the northern portion of the transect at depths below the shallow traps.     

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.     

Apparent calcite supersaturation at the ocean surface: Why the present solubility product of pure calcite in seawater does not predict the correct solubility of the salt in nature

It is generally accepted that seawaters near the ocean surface are supersaturated with calcite and that increasing atmospheric CO₂ will not overcome this condition until late in the 21st century. These expectations are based on comparisons of the ion activity products (IAPs) of various seawaters to the solubility product (K) of seawater saturated with pure calcite at 1 atm and a given temperature. It has been shown in recent papers, however, that calcites in contact with natural seawater in the surface oceans are not pure, but are magnesian calcite compositions. As a result, the presently accepted values of the solubility product of calcite in seawater cannot be used to obtain a correct, or even a reasonable estimate of the saturation state of sea water relative to either pure or magnesian calcite. Data are presented demonstrating that use of the currently accepted solubility product of calcite in seawater to determine seawater's relative calcite saturation leads to gross overestimates of its extent.     

Small Scale Field Study of an Ocean CO<Subscript>2</Subscript> Plume

We have carried out a small-scale (∼20 l) CO₂ sequestration experiment off northern California (684 m depth, ∼5°C, background ocean pH ∼7.7) designed as an initial investigation of the effects of physical forcing of the fluid, and the problem of sensing the formation of a low pH plume. The buoyant CO₂ was contained in a square frame 1.2 m high, exposing 0.21 m² to ocean flow. Two pH electrodes attached to the frame recorded the signal; a second frame placed 1.9 m south of the CO₂ pool was also equipped with two recording pH electrodes. An additional pH electrode was held in the ROV robotic arm to probe the fluid interface. Local water velocities of up to 40 cm sec⁻¹ were encountered, creating significant eddies within the CO₂ box, and forcing wavelets at the fluid interface. This resulted in rapid CO₂ dissolution, with all CO₂ being depleted in a little more than 2 days. The pH record from the sensor closest (∼10 cm) to the CO₂ showed many spikes of low pH water, the extreme value being ∼5.9. The sensor 1 m immediately below this showed no detectable response. The electrodes placed 1.9 m distant from the source also recorded very small perturbations. The results provide important clues for the design of future experiments for CO₂ disposal and biogeochemical impact studies. These include the need for dealing with the slow CO₂ hydration kinetics, better understanding of the fluid dynamics of the CO₂-water interface, and non-point source release designs to provide more constant, controlled local CO₂ enrichments within the experimental area. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

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.     

Effects of Direct Ocean CO<Subscript>2</Subscript> Injection on Deep-Sea Meiofauna

Purposeful deep-sea carbon dioxide sequestration by direct injection of liquid CO₂ into the deep waters of the ocean has the potential to mitigate the rapid rise in atmospheric levels of greenhouse gases. One issue of concern for this carbon sequestration option is the impact of changes in seawater chemistry caused by CO₂ injection on deep-sea ecosystems. The effects of deep-sea carbon dioxide injection on infaunal deep-sea organisms were evaluated during a field experiment in 3600 m depth off California, in which liquid CO₂ was released on the seafloor. Exposure to the dissolution plume emanating from the liquid CO₂ resulted in high rates of mortality for flagellates, amoebae, and nematodes inhabiting sediments in close proximity to sites of CO₂ release. Results from this study indicate that large changes in seawater chemistry (i.e. pH reductions of ∼0.5–1.0 pH units) near CO₂ release sites will cause high mortality rates for nearby infaunal deep-sea communities. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Effects of CO<Subscript>2</Subscript> on Marine Fish: Larvae and Adults

CO₂-enriched seawater was far more toxic to eggs and larvae of a marine fish, silver seabream, Pagrus major, than HCl-acidified seawater when tested at the same seawater pH. Data on the effects of acidified seawater can therefore not be used to estimate the toxicity of CO₂, as has been done in earlier studies. Ontogenetic changes in CO₂ tolerance of two marine bony fishes (Pag. major and Japanese sillago, Sillago japonica) showed a similar, characteristic pattern: the cleavage and juvenile stages were most susceptible, whereas the preflexion and flexion stages were much more tolerant to CO₂. Adult Japanese amberjack, Seriola quinqueradiata, and bastard halibut, Paralichthys olivaceus, died within 8 and 48 h, respectively, during exposure to seawater equilibrated with 5% CO₂. Only 20% of a cartilaginous fish, starspotted smooth-hound, Mustelus manazo, died at 7% CO₂ within 72 h. Arterial pH initially decreased but completely recovered within 1-24 h for Ser. quinqueradiata and Par. olivaceus at 1 and 3% CO₂, but the recovery was slower and complete only at 1% for M. manazo. During exposure to 5% CO₂, Par. olivaceus died after arterial pH had been completely restored. Exposure to 5% CO₂ rapidly depressed the cardiac output of Ser. quinqueradiata, while 1% CO₂ had no effect. Both levels of ambient CO₂ had no effect on blood O₂ levels. We tentatively conclude that cardiac failure is important in the mechanisms by which CO₂ kills fish. High CO₂ levels near injection points during CO₂ ocean sequestration are likely to have acute deleterious effects on both larvae and adults of marine fishes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preindustrial, historical, and fertilization simulations using a global ocean carbon model with new parameterizations of iron limitation, calcification, and N2 fixation

The Canadian Model of Ocean Carbon (CMOC) has been developed as part of a global coupled climate carbon model. In a stand-alone integration to preindustrial equilibrium, the model ecosystem and global ocean carbon cycle are in general agreement with estimates based on observations. CMOC reproduces global mean estimates and spatial distributions of various indicators of the strength of the biological pump; the spatial distribution of the air-sea exchange of CO₂ is consistent with present-day estimates. Agreement with the observed distribution of alkalinity is good, consistent with recent estimates of the mean rain ratio that are lower than historic estimates, and with calcification occurring primarily in the lower latitudes. With anthropogenic emissions and climate forcing from a 1850-2000 climate model simulation, anthropogenic CO₂ accumulates at a similar rate and with a similar spatial distribution as estimated from observations. A hypothetical scenario for complete elimination of iron limitation generates maximal rates of uptake of atmospheric CO₂ of less than 1 PgC y⁻¹, or about 11% of 2004 industrial emissions. Even a ‘perfect’ future of sustained fertilization would have a minor impact on atmospheric CO₂ growth. In the long term, the onset of fertilization causes the ocean to take up an additional 77 PgC after several thousand years, compared with about 84 PgC thought to have occurred during the transition into the last glacial maximum due to iron fertilization associated with increased dust deposition.     

Uptake mechanism of anthropogenic CO<Subscript>2</Subscript> in the Kuroshio Extension region in an ocean general circulation model

The uptake mechanism of anthropogenic CO₂ in the Kuroshio Extension is examined by a Lagrangian approach using a biogeochemical model embedded in an ocean general circulation model. It is found that the uptake of anthropogenic CO₂ is caused mainly by the increase of pCO₂ dependency of seawater on temperature, which is caused by greater dissolved inorganic carbon concentration in the modern state than in the pre-industrial state. In contrast with the view of previous studies, the effect of the vertical entrainment, which brings waters that last contacted the atmosphere with the past lower CO₂ concentration, is comparatively small. Winter uptake of anthropogenic CO₂ increases with the rise of the atmospheric CO₂ level, while summer uptake is relatively stable, resulting in a larger seasonal cycle of the uptake. This increase is significant, especially in the Kuroshio Extension region. It is newly suggested that this increase in the Kuroshio Extension region is largely caused by the combined effects of the increased pCO₂ dependency of the sea water on the temperature and the seasonal difference in cooling.     

Effects of seawater acidification by ocean CO<Subscript>2</Subscript> sequestration on bathypelagic prokaryote activities

We investigated the effects of seawater acidification induced by ocean CO₂ sequestration on bathypelagic prokaryotes. We simulated acidification conditions by bubbling high-CO₂ air or adding chemical buffer solutions to seawater samples in order to examine changes in total cell counts, heterotrophic production rate, direct viable cell count, and relative abundance of Bacteria and Archaea. Considerable suppression of prokaryotic activities was observed at pH 7.0 or lower, especially in samples enriched with organic matter. The relative abundance of Archaea increased with increasing CO₂ concentration. We found that seawater acidification can potentially alter heterotrophic activities and community structure of bathypelagic prokaryotes.     

Deep ocean fluxes and their link to surface ocean processes and the biological pump

Intense studies of upper and deep ocean processes were carried out in the Northwestern Indian Ocean (Arabian Sea) within the framework of JGOFS and related projects in order to improve our understanding of the marine carbon cycle and the ocean’s role as a reservoir for atmospheric CO₂. The results show a pronounced monsoon-driven seasonality with enhanced organic carbon fluxes into the deep-sea during the SW Monsoon and during the early and late NE Monsoon north of 10°N. The productivity is mainly regulated by inputs of nutrients from subsurface waters into the euphotic zone via upwelling and mixed layer-deepening. Deep mixing introduces light limitation by carrying photoautotrophic organisms below the euphotic zone during the peak of the NE Monsoon. Nevertheless, deep mixing and strong upwelling during the SW Monsoon provide an ecological advantage for diatoms over other photoautotrophic organisms by increasing the silica concentrations in the euphotic zone. When silica concentrations fall below 2 μmol l⁻¹, diatoms lose their dominance in the plankton community. During diatom-dominated blooms, the biological pathway of uptake of CO₂ (the biological pump) appears to be more efficient than during blooms of other organisms, as indicated by organic carbon to carbonate carbon (rain) ratios. Due to the seasonal alternation of diatom and non-diatom dominated exports, spatial variations of the annual mean rain ratios are hardly discernible along the main JGOFS transect.Data-based estimates of the annual mean impact of the biological pump on the fCO₂ in the surface water suggest that the biological pump reduces the increase of fCO₂ in the surface water caused by intrusion of CO₂-enriched subsurface water by 50–70%. The remaining 30 to 50% are attributed to CO₂ emissions into the atmosphere. Rain ratios up to 60% higher in river-influenced areas off Pakistan and in the Bay of Bengal than in the open Arabian Sea imply that riverine silica inputs can further enhance the impact of the biological pump on the fCO₂ in the surface water by supporting diatom blooms. Consequently, it is assumed that reduced river discharges caused by the damming of major rivers increase CO₂ emission by lowering silica inputs to the Arabian Sea; this mechanism probably operates in other regions of the world ocean also.     

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.