Seasonal observations of surface waters in two Gulf of Maine estuary-plume systems: Relationships between watershed attributes,optical measurements and surface pCO2

The partial pressure of carbon dioxide (pCO₂) in estuary-plume systems is related to the internal processes of net organic metabolism and physical mixing, but is also strongly influenced by biogeochemical inputs from the land and ocean. Surface layer pCO₂, stimulated fluorescence of chlorophyll (f-chl) and colored organic matter (f-com), and beam attenuation at 660 nm (c-660) were measured during three seasonal surveys of the Kennebec (ME) and Merrimack (MA) estuary-plume systems. These estuaries are both supplied by large New England Rivers and separated by less than 150 km, but significant differences were often observed in the distributions of surface pCO₂ and optical variables. High pCO₂ concentrations were generally associated with high f-com, while lower pCO₂ concentrations were associated with high f-chl and c-660. Using simple regression models, optical measurements were used to estimate chlorophyll and total organic carbon concentrations. Results suggest that labile riverine carbon is responsible for sustaining supersaturated pCO₂ conditions and that phytoplankton productivity, likely driven by inputs of riverine dissolved inorganic nitrogen, is responsible for pCO₂ undersaturation. Although optical variables are often related to surface pCO₂, the results suggest that efforts to retrieve pCO₂ in complex waters using optical data may be enhanced using a site-specific, multivariate approach.     

Influence of giant kelp beds (Macrocystis pyrifera) on diel cycles of pCO2 and DIC in the Sub-Antarctic coastal area

The partial pressure of CO₂ (pCO₂) and dissolved inorganic carbon (DIC) were monitored in shallow coastal waters located inside and outside giant kelp beds (Macrocystis pyrifera) located in the Kerguelen Archipelago (Southern Ocean). Photosynthesis and respiration by microplankton and kelp lead to marked pCO₂ and DIC diel cycles. Daily variations of pCO₂ and DIC are significant in the spring and summer, but absent in the winter, reflecting the seasonal cycle of biological activity in the kelp beds. If the kelp beds seem to favour the onset of phytoplankton blooms, most of the primary production inside the kelp beds is due to the kelp itself. The primary production of Macrocystis kelp beds in the Sub-Antarctic high-nutrient, low-chlorophyll (HNLC) waters off the Kerguelen Archipelago is elevated and closely linked to light availability. This production is significant from October to March and reaches its climax in December at the solar radiation maximum.     

Effects of the Anticyclonic Eddies on Water Masses, Chemical Parameters and Chlorophyll Distributions in the Oyashio Current Region

Data from the R/V Mirai cruise (May–June 2000) have been examined to discover how mesoscale processes associated with eddy dynamics direct affect the water masses, the distributions and the vertical fluxes of the dissolved oxygen, nutrients and dissolved inorganic carbon in the western subarctic Pacific. Using maps of the temperature, salinity, dissolved oxygen, nutrients, chlorophyll and sea-air pCO₂ difference we show that the boundaries of the anticyclone eddies in the study region were composed of high productivity coastal Oyashio water. The coastal waters were wrapped around the anticyclone eddies (thus creating a high productivity belt) and intruded inside of them. Using SeaWifs data we demonstrate that temporal variations in the position and the strength of anticyclone eddies advected the Kuril island coastal high productivity waters to the pelagic part, resulting in temporal variations of the chlorophyll in the Oyashio region. Computed vertical fluxes of the dissolved oxygen (DO), inorganic carbon (DIC) and silicate show that the anticylonic eddies in the Kuroshio-Oyashio Zone are characterized by enhanced vertical fluxes of the DO and DIC between the upper (σ_θ = 26.7–27.0) and lower (σ_θ = 27.1–27.5) intermediate layer, probably due to the intrusions of the Oyashio waters into the eddies. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comments on: “Underwater measurements of carbon dioxide evolution in marine plant communities: A new method” by J. Silva and R. Santos [Estuarine,Coastal and Shelf Science 78(2008) 827–830]

Silva et al. propose a new method for quantifying benthic net community production (NCP) of tidal flats under submerged condition, based on the monitoring of water pCO₂ in a transparent benthic chamber around high tide. I demonstrate here with theoretical considerations that this method is inappropriate for coastal environments, because it allows only the quantification of the change in the dissolved CO₂ which, at classical seawater pH, is only ∼10% of the change of the dissolved inorganic carbon (DIC). Total Alkalinity and/or DIC must be measured at the beginning and end of incubations in order to compute NCP in coastal environments. However, I also demonstrate that when pH is below 7, more than 95% of the DIC change occurs in the CO₂ pool. The method proposed by Silva et al. is thus valuable for freshwater environments with acidic, low alkalinity waters, where monitoring the water pCO₂ in a vial or chamber provides alone a very close approximation of the planktonic or benthic net community production.     

Carbon dioxide in surface seawaters of the Seto Inland Sea,Japan

Observations were made of time variations of carbon dioxide in seawater, pCO₂, and in the atmosphere, PCO₂, in the Seto Inland Sea of Japan. The pCO₂ data showed well defined diurnal variation; high values at nighttime and low values during daylight hours. The pCO₂ correlated negatively with dissolved oxygen. These results denote that the diurnal variation of pCO₂ is associated with effects of photoplankton's activity in seawater. The pCO₂ measured in the Seto Inland Sea showed higher values than the PCO₂ during June to November, denoting transport of carbon dioxide from the sea surface to the atmosphere, and lower values during December to May, denoting transport of carbon dioxide from the atmosphere to the sea surface. The exchange rates of carbon dioxide were calculated using working formula given by Andriéet al. (1986). The results showed that the Seto Inland Sea gained carbon dioxide of 1.0 m-mol m^–2 d^–1 from the atmosphere in March and lost 1.7 m-mol m^–2 d^–1 to the atmosphere in August.     

The carbonate system of Amur Bay (sea of Japan) under conditions of hypoxia

In the course of the expedition of the Pacific Oceanological Institute in August 2007, extensive hypoxia was found in the near-bottom layer of the Amur Bay water mass. The hypoxia’s formation was immediately reflected in the values and distribution of the carbonate parameters in the near-bottom waters of the bay. The maximum values of the carbon dioxide partial pressure, the dissolved inorganic carbon, and the total alkalinity were associated with the areas of the minimum oxygen content. The microbial destruction of the dead phytoplankton greatly increased the partial pressure of carbon dioxide, which was over 2000 μatm in the hypoxia centers at a depth of about 20 m. At the same time, the carbon dioxide partial pressure in the surface waters of Amur Bay was considerably lower than that in the atmosphere. Hence, the bay’s aquatic area was a sink for the atmospheric CO₂ despite its high content in the near-bottom waters. It was shown that the excess alkalinity associated with the hypoxia sites in the near-bottom layer of water was caused by the sulfate reduction proceeding in the upper layer of the sediment.     

CO2 outgassing off central Chile (31–30°S) and northern Chile (24–23°S) during austral summer 1997: the effect of wind intensity on the upwelling and ventilation of CO2-rich waters

The distribution of pH and alkalinity has been used to calculate the distribution of total inorganic carbon (TC) and fugacity of carbon dioxide (fCO₂) in the upper 200 m of the water column in coastal upwelling areas off northern Chile (23–24°S, near Antofagasta) and central Chile (30–31°S, near Coquimbo) during austral summer 1997. In these upwelling areas, colder surface waters were oxygen poor and strongly CO₂ supersaturated (100% near Antofagasta and 200% near Coquimbo), although below the pycnocline the CO₂ supersaturation invariably exceeded 200% in both areas. The larger surface CO₂ supersaturation and outgassing at 30°S were associated with stronger winds that promoted the upwelling of denser water (richer in CO₂) as well as a higher air–sea CO₂ transfer velocity. The consistent decrease in intensity of the southerly winds (as derived from NSCAT scatterometer data) from 30–31°S to 23–24°S suggests a corresponding decline in the intensity of the CO₂ outgassing due to upwelling. Additionally, we suggest here that the intensity of the local upwelling forcing (i.e. alongshore–equatorward winds) plays a role in determining the water mass composition and phytoplankton biomass of the coastal waters. Thus, while deep upwelling of salty and cold water resulted in high fCO₂ (up to 1000 μatm) and very low phytoplankton biomass (chlorophyll a concentration lower than 0.5 mg m⁻³), the shallow upwelling of less salty (e.g. salinity <34.5) and less CO₂-supersaturated water resulted in a higher phytoplankton biomass, which further reduced surface water fCO₂ by photosynthesis.     

Measurements of carbon dioxide in the Seto Inland Sea of Japan

The carbon dioxide in seawater (pCO₂) was measured in the Seto Inland Sea of Japan using newly developed equilibrator instrument designed to be free from the correction for addition or extraction of the carbon dioxide from carrier gas. The temperature dependence of pCO₂ was about 4.5%pCO₂/°C for a single seawater sample which was processed as free from biological activity and change in total carbon dioxide content during an experiment. The decrease in pCO₂ during daylight hours due to the photosynthetic fixation was about 30% of the daily mean of pCO₂ during warm months and about 15% during cold months. The effect of carbon dioxide exchange between air and seawater on pCO₂ was about 0.6 ppm in August and about 0.1 ppm in March. This is negligible small compared with the daily oscillation of carbon dioxide in seawater.     

Impacts of elevated CO2 on particulate and dissolved organic matter production: microcosm experiments using iron-deficient plankton communities in open subarctic waters

Response of phytoplankton to increasing CO₂ in seawater in terms of physiology and ecology is key to predicting changes in marine ecosystems. However, responses of natural plankton communities especially in the open ocean to higher CO₂ levels have not been fully examined. We conducted CO₂ manipulation experiments in the Bering Sea and the central subarctic Pacific, known as high nutrient and low chlorophyll regions, in summer 2007 to investigate the response of organic matter production in iron-deficient plankton communities to CO₂ increases. During the 14-day incubations of surface waters with natural plankton assemblages in microcosms under multiple pCO₂ levels, the dynamics of particulate organic carbon (POC) and nitrogen (PN), and dissolved organic carbon (DOC) and phosphorus (DOP) were examined with the plankton community compositions. In the Bering site, net production of POC, PN, and DOP relative to net chlorophyll-a production decreased with increasing pCO₂. While net produced POC:PN did not show any CO₂-related variations, net produced DOC:DOP increased with increasing pCO₂. On the other hand, no apparent trends for these parameters were observed in the Pacific site. The contrasting results observed were probably due to the different plankton community compositions between the two sites, with plankton biomass dominated by large-sized diatoms in the Bering Sea versus ultra-eukaryotes in the Pacific Ocean. We conclude that the quantity and quality of the production of particulate and dissolved organic matter may be altered under future elevated CO₂ environments in some iron-deficient ecosystems, while the impacts may be negligible in some systems.     

Seasonal dissolved inorganic carbon variations in the Greenland Sea and implications for atmospheric CO2 exchange

During the 1993–1995 period of minimal deep convection in the Greenland Sea, the dissolved inorganic carbon concentration within the surface waters varied dramatically on the seasonal time scale, with average summer and winter values of 2064 (±10) and 2150 (±5) μmol kg⁻¹, respectively, indicative of a vigorous annual carbon cycle. In contrast, there was very little interannual variability throughout these three years. While primary production largely depleted the surface nutrient supplies in spring and summer, generating a strong seasonal CO₂ drawdown, a combination of relatively shallow remineralization and mixed-layer deepening brought essentially all of the carbon consumed by photosynthesis back into contact with the atmosphere before winter. This re-release of the inorganic carbon that had been consumed by phytoplankton earlier in the year was more than sufficient to counteract the cooling-induced increase in the carbon carrying capacity of the water during fall and winter, reducing the potential for atmospheric carbon dioxide absorption by the Greenland Sea over the same period.     

Effects of upwelling,tides and biological processes on the inorganic carbon system of a coastal lagoon in Baja California

The role of coastal lagoons and estuaries as sources or sinks of inorganic carbon in upwelling areas has not been fully understood. During the months of May–July, 2005, we studied the dissolved inorganic carbon system in a coastal lagoon of northwestern Mexico during the strongest period of upwelling events. Along the bay, different scenarios were observed for the distributions of pH, dissolved inorganic carbon (DIC) and apparent oxygen utilization (AOU) as a result of different combinations of upwelling intensity and tidal amplitude. DIC concentrations in the outer part of the bay were controlled by mixing processes. At the inner part of the bay DIC was as low as 1800 μmol kg⁻¹, most likely due to high water residence times and seagrass CO₂ uptake. It is estimated that 85% of San Quintín Bay, at the oceanic end, acted as a source of CO₂ to the atmosphere due to the inflow of CO₂-rich upwelled waters from the neighboring ocean with high positive fluxes higher than 30 mmol C m⁻² d⁻¹. In contrast, there was a net uptake of CO₂ and HCO₃⁻ by the seagrass bed Zostera marina in the inner part of the bay, so the pCO₂ in this zone was below the equilibrium value and slightly negative CO₂ fluxes of −6 mmol C m⁻² d⁻¹. Our positive NEP and ΔDIC values indicate that Bahía San Quintín was a net autotrophic system during the upwelling season during 2005.     

Episodic riverine influence on surface DIC in the coastal Gulf of Maine

Anomalously high precipitation and river discharge during the spring of 2005 caused considerable freshening and depletion of dissolved inorganic carbon (DIC) in surface waters along the coastal Gulf of Maine. Surface pCO₂ and total alkalinity (TA) were monitored by repeated underway sampling of a cross-shelf transect in the western Gulf of Maine (GOM) during 2004–05 to examine how riverine fluxes, mixing, and subsequent biological activity exert control on surface DIC in this region. Most of the variability in surface DIC concentration was attributable to mixing of low DIC river water with higher DIC, saline GOM waters, but net biological uptake of DIC was significant especially during the spring and summer seasons. The extent and persistence of the coastal freshwater intrusion exerted considerable influence on net carbon dynamics. Integrated over the 10-m surface layer of our study region (∼5 × 10⁴ km²), net biological DIC uptake was 0.48 × 10⁸ mol C during April–July of 2004 compared to 1.33 × 10⁸ mol C during April–July of 2005. We found the temporal signature and magnitude of DIC cycling to be different in adjacent plume-influenced and non-plume regions. Extreme events such as the freshwater anomaly observed in 2005 will affect mean estimates of coastal carbon fluxes, thus budgets based on short time series of observations may be skewed and should be viewed with caution.     

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.     

The inorganic carbon system in the coastal upwelling region west of Vancouver Island,Canada

We present inorganic carbon data from the coastal upwelling region west of Vancouver Island, Canada $\text{(∼48.5°}\text{N}\text{,}\text{126°}\text{W}\text{)}$ directly after an upwelling event and during summer downwelling in July 1998. The inner-shelf buoyancy current, the outer-shelf and the slope regions are contrasted for both wind regimes (up- and downwelling). Results show strong biological drawdown of the partial pressure of carbon dioxide (pCO₂) in response to upwelling over the outer-shelf. In contrast, measured pCO₂ is exceptionally high $\text{(p}\text{CO}{}_2\text{>1000}\text{ppm}\text{)}$ in the inner-shelf current, where biological uptake of carbon is consistently large. The biological C:N uptake ratio appears to increase when nitrogen becomes limiting (during downwelling), while the POC:PON ratio is relatively constant (slightly lower than the Redfield ratio) suggesting that excess carbon uptake does not go into the POC pool. As expected, large cells dominate where measured primary productivity is greatest. Sub-surface inorganic carbon (and pCO₂) is high over the shelf. We suggest that carbon concentrations may be higher in coastal waters because of remineralization associated with high productivity that is confined to a smaller volume of water by bathymetry. At the coast these sub-surface concentrations are more efficiently mixed into the surface (especially during winter) relative to deeper offshore regions. Thus, despite high primary production, coastal waters may not aid in sequestration of atmospheric carbon.     

A numerical analysis of carbon dynamics of the Southern Ocean phytoplankton community: the roles of light and grazing in effecting both sequestration of atmospheric CO2 and food availability to larval krill

Reduced ice extent within coastal regions of the Southern Ocean may lead to deeper surface mixed layers (SML), as prevail in offshore areas. A future decline of ice melt-induced stability of the water column may be associated with a shift in dominant food webs, from larger, sun-adapted diatoms grazed by euphausiids to smaller, shade-adapted flagellates consumed by salps. A basically one-dimensional numerical model of three dominant groups of the Antarctic phytoplankton community (diatoms, cryptophytes, and colonial prymnesiophytes) and four types of herbivore (protozoans, salps, copepods, and euphausiids) is used to explore the seasonal importance of both light limitation and grazing pressure on the amount of annual carbon sequestration and larval krill survival within contrasting oceanic and neritic waters, where respective validation data have been gathered during austral spring by the European JGOFS and RACER programs. With imposition of moderate and large grazing stresses, thought to be typical of offshore waters, we were able to replicate the European JGOFS 1992 observations of light penetration, phytoplankton biomass, primary production, pCO₂, bacterial biomass, labile DOC, ammonium, and total particle effluxes at 100 m within the deep SML of our model. The fidelity of such a large set of simulated state variables suggests that multiple limiting factors are indeed operating on different components of the oceanic phytoplankton community — selective grazing losses on the flagellates, but light limitation of diatoms. Release of protozoan grazing pressure in our model instead leads to unobserved spring blooms of cryptophytes, found only in laboratory enclosures. On an annual basis, weak sequestration of atmospheric CO₂ is simulated in a habitat typical of the Polar Front, while evasion of carbon dioxide occurs under biophysical conditions of the Antarctic Circumpolar Current. Stratification in shallow SML and the same absolute grazing demands by krill and copepods allows sun-adapted diatoms of our model to bloom at the expense of shade-adapted cryptophytes and prymnesiophytes, eaten by salps and protozoans. We were also able to replicate RACER-I observations of the same suite of variables in 1986–1987, as well as the observed 10-fold range of detrital fluxes caught by other sediment trap deployments during 1980 and 1983 along the Antarctic Peninsula. In western Bransfield Strait, coastal waters are a strong sink for atmospheric CO₂ within parcels of Bellingshausen Sea origin, but not perhaps in those from the Weddell Sea, which resemble the oceanic regime of deep SML. We conclude that even in shallow neritic SML, some protozoan rivals of larval krill must still crop flagellates to ensure sufficient abundance of diatom food for both euphausiid survival and possible clogging of the mucous nets of other salp rivals.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Wet-oxidation and automated colorimetry for simultaneous determination of organic carbon, nitrogen and phosphorus dissolved in seawater

We developed a simple and reliable method which allows simultaneous determination of organic forms of carbon (DOC), nitrogen (DON) and phosphorus (DOP) dissolved in seawater. Conversion of dissolved organic matter (DOM) to inorganic products (carbon dioxide, nitrate+nitrite and soluble reactive phosphate) is performed by a persulfate wet-oxidation in low alkaline condition. After oxidation, the concentration of the inorganic products dissolved in the sample was measured automatically by colorimetry using a 3-channel Technicon AutoAnalyzer system. A number of pure organic compounds were tested in the concentration range encountered in coastal and open ocean, indicating a high efficiency of the digestion procedure. The recovery range is similar to that obtained by other wet-oxidation procedures and by high-temperature catalytic oxidation techniques. Direct comparisons with usual methods used for separate determination of DOC, DON and DOP indicated a high efficiency of the procedure. Reproducibility tests demonstrated a very good precision (around 5%) for lagoonal and coastal waters, while precision was sometimes around 10–25% in oligotrophic oceanic waters, especially for DOP where values approached limits of detection for measuring phosphate. This method is highly suitable for routine analysis and especially appropriate for shipboard work.     

Biogeochemical characteristics of coastal waters adjacent to small river–mangrove systems, East Brazil

This study addresses the composition of biogenic matter and the metabolic activity of coastal waters of the eastern Brazilian shelf, bordered by small river–mangrove systems. Oceanic Brazil Current waters induce oligotrophic and near to homogeneous conditions of chemical constituents along the inner shelf. The impact of small river–mangrove systems upon coastal waters is minor and of local nature. Bottom topography, coral reef habitats, and local upwelling also induce minor local spatial variability of dissolved inorganic and organic nutrients and O₂ and CO₂ saturation levels in the coastal waters. Metabolic activity during the daylight period, inferred from O₂ and CO₂ saturation levels, varied from slightly autotrophic to heterotrophic.     

An Ecosystem Model Coupled with Nitrogen-Silicon-Carbon Cycles Applied to Station A7 in the Northwestern Pacific

A model based on that of Kishi et al. (2001) has been extended to 15 compartments including silicon and carbon cycles. This model was applied to Station A7 off Hokkaido, Japan, in the Northwestern Pacific. The model successfully simulated the observations of: 1. a spring bloom of diatoms; 2. large seasonal variations of nitrate and silicate concentrations in the surface water; and 3. large inter-annual variations in chlorophyll-a. It also reproduced the observed features of the seasonal variations of carbon dioxide partial pressure (pCO₂)—a peak in pCO₂ in winter resulting from deep winter convection, a rapid decrease in pCO₂ as a result of the spring bloom, and an almost constant pCO₂ from summer through fall (when the effect of increasing temperature cancels the effect of biological production). A comparison of cases with and without silicate limitation shows that including silicate limitation in the model results in: 1. decreased production by diatoms during summer; and 2. a transition in the dominant phytoplankton species, from diatoms to other species that do not take up silicate. Both of these phenomena are observed at Station A7, and our results support the hypothesis that they are caused by silicate limitation of diatom growth. This revised version was published online in July 2006 with corrections to the Cover Date.     

The carbonate system in the East China Sea in winter

Measurements of dissolved inorganic carbon (DIC), pH, total alkalinity (TA), and partial pressure of CO₂ (pCO₂) were conducted at a total of 25 stations along four cross shelf transects in the East China Sea (ECS) in January 2008. Results showed that their distributions in the surface water corresponded well to the general circulation pattern in the ECS. Low DIC and pCO₂ and high pH were found in the warm and saline Kuroshio Current water flowing northeastward along the shelf break, whereas high DIC and pCO₂ and low pH were mainly observed in the cold and less saline China Coastal Current water flowing southward along the coast of Mainland China. Difference between surface water and atmospheric pCO₂ (ΔpCO₂), ranging from ~ 0 to ? 111 μatm, indicated that the entire ECS shelf acted as a CO₂ sink during winter with an average flux of CO₂ of ?13.7 ± 5.7 (mmol C m^? 2 day^? 1), and is consistent with previous studies. However, pCO₂ was negatively correlated with temperature for surface waters lower than 20 °C, in contrast to the positive correlation found in the 1990s. Moreover, the wintertime ΔpCO₂ in the inner shelf near the Changjiang River estuary has appreciably decreased since the early 1990s, suggesting a decline of CO₂ sequestration capacity in this region. However, the actual causes for the observed relationship between these decadal changes and the increased eutrophication over recent decades are worth further study.