High Dissolved Inorganic Carbon Research Articles

Vanishing coccolith vital effects with alleviated carbon limitation

Abstract. By recreating a range of geologically relevant concentrations of dissolved inorganic carbon (DIC) in the laboratory, we demonstrate that the magnitude of the vital effects in both carbon and oxygen isotopes of coccolith calcite of multiple species relates to ambient DIC concentration. Under high DIC levels, all the examined coccoliths exhibit significantly reduced isotopic offsets from inorganic calcite compared to the substantial vital effects expressed at low (preindustrial and present-day) DIC concentrations. The supply of carbon to the cell exerts a primary control on biological fractionation in coccolith calcite via the modulation of coccolithophore growth rate, cell size and carbon utilisation by photosynthesis and calcification, altogether accounting for the observed interspecific differences between coccolith species. These laboratory observations support the recent hypothesis from field observations that the appearance of interspecific vital effect in coccolithophores coincides with the long-term Neogene decline of atmospheric CO2 concentrations and bring further valuable constraints by demonstrating a convergence of all examined species towards inorganic values at high pCO2 regimes. This study provides palaeoceanographers with a biogeochemical framework that can be utilised to further develop the use of calcareous nannofossils in palaeoceanography to derive sea surface temperature and pCO2 levels, especially during periods of relatively elevated pCO2 concentrations, as they prevailed during most of the Meso-Cenozoic.

DINAMIKA DISSOLVED INORGANIC CARBON (DIC) DI EKOSISTEM LAMUN PULAU PARI

Coastal water represents 8% of the global ocean. The one of coastal ecosystem is seagrass ecosystem. The role of coastals ecosystem, such as seagrass ecosystem as source or sink carbondioxide (CO2) from atmospher to sea and dynamic of Dissolved Inorganic Carbon (DIC) has not been fully understood. The objective of study is analyzed DIC data and ancillary environmnet data in seagrass ecosystem at temporal represent west , east and trantition monsoon season as long as 2011 – 2012 in seawater and porewater. The higher DIC in seawater and porewater is east monsoon season. The lowest DIC in seawater and porewater is west monsoon season. Total alkalinity (TA) and partial pressure of CO2 (pCO2) have the same pattern with DIC, they are high in east monsoon season and low in west monsoon seasoon. Dynamic of DIC and (TA) every seasonin seawater are affected temperature, while in porewater is not visible factors affecting of DIC. Parameter of TA in porewater is influenced by total suspended solid (TSS). West monsoon season, seagrass ecosystem roles as CO2 sink with the flux is 3.237 mmolC/m2/day. East and trantition monsoon season, seagrass ecosystem plays a role as CO2 source with the flux of 11.669 mmolC/m2/hari.

Leaky savannas: the significance of lateral carbon fluxes in the seasonal tropics

Globally, dissolved inorganic carbon (DIC) accounts for more than half the annual flux of carbon exported from terrestrial ecosystems via rivers. Here, we assess the relative influences of biogeochemical and hydrological processes on DIC fluxes exported from a tropical river catchment characterized by distinct land cover, climate and geology transition from the wet tropical mountains to the low-lying savanna plains. Processes controlling changes in river DIC were investigated using dissolved organic carbon, particulate organic carbon and DIC concentrations and stable isotope ratios of DIC (δ13CDIC) at two time scales: seasonal and diel. The recently developed Isotopic Continuous Dissolved Inorganic Carbon Analyser was used to measure diel DIC concentration and δ13CDIC changes at a 15-min temporal resolution. Results highlight the predominance of biologically mediated processes (photosynthesis and respiration) controlling diel changes in DIC. These resulted in DIC concentrations varying between 3.55 and 3.82 mg/l and δ13CDIC values ranging from −19.7 ± 0.31‰ to −17.1 ± 0.08‰. In contrast, at the seasonal scale, we observed wet season DIC variations predominantly from mixing processes and dry season DIC variations due to both mixing processes and biological processes. The observed wet season increases in DIC concentrations (by 6.81 mg/l) and δ13CDIC values of river water (by 5.4‰) largely result from proportional increases in subsurface inflows from the savanna plains (C4 vegetation) region relative to inflows from the rainforest (C3 vegetation) highlands. The high DIC river load during the wet season resulted in the transfer of 97% of the annual river carbon load. Therefore, in this gaining river, there are significant seasonal variations in both the hydrological and carbon cycles, and there is evidence of substantial coupling between the carbon cycles of the terrestrial and the fluvial environments. Recent identification of a substantial carbon sink in the savannas of northern Australia during wetter years in the recent past does not take into account the possibility of a substantial, rapid, lateral flux of carbon to rivers and back to the atmosphere.

The physiological response of two green calcifying algae from the Great Barrier Reef towards high dissolved inorganic and organic carbon (DIC and DOC) availability.

Increasing dissolved inorganic carbon (DIC) concentrations associated with ocean acidification can affect marine calcifiers, but local factors, such as high dissolved organic carbon (DOC) concentrations through sewage and algal blooms, may interact with this global factor. For calcifying green algae of the genus Halimeda, a key tropical carbonate producer that often occurs in coral reefs, no studies on these interactions have been reported. These data are however urgently needed to understand future carbonate production. Thus, we investigated the independent and combined effects of DIC (pCO2 402 μatm/ pHtot 8.0 and 996 μatm/ pHtot 7.7) and DOC (added as glucose in 0 and 294 μmol L-1) on growth, calcification and photosynthesis of H. macroloba and H. opuntia from the Great Barrier Reef in an incubation experiment over 16 days. High DIC concentrations significantly reduced dark calcification of H. opuntia by 130 % and led to net dissolution, but did not affect H. macroloba. High DOC concentrations significantly reduced daily oxygen production of H. opuntia and H. macroloba by 78 % and 43 %, respectively, and significantly reduced dark calcification of H. opuntia by 70%. Combined high DIC and DOC did not show any interactive effects for both algae, but revealed additive effects for H. opuntia where the combination of both factors reduced dark calcification by 162 % compared to controls. Such species-specific differences in treatment responses indicate H. opuntia is more susceptible to a combination of high DIC and DOC than H. macroloba. From an ecological perspective, results further suggest a reduction of primary production for Halimeda-dominated benthic reef communities under high DOC concentrations and additional decreases of carbonate accretion under elevated DIC concentrations, where H. opuntia dominates the benthic community. This may reduce biogenic carbonate sedimentation rates and hence the buffering capacity against further ocean acidification.

Response of dissolved inorganic carbon (DIC) and δ13CDIC to changes in climate and land cover in SW China karst catchments

Monthly hydrochemical data and δ13C of dissolved inorganic carbon (DIC) in karst water samples from September 2007 to October 2012 were obtained to reveal the controlling mechanisms on DIC geochemistry and δ13CDIC under different conditions of climate and land cover in three karst catchments: Banzhai, Dengzhanhe and Chenqi, in Guizhou Province, SW China. DIC of karst water at the Banzhai site comes mainly from carbonate dissolution under open system conditions with soil CO2 produced by root respiration and organic carbon decomposition with lowest δ13C values under its dense virgin forest coverage. Weaker carbonate bedrock dissolution due to sparse and thin soil cover results in lower δ13CDIC, pCO2, DIC and EC, and lower cation and anion concentrations. At the Chenqi site, larger soil CO2 input from a thick layer of soil results in high pCO2 and DIC, and low pH, SIc and δ13CDIC in the karst water. At the Dengzhanhe site, a lesser soil CO2 input due to stronger karst rock desertification and strong gypsum dissolution contribute to higher δ13CDIC, high EC and high cation and anion concentrations. Soil CO2 inputs, controlled by biological activity and available soil moisture, carbonate bedrock dissolution, dilution and degassing effects, vary seasonally following rainfall and temperature changes. Consequently, there are seasonal cycles in hydrochemistry and δ13CDIC of the karst water, with high pCO2 and low pH, EC, SIc, and δ13CDIC values in the warm and rainy seasons, and vice versa during the cold and dry seasons. A strongly positive shift (>3‰) in δ13CDIC occurred in the drought year, 2011, indicating that δ13CDIC in groundwater systems can be an effective indicator of environmental and/or climate changes.

The seasonal cycle of ocean‐atmosphere CO2 flux in Ryder Bay, west Antarctic Peninsula

AbstractApproximately 15 million km2 of the Southern Ocean is seasonally ice covered, yet the processes affecting carbon cycling and gas exchange in this climatically important region remain inadequately understood. Here, 3 years of dissolved inorganic carbon (DIC) measurements and carbon dioxide (CO2) fluxes from Ryder Bay on the west Antarctic Peninsula (WAP) are presented. During spring and summer, primary production in the surface ocean promotes atmospheric CO2 uptake. In winter, higher DIC, caused by net heterotrophy and vertical mixing with Circumpolar Deep Water, results in outgassing of CO2 from the ocean. Ryder Bay is found to be a net sink of atmospheric CO2 of 0.90–1.39 mol Cm−2 yr−1 (average of 3 years). Seasonal sea ice cover modifies the net annual CO2 uptake, but its effect on gas exchange remains poorly constrained. A reduction in sea ice on the WAP shelf may reduce the strength of the oceanic CO2 sink in this region.

The formation of aggregates in coral reef waters under elevated concentrations of dissolved inorganic and organic carbon: A mesocosm approach

The transformation of dissolved organic carbon (DOC) to particulate organic carbon is the major mechanism through which large sinking organic particles are formed in aquatic systems. Global stressors, such as high concentrations of dissolved inorganic carbon (DIC) due to ocean acidification, as well as local stressors, such as high DOC concentrations due to coastal eutrophication, can significantly affect the formation and settling of aggregates and thereby the marine biogeochemical carbon cycle. Increasing aggregate formation rates can contribute to the mortality of benthic organisms in coral reef ecosystems, but relevant knowledge is scarce. Therefore, the present study addresses this issue and studies the individual and combined effects of high DIC (900 μatm) and DOC (150μM glucose) on organic matter dynamics as well as the formation of organic aggregates in a manipulative study over 42days using 24 mesocosms dominated by either benthic calcifying algae or by hard corals. Organic aggregates in terms of transparent exopolymer particle (TEP) concentrations and total aggregated volume were measured. Results showed lower TEP concentrations and aggregated volume under high DIC concentrations. By contrast, under DOC enrichment higher rates of aggregate formation and microbial oxygen uptake were observed. Surprisingly, the highest aggregate formation rates were observed under the combined DIC and DOC enrichment. Furthermore, benthic organisms influenced the availability of DOC resulting in higher aggregate formation in coral compared to calcifying algae mesocosms. These experiments simulate future ocean conditions in coastal ecosystems where elevated DOC concentrations could aggravate the effect of high DIC on aggregate formation. In coral reef ecosystems, this may have important consequences on benthic organisms.

Drake Passage and Central American Seaway controls on the distribution of the oceanic carbon reservoir

A coupled carbon/climate model is used to explore the impact of Drake Passage opening and Central American Seaway closure on the distribution of carbon in the global oceans. We find that gateway evolution likely played an important role in setting the modern day distribution of oceanic dissolved inorganic carbon (DIC), which is currently characterized by relatively low concentrations in the Atlantic Ocean, and high concentrations in the Southern, Indian, and Pacific oceans. In agreement with previous studies, we find a closed Drake Passage in the presence of an open Central American Seaway results in suppressed Atlantic meridional overturning and enhanced southern hemispheric deep convection. Opening of the Drake Passage triggers Antarctic Circumpolar Current flow and a weak Atlantic meridional overturning circulation (AMOC). Subsequent Central American Seaway closure reinforces the AMOC while also stagnating equatorial Pacific subsurface waters. These gateway-derived oceanographic changes are reflected in large shifts to the global distribution of DIC. An initially closed Drake Passage results in high DIC concentrations in the Atlantic and Arctic oceans, and lower DIC concentrations in the Pacific/Indian/Southern oceans. Opening Drake Passage reverses this gradient by lowering mid-depth Atlantic and Arctic DIC concentrations and raising deep Pacific/Indian/Southern Ocean DIC concentrations. Central American Seaway closure further reinforces this trend through additional Atlantic mid-depth DIC decreases, as well as Pacific mid-depth DIC concentration increases, with the net effect being a transition to a modern distribution of oceanic DIC.

Effect of a controlled sub-seabed release of CO2 on the biogeochemistry of shallow marine sediments, their pore waters, and the overlying water column

The potential for leakage of CO2 from a storage reservoir into the overlying marine sediments and into the water column and the impacts on benthic ecosystems are major challenges associated with carbon capture and storage (CCS) in subseafloor reservoirs. We have conducted a field-scale controlled CO2 release experiment in shallow, unconsolidated marine sediments, and documented the changes to the chemical composition of the sediments, their pore waters and overlying water column before, during and up to 1 year after the 37-day long CO2 release. Increased levels of dissolved inorganic carbon (DIC) were detected in the pore waters close to the sediment-seawater interface in sediments sampled closest to the subsurface injection point within 5 weeks of the start of the CO2 release. Highest DIC concentrations (28.8mmolL−1, compared to background levels of 2.4mmolL−1) were observed 6 days after the injection had stopped. The high DIC pore waters have high total alkalinity, and low δ13CDIC values (−20‰, compared to a background value of −2‰), due to the dissolution of the injected CO2 (δ13C=−26.6‰). The high DIC pore waters have enhanced concentrations of metals (including Ca, Fe, Mn) and dissolved silicon, relative to non-DIC enriched pore waters, indicating that dissolution of injected CO2 promotes dissolution of carbonate and silicate minerals. However, in this experiment, the pore water metal concentrations did not exceed levels considered to be harmful to the environment. The spatial extent of the impact of the injected CO2 in the sediments and pore waters was restricted to an area within 25m of the injection point, and no impact was observed in the overlying water column. Concentrations of all pore water constituents returned to background values within 18 days after the CO2 injection was stopped.

Coastal acidification induced by tidal-driven submarine groundwater discharge in a coastal coral reef system.

We identified a barely noticed contributor, submarine groundwater discharge (SGD), to acidification of a coastal fringing reef system in Sanya Bay in the South China Sea based on time-series observations of Ra isotopes and carbonate system parameters. This coastal system was characterized by strong diel changes throughout the spring to neap tidal cycle of dissolved inorganic carbon (DIC), total alkalinity, partial pressure of CO2 (pCO2) and pH, in the ranges of 1851-2131 μmol kg(-1), 2182-2271 μmol kg(-1), 290-888 μatm and 7.72-8.15, respectively. Interestingly, the diurnal amplitudes of these parameters decreased from spring to neap tides, governed by both tidal pumping and biological activities. In ebb stages during the spring tide, we observed the lowest salinities along with the highest DIC, pCO2 and Ra isotopes, and the lowest pH and aragonite saturation state. These observations were consistent with a concurrent SGD rate up to 25 and 44 cm d(-1), quantified using Darcy's law and (226)Ra, during the spring tide ebb, but negligible at flood tides. Such tidal-driven SGD of low pH waters is another significant contributor to coastal acidification, posing additional stress on coastal coral systems, which would be even more susceptible in future scenarios under higher atmospheric CO2.

Ecophysiology of gelatinous Nostoc colonies: unprecedented slow growth and survival in resource-poor and harsh environments.

The cyanobacterial genus Nostoc includes several species forming centimetre-large gelatinous colonies in nutrient-poor freshwaters and harsh semi-terrestrial environments with extended drought or freezing. These Nostoc species have filaments with normal photosynthetic cells and N2-fixing heterocysts embedded in an extensive gelatinous matrix of polysaccharides and many other organic substances providing biological and environmental protection. Large colony size imposes constraints on the use of external resources and the gelatinous matrix represents extra costs and reduced growth rates. The objective of this review is to evaluate the mechanisms behind the low rates of growth and mortality, protection against environmental hazards and the persistence and longevity of gelatinous Nostoc colonies, and their ability to economize with highly limiting resources. Simple models predict the decline in uptake of dissolved inorganic carbon (DIC) and a decline in the growth rate of spherical freshwater colonies of N. pruniforme and N. zetterstedtii and sheet-like colonies of N. commune in response to a thicker diffusion boundary layer, lower external DIC concentration and higher organic carbon mass per surface area (CMA) of the colony. Measured growth rates of N. commune and N. pruniforme at high DIC availability comply with general empirical predictions of maximum growth rate (i.e. doubling time 10-14 d) as functions of CMA for marine macroalgae and as functions of tissue thickness for aquatic and terrestrial plants, while extremely low growth rates of N. zetterstedtii (i.e. doubling time 2-3 years) are 10-fold lower than model predictions, either because of very low ambient DIC and/or an extremely costly colony matrix. DIC uptake is limited by diffusion at low concentrations for all species, although they exhibit efficient HCO3(-) uptake, accumulation of respiratory DIC within the colonies and very low CO2 compensation points. Long light paths and light attenuation by structural substances in large Nostoc colonies cause lower quantum efficiency and assimilation number and higher light compensation points than in unicells and other aquatic macrophytes. Extremely low growth and mortality rates of N. zetterstedtii reflect stress-selected adaptation to nutrient- and DIC-poor temperate lakes, while N. pruniforme exhibits a mixed ruderal- and stress-selected strategy with slow growth and year-long survival prevailing in sub-Arctic lakes and faster growth and shorter longevity in temperate lakes. Nostoc commune and its close relative N. flagelliforme have a mixed stress-disturbance strategy not found among higher plants, with stress selection to limiting water and nutrients and disturbance selection in quiescent dry or frozen stages. Despite profound ecological differences between species, active growth of temperate specimens is mostly restricted to the same temperature range (0-35 °C; maximum at 25 °C). Future studies should aim to unravel the processes behind the extreme persistence and low metabolism of Nostoc species under ambient resource supply on sediment and soil surfaces.

Total Alkalinity and Dissolved Inorganic Carbon Production in Groundwaters Discharging through a Sandy Beach

The paper presents evidence of the complexity of describing carbon transport from submarine groundwater discharge and chemical reactions in the subterranean estuary. Vertical and horizontal profiles of total alkalinity (TA) and dissolved inorganic carbon (DIC) concentrations were analyzed in a cross-shore transect of a sandy beach and an evaluation of DIC and TA fluxes to coastal waters is proposed based on groundwater discharge velocities and beach hydrogeology. The study was conducted in the Magdalen Islands in the Gulf of St. Lawrence (QC, Canada) where an unconfined sandstone aquifer rapidly discharges to the coastal ocean with a rate of ∼3000 m3 d-1. Increases in DIC and TA observed along the discharge pathway exceed the expected conservative mixing between inland groundwaters and seawater. This local production is attributed to anaerobic respiration. Slow groundwater velocity (1 to 9cm d-1), low oxygen conditions (∼20%) and redox oscillations probably induced by tidal pumping present a suitable environment for bacterially-mediated carbon oxidation and anaerobic respiration. Depleted δ13C-DIC (from −14‰ to −28‰) and the characteristic odour of H2S during sample collection support the idea that sulphate reduction may generate high alkalinity and DIC concentrations at the seepage face, leading to potentially high discharge to the coastal ocean at this beach (2.0 to 8.2mol DIC/day and 1.9 to 7.9 mmol TA/day). To our knowledge, this study is the first attempt to estimate the transport and transformations of dissolved inorganic carbon by biogeochemical processes in the subterranean estuary of a northern sandy beach.

Inorganic carbon parameters responding to summer hypoxia outside the Changjiang Estuary and the related implications

The eutrophication, hypoxia and coastal acidification are attracting more and more attention. In this study, inorganic carbon parameters, including dissolved inorganic carbon (DIC), total alkalinity (TA) and calculated partial pressure of CO2 (pCO(2)), obtained from a summer cruise in August, 2009, were used to investigate their integrated response to biological processes accompanying the oxygen depletion in the areas off the Changjiang Estuary. According to the observations, the typical hypoxia occurred in the bottom water just outside the Changjiang Estuary with Dissolved Oxygen (DO) lower than 2.00 mg L-1. The biological uptake in the surface water and the decomposition of organic matter in the bottom water were fully coupled with each other. The high concentration of Chl_a (Chl_a = 10.9 mu g L-1) and DO (9.25 mg L-1), profoundly decreased DIC concentration (1828 mu mol kg(-1)) and elevated pH (8.42) was observed in the surface water. The correspondingly increased DIC and depletion of oxygen were observed in the bottom water. The semi-quantitative analysis proved that the locally-produced phytoplankton, determined by primary productivity, was deposited to the bottom and contributed about 76% of total amount of the organic carbon decomposition in the bottom. However, in the bottom hypoxia (DO = 2.05 mg L-1) area observed in the Southern Zhejiang coastal water, the responding patterns of inorganic carbon parameters deviated from the previous one. The expanding of Changjiang Diluted Water (CDW), the adding of Hangzhou Bay water (with high DIC concentration) and Coastal Current together modify the DIC background value in this area, and the local degeneration and upwelling process may also help to offset the local DIC removed by net biological uptake in surface water. In addition, when the mixing occurring in autumn, which may break the summer stratification, the excess release of high DIC in the bottom water to the subsurface water could have an important influence on coastal acidification and the CO2 uptake capacity in this area.

Uranium adsorption by Shewanella oneidensis MR-1 as a function of dissolved inorganic carbon concentration

Although the existence of uranyl-carbonate surface complexes on bacterial cell walls has been documented, the identities and thermodynamic stabilities of those complexes are poorly constrained by previous studies. We measured the adsorption of aqueous uranium [U(VI)] onto Shewanella oneidensis MR-1 with different initial concentrations of NaHCO3. Experiments were conducted in 0.1M NaClO4 to buffer ionic strength, and pH was varied from 3 to 9. The observed extent of U(VI) adsorption onto S. oneidensis was independent of dissolved inorganic carbon (DIC) concentration below pH5. Above pH5, the extent of adsorbed U(VI) decreased with increasing DIC concentration. A thermodynamic surface complexation modeling approach was used to interpret the adsorption data. A series of uranyl-, uranyl-hydroxide-, and uranyl-hydroxide-carbonate-bacterial surface complexes are required in order to account for the observed adsorption behavior, and we used the adsorption measurements to constrain values for the stability constants of these complexes. The modeling results suggest that uranyl-hydroxide-carbonate-bacterial surface complexes form and that competition between these complexes and uranyl-carbonate aqueous complexes controls the U(VI) adsorption behavior under high pH conditions in systems with high DIC concentrations. Hence, our results may be used to predict the extent of U(VI) adsorption onto bacteria in a range of natural and engineered DIC-bearing systems.

Isotopic biosignatures in carbonate‐rich, cyanobacteria‐dominated microbial mats of the Cariboo Plateau, B.C.

Photosynthetic activity in carbonate-rich benthic microbial mats located in saline, alkaline lakes on the Cariboo Plateau, B.C. resulted in pCO2 below equilibrium and δ(13) CDIC values up to +6.0‰ above predicted carbon dioxide (CO2 ) equilibrium values, representing a biosignature of photosynthesis. Mat-associated δ(13) Ccarb values ranged from ~4 to 8‰ within any individual lake, with observations of both enrichments (up to 3.8‰) and depletions (up to 11.6‰) relative to the concurrent dissolved inorganic carbon (DIC). Seasonal and annual variations in δ(13) C values reflected the balance between photosynthetic (13) C-enrichment and heterotrophic inputs of (13) C-depleted DIC. Mat microelectrode profiles identified oxic zones where δ(13) Ccarb was within 0.2‰ of surface DIC overlying anoxic zones associated with sulphate reduction where δ(13) Ccarb was depleted by up to 5‰ relative to surface DIC reflecting inputs of (13) C-depleted DIC. δ(13) C values of sulphate reducing bacteria biomarker phospholipid fatty acids (PLFA) were depleted relative to the bulk organic matter by ~4‰, consistent with heterotrophic synthesis, while the majority of PLFA had larger offsets consistent with autotrophy. Mean δ(13) Corg values ranged from -18.7±0.1 to -25.3±1.0‰ with mean Δ(13) Cinorg-org values ranging from 21.1 to 24.2‰, consistent with non-CO2 -limited photosynthesis, suggesting that Precambrian δ(13) Corg values of ~-26‰ do not necessitate higher atmospheric CO2 concentrations. Rather, it is likely that the high DIC and carbonate content of these systems provide a non-limiting carbon source allowing for expression of large photosynthetic offsets, in contrast to the smaller offsets observed in saline, organic-rich and hot spring microbial mats.

High-Frequency Spectrophotometric Measurements of Total Dissolved Inorganic Carbon in Seawater

A new spectrophotometric method was developed to achieve continuous measurements of total dissolved inorganic carbon (DIC) in seawater. It uses a countercurrent flow design and a highly CO2-permeable membrane (Teflon AF 2400) to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a fast response time of ~22 s. This method improves the spatiotemporal resolution by more than 1 order of magnitude compared to the existing spectrophotometric method. The flow-through equilibration allows for continuous (~1 Hz) detection and real-time data smoothing. The method had a short-term precision of ± 2.0 μmol kg(-1) for a given flow-through sample. It achieved a field precision of ± 3.6 μmol kg(-1) and successfully captured high DIC variability down to minute scales. Measurements by the new method over the typical range of oceanic DIC showed good agreement with measurements made by an established method (mean differences -1.6 to 0.3 μmol kg(-1) with 1σ ± 6.0-6.7 μmol kg(-1)). This level of precision and accuracy is comparable to that of the existing spectrophotometric method. The characteristics of the new method make it particularly suitable for high-frequency, submerged measurements required for mobile observing platforms in the ocean. It can also be adapted for high-frequency, spectrophotometric measurements of seawater CO2 fugacity.

Seasonality of CO<sub>2</sub> in coastal oceans altered by increasing anthropogenic nutrient delivery from large rivers: evidence from the Changjiang–East China Sea system

Abstract. Model studies suggested that human-induced increase in nutrient load may have stimulated primary production and thus enhanced the CO2 uptake capacity in the coastal ocean. In this study, we investigated the seasonal variations of the surface water's partial pressure of CO2 (pCO2sw) in the highly human-impacted Changjiang–East China Sea system between 2008 and 2011. The seasonality of pCO2sw has large spatial variations, with the largest extreme of 170 ± 75 μatm on the inner shelf near the Changjiang Estuary (from 271 ± 55 μatm in summer to 441 ± 51 μatm in autumn) and the weakest extreme of 53 ± 20 μatm on the outer shelf (from 328 ± 9 μatm in winter to 381 ± 18 μatm in summer). During the summer period, stronger stratification and biological production driven by the eutrophic Changjiang plume results in a very low dissolved inorganic carbon (DIC) in surface waters and a very high DIC in bottom waters of the inner shelf, with the latter returning high DIC to the surface water during the mixed period. Interestingly, a comparison with historical data shows that the average pCO2sw on the inner shelf near the Changjiang Estuary has decreased notably during summer, but has increased during autumn and winter from the 1990s to the 2000s. We suggest that this decadal change is associated with recently increased eutrophication. This would increase both the photosynthetic removal of DIC in surface waters and the respiratory release of DIC in bottom waters during summertime, thereby returning more DIC to the surface during the subsequent mixing seasons and/or episodic extreme weather events (e.g., typhoons). Our finding demonstrates that increasing anthropogenic nutrient delivery from a large river may enhance the sequestration capacity of CO2 in summer but may reduce it in autumn and winter. Consequently, the coastal ocean may not necessarily take up more atmospheric CO2 in response to increasing eutrophication, and the net effect largely depends on the relative timescale of air–sea gas exchange and offshore transport of the shelf water. Finally, the case we report for the Changjiang system may have general ramifications for other eutrophic coastal oceans.

Copper and lead internalisation by freshwater microalgae at different carbonate concentrations

Environmental context Metal–carbonato complexes have been reported to contribute to metal uptake and toxicity in aquatic organisms. We show that in the presence of lead–carbonato complexes, Pb internalisation by the microalga Chlamydomonas reinhardtii is higher than that predicted on the basis of the free Pb2+ concentration. This effect, which was not observed for another microalga that takes up Pb more slowly, is attributed to the very high rates of Pb uptake by C. reinhardtii, which result in diffusion limitation. Abstract The possible contribution of metal–carbonato complexes to metal uptake or toxicity has been mentioned several times in the literature, often in studies where dissolved inorganic carbon (DIC) concentrations and pH were varied together, but a thorough study of the effect on DIC on metal bioavailability to aquatic organisms has not been done. By using closed systems – allowing changes in DIC concentrations at fixed pH – and ion selective electrodes to determine free metal ion concentrations, we show that lead internalisation by the unicellular alga Chlamydomonas reinhardtii in the presence of high DIC concentrations is higher than predicted by the free Pb2+ ion concentration at bulk [Pb2+] lower than 50nM, but not at higher [Pb2+]. This effect is not observed for another microalga, Chlorella vulgaris, which shows a lower rate of Pb internalisation. Copper internalisation by C. reinhardtii seems also to be slightly higher than predicted on the basis of free Cu2+ at low (20nM) bulk Cu2+ concentrations but not at higher ones. The possibility that Pb (and Cu) internalisation by C. reinhardtii is partially limited by diffusion from the bulk solution to the algal surface is identified and discussed as a possible explanation for these results.

Variability of Air-Sea CO<sub>2</sub> Fluxes and Dissolved Inorganic Carbon Distribution in the Atlantic Basin: A Coupled Model Analysis

The biogeochemical dynamics of carbon in the ocean is a subject of fundamental interest to environmental studies. In this context, we have implemented a ten year run of the Brazilian Earth System Coupled Ocean-Atmosphere Model (BESM-OA2.3) integrated with TOPAZ biogeochemical model for the Atlantic basin. The modeled ΔpCO2 for the tropical Atlantic shows very clearly a high dominance of positive fluxes, that is, the CO2 fluxes are sea-to-air throughout the tropical region and for both winter and summer periods. In the mid-latitudes regions negatives fluxes (air-to-sea) were observed for both seasons. An exception to this pattern is an extensive negative tongue on the latitude 10N. The occurrence of this negative ΔpCO2 tongue region in the Tropical Atlantic is highly correlated to negative Evaporation-Precipitation values during this season. In the northern hemisphere (NH) summer the negative values of ΔpCO2 in the tropical Atlantic region are concentrated in the adjacent zone of the Amazon river mouth due to the North Equatorial Counter Current intensification. This process favors the formation of a carbon sink in the adjacent region of the Amazon river mouth. Model results show lowest values of dissolved inorganic carbon (DIC) in a surface layer (100 - 150 m). Highest DIC values are observed in deeper layers and concentrated in an equatorial band. The chlorophyll bloom in equatorial zones was well represented by the model. These blooms are the result of equatorial upwelling that brings the high concentration tongues of DIC present in the equatorial band towards the euphotic zone. This is the first published paper about the BESM-OA2.3 integrated with TOPAZ. The presented results suggest that this modeling system is able to reproduce the main regional carbon dynamics features of the mid-latitude/tropical Atlantic.

Effects of dissolved inorganic carbon on competition of the bloom-forming cyanobacterium Microcystis aeruginosa with the green alga Chlamydomonas microsphaera

The availability of dissolved inorganic carbon (DIC) may have a considerable impact on species competition in phytoplankton communities. The growth, photosynthetic characteristics and competition of three strains, the toxic Microcystis aeruginosa FACHB 912, nontoxic M. aeruginosa FACHB 469 and Chlamydomonas microsphaera FACHB 52, were investigated under two different DIC concentrations (0.365 and 7.658 mmol l−1 KHCO3). In monoculture, DIC concentration did not affect the specific growth rates of any of the three strains. However, when grown in mixed culture with C. microsphaera, both toxic and nontoxic Microcystis strains showed increased percentages under low DIC concentration but decreased percentages under high DIC concentration. After 12 days’ mixed culture, the percentage of M. aeruginosa FACHB 912 or FACHB 469 decreased by 9−22% in high DIC medium, but increased by 6–11% in low DIC medium. Low DIC concentration decreased the cell size, cellular chlorophyll fluorescence and photosynthetic capacity of C. microsphaera, but it had little effect on those of M. aeruginosa FACHB 912 and FACHB 469. The apparent photosynthetic affinities for DIC were significantly higher in the two M. aeruginosa strains than in C. microsphaera. From the higher DIC affinity, more efficient photosynthetic capacity and increased percentages in competition experiments under low DIC concentration, it can be concluded that the bloom-forming M. aeruginosa possesses a competitive advantage in DIC-limited conditions.