Increase In Atmospheric pCO2 Research Articles

Preliminary investigation on the potential involvement of an ABC-like gene in Halomicronema metazoicum (Cyanobacteria) tolerance to low seawater pH in an ocean acidification scenario

Decreasing ocean surface pH, called ocean acidification (OA), is among the major risks for marine ecosystems due to human-driven atmospheric pCO2 increase. Understanding the molecular mechanisms of adaptation enabling marine species to tolerate a lowered seawater pH could support predictions of consequences of future OA scenarios for marine life. This study examined whether the ATP-binding cassette (ABC)-like gene slr2019 confers tolerance to the marine cyanobacterium Halomicronema metazoicum to low seawater pH conditions (7.7, 7.2, 6.5) in short- and long-term exposures (7 and 30 d). Photosynthetic pigment content indicated that the species can tolerate all three lowered-pH conditions. At day 7, slr2019 was up-regulated at pH 7.7 while no changes were observed at lower pH. After 30-d exposure, a significant decrease in slr2019 transcript levels was observed in all low-pH treatments. These first results indicate an effect of low pH on the examined transporter expression in H. metazoicum.

Assessing transient changes in the ocean carbon cycle during the last deglaciation through carbon isotope modeling

Abstract. Atmospheric carbon dioxide concentration (pCO2) has increased by approximately 80 ppm from the Last Glacial Maximum (LGM) to the early Holocene. The change in this atmospheric greenhouse gas is recognized as a climate system response to gradual change in insolation. Previous modeling studies suggested that the deglacial increase in atmospheric pCO2 is primarily attributed to the release of CO2 from the ocean. Additionally, it has been suggested that abrupt change in the Atlantic meridional overturning circulation (AMOC) and associated interhemispheric climate changes are involved in the release of CO2. However, understanding remains limited regarding oceanic circulation changes and the factors responsible for changes in chemical tracers in the ocean during the last deglaciation and their impact on atmospheric pCO2. In this study, we investigate the evolution of the ocean carbon cycle during the last deglaciation (21 to 11 ka BP) using three-dimensional ocean fields from the transient simulation of the MIROC 4m climate model, which exhibits abrupt AMOC changes similar to those observed in reconstructions. We investigate the reliability of simulated changes in the ocean carbon cycle by comparing the simulated carbon isotope ratios with sediment core data, and we examine potential biases and overlooked or underestimated processes in the model. Qualitatively, the modeled changes in atmospheric pCO2 are consistent with ice core records. For example, during Heinrich Stadial 1 (HS1), atmospheric pCO2 increases by 10.2 ppm, followed by a reduction of 7.0 ppm during the Bølling–Allerød (BA) period and then by an increase of 6.8 ppm during the Younger Dryas (YD) period. However, the model underestimates the changes in atmospheric pCO2 during these events compared to values derived from ice core data. Radiocarbon and stable isotope signatures (Δ14C and δ13C) indicate that the model underestimates both the activated deep-ocean ventilation and reduced efficiency of biological carbon export in the Southern Ocean and the active ventilation in the North Pacific Intermediate Water (NPIW) during HS1. The relatively small changes in simulated atmospheric pCO2 during HS1 might be attributable to these underestimations of ocean circulation variation. The changes in Δ14C associated with strengthening and weakening of the AMOC during the BA and YD periods are generally consistent with values derived from sediment core records. However, although the data indicate continuous increase in δ13C in the deep ocean throughout the YD period, the model shows the opposite trend. It suggests that the model either simulates excessive weakening of the AMOC during the YD period or has limited representation of geochemical processes, including marine ecosystem response and terrestrial carbon storage. Decomposing the factors behind the changes in ocean pCO2 reveals that variations in temperature and alkalinity have the greatest impact on change in atmospheric pCO2. Compensation for the effects of temperature and alkalinity suggests that the AMOC changes and the associated bipolar climate changes contribute to the decrease in atmospheric pCO2 during the BA and the increase in atmospheric pCO2 during the YD period.

Enhanced Carbonate Counter Pump and upwelling strengths in the Indian sector of the Southern Ocean during MIS 11

While numerous studies have highlighted the central role of Southern Ocean (SO) dynamics in modulating rapid increases in atmospheric CO2 concentrations during deglaciations, fewer studies have yet focused on the impact of the Biological Carbon Pump - and more specifically the Carbonate Counter Pump (CCP) - in contributing to increase the CO2 concentration in oceanic surface waters and thus, in the atmosphere. Here, we present micropaleontological (coccolith, planktonic foraminifera) and geochemical (CaCO3, CaXRF, δ13CN. pachyderma) constraints from sediment core MD04-2718 retrieved in the Polar Front Zone of the Indian Ocean covering the time interval spanning Marine Isotope Stage (MIS) 12 to MIS 10 (440,000–360,000 years). We compare our results with published records from the SO to reconstruct past changes in CCP and upwelling dynamics and understand their leverage on the ocean-atmosphere portioning of CO2. We demonstrate that the sharp increase in atmospheric pCO2 during Termination V was likely associated with enhanced deep-water ventilation in the SO, that promoted the release of previously sequestered CO2 to the ocean surface as the westerly wind belt and the frontal system migrated southwards. Enhanced CCP is observed later, during MIS 11, and is likely the consequence of higher sea surface temperature and higher nutrient availability due to the reinvigoration of SO upwelling leading to increased coccolith (and to a lesser degree, planktonic foraminifera) production and export. The low eccentricity signal recorded during MIS 11 might have additionally strengthened the CCP, exerting a specific control on Gephyrocapsa morphotypes. In addition to the strong global biological productivity and higher carbon storage on land, these synergistic mechanisms may have permitted to shape the distinctive 30 ka-long pCO2 plateau characteristic of MIS 11.

Atmospheric pCO2 Reconstruction of Early Cretaceous Terrestrial Deposits in Texas and Oklahoma Using Pedogenic Carbonate and Occluded Organic Matter

Pedogenic carbonate samples collected from three Lower Cretaceous (Aptian–Albian) fossil localities in Texas and Oklahoma were analyzed to develop paleoatmospheric pCO2 estimates by measuring the stable carbon isotopes of pedogenic calcite and their co-existing occluded organic matter. Calcite δ13C values ranged from −10.9‰ to −4.4‰ while occluded organic matter δ13C values ranged from −27.3‰ to −21.1‰. These stable carbon isotope measurements combined with temperature (30 °C) and soil-respired CO2 concentration (839–6047 ppmV) values provided atmospheric pCO2 estimates ranging from 67 ppmV to over 1100 ppmV. These estimates show a significant increase in atmospheric pCO2 during the late Aptian followed by a decrease in atmospheric pCO2 during the late Aptian to early Albian transition period, roughly correlating with the OEA1b event. Given the lack of chronostratigraphic constraints of the Lower Cretaceous geologic units in the study area, these data provide further evidence for the approximate age of the units as well as pertinent paleoclimate insights into greenhouse climate conditions.

Long-Term Trends in Estuarine Carbonate Chemistry in the Northwestern Gulf of Mexico

A four-decade dataset that spans seven estuaries along a latitudinal gradient in the northwestern Gulf of Mexico and includes measurements of pH and total alkalinity was used to calculate partial pressure of CO2 (pCO2), dissolved inorganic carbon (DIC), saturation state of aragonite (ΩAr), and a buffer factor (βDIC, which measures the response of proton concentration or pH to DIC concentration change) and examine long-term trends and spatial patterns in these parameters. With the notable exception of the northernmost and southernmost estuaries (and selected stations near freshwater input), these estuaries have generally experienced long-term increases in pCO2 and decreases in DIC, ΩAr, and βDIC, with the magnitude of change generally increasing from north to south. At all stations with increasing pCO2, the rate of increase exceeded the rate of increase in atmospheric pCO2, indicating that these estuaries have become a greater source of CO2 to the atmosphere over the last few decades. The decreases in ΩAr have yet to cause ΩAr to near undersaturation, but even the observed decreases may have the potential to decrease calcification rates in important estuarine calcifiers like oysters. The decreases in βDIC directly indicate that these estuaries have experienced continually greater change in pH in the context of ocean acidification.

Drivers of Air‐Sea CO2 Flux Seasonality and its Long‐Term Changes in the NASA‐GISS Model CMIP6 Submission

AbstractClimate change will affect both the mean state and seasonality of marine physical and biogeochemical properties, with important implications for the oceanic sink of atmospheric CO2. Here, we investigate the seasonal cycle of the air‐sea exchange of CO2 and pCO2,sw (surface seawater pCO2) and their long term changes using the CMIP6 submission of the NASA‐GISS modelE (GISS‐E2.1‐G). In comparison to the CMIP5 submission (GISS‐E2‐R), we find that on the global scale, the seasonal cycles of the CO2 flux and NPP have improved, while the seasonal cycles of dissolved inorganic carbon (DIC), alkalinity, and macronutrients have deteriorated. Moreover, for all ocean biogeochemistry fields, changes in skill between E2.1‐G and E2‐R display large regional variability. For E2.1‐G, we find similar modeled and observed CO2 flux seasonal cycles in the subtropical gyres, where seasonal anomalies of pCO2,sw and the flux are temperature‐driven, and the Southern Ocean, where anomalies are DIC‐driven. Biases in these seasonal cycles are largest in the subpolar and equatorial regions, driven by a combination of biases in temperature, DIC, alkalinity, and wind speed. When comparing the historical simulation to a simulation with an idealized increase in atmospheric pCO2, we find that the seasonal amplitudes of the CO2 flux and pCO2,sw generally increase. These changes are produced by increases in the sensitivity of pCO2,sw to its respective drivers. These findings are consistent with the notion that the seasonality of pCO2,sw is expected to increase due to the increase of atmospheric pCO2, with changes in the seasonality of temperature, DIC, and alkalinity having secondary influences.

Future acidification of the Baltic Sea – A sensitivity study

Abstract Future acidification of coastal seas will depend not only on the development of atmospheric CO2 partial pressure (pCO2), but also on changes in the catchment areas, exchange with the adjacent ocean, and internal cycling of carbon and nutrients. Here we use a coupled physical-biogeochemical Baltic Sea model to quantify the sensitivity of pH to changes both in external forcing and internal processes. The experiments include changes in runoff, supply of dissolved inorganic carbon (DIC) and total alkalinity (AT), nutrient loads, exchange between the Baltic and North Seas, and atmospheric pCO2. We furthermore address the potential different future developments of runoff and river loads in boreal and continental catchments, respectively. Changes in atmospheric pCO2 exert the strongest control on future pH according to our calculations. This CO2-induced acidification could be further enhanced in the case of desalination of the Baltic Sea, although increased concentrations of AT in the river runoff due to increased weathering to some extent could counteract acidification. Reduced nutrient loads and productivity would reduce the average annual surface water pH but at the same time slightly increase wintertime surface water pH (the annual pH minimum). The response time of surface water pH to sudden changes in atmospheric pCO2 is approximately one month, whereas response times to changes in e.g. runoff and AT/DIC loads are more related to residence times of water and salt (>30 years). It seems unlikely that the projected future increase in atmospheric pCO2 and associated pH reduction could be fully counteracted by any of the other processes addressed in our experiments.

Stripping back the modern to reveal the Cenomanian–Turonian climate and temperature gradient underneath

Abstract. During past geological times, the Earth experienced several intervals of global warmth, but their driving factors remain equivocal. A careful appraisal of the main processes controlling past warm events is essential to inform future climates and ultimately provide decision makers with a clear understanding of the processes at play in a warmer world. In this context, intervals of greenhouse climates, such as the thermal maximum of the Cenomanian–Turonian (∼94 Ma) during the Cretaceous Period, are of particular interest. Here we use the IPSL-CM5A2 (IPSL: Institut Pierre et Simon Laplace) Earth system model to unravel the forcing parameters of the Cenomanian–Turonian greenhouse climate. We perform six simulations with an incremental change in five major boundary conditions in order to isolate their respective role on climate change between the Cenomanian–Turonian and the preindustrial. Starting with a preindustrial simulation, we implement the following changes in boundary conditions: (1) the absence of polar ice sheets, (2) the increase in atmospheric pCO2 to 1120 ppm, (3) the change in vegetation and soil parameters, (4) the 1 % decrease in the Cenomanian–Turonian value of the solar constant and (5) the Cenomanian–Turonian palaeogeography. Between the preindustrial simulation and the Cretaceous simulation, the model simulates a global warming of more than 11 ∘C. Most of this warming is driven by the increase in atmospheric pCO2 to 1120 ppm. Palaeogeographic changes represent the second major contributor to global warming, whereas the reduction in the solar constant counteracts most of geographically driven warming. We further demonstrate that the implementation of Cenomanian–Turonian boundary conditions flattens meridional temperature gradients compared to the preindustrial simulation. Interestingly, we show that palaeogeography is the major driver of the flattening in the low latitudes to midlatitudes, whereas pCO2 rise and polar ice sheet retreat dominate the high-latitude response.

Impact of physical and biological processes on temporal variations of the ocean carbon sink in the mid-latitude North Atlantic (2002–2016)

The ocean is currently a significant net sink for anthropogenically remobilised CO2, taking up around 24% of global emissions. Numerical models predict a diversity of responses of the ocean carbon sink to increased atmospheric concentrations in a warmer world. Here, we tested the hypothesis that increased atmospheric forcing is causing a change in the ocean carbon sink using a high frequency observational dataset derived from underway pCO2 (carbon dioxide partial pressure) instruments on ships of opportunity (SOO) and a fixed-point mooring between 2002 and 2016. We calculated an average carbon flux of 0.013 Pg yr−1 into the ocean at the Porcupine Abyssal Plain (PAP) site, consistent with past estimates. In spite of the increase in atmospheric pCO2, monthly average seawater pCO2 did not show a statistically significant increasing trend, but a higher annual variability, likely due to the decreasing buffer capacity of the system. The increasing ΔpCO2 led to an increasing trend in the estimated CO2 flux into the ocean of 0.19 ± 0.03 mmol m−2 day−1 per year across the entire 15 year time series, making the study area a stronger carbon sink. Seawater pCO2 variability is mostly influenced by temperature, alkalinity and dissolved inorganic carbon (DIC) changes, with 77% of the annual seawater pCO2 changes explained by these terms. DIC is in turn influenced by gas exchange and biological production. In an average year, the DIC drawdown by biological production, as determined from nitrate uptake, was higher than the DIC increase due to atmospheric CO2 dissolution into the surface ocean. This effect was enhanced in years with high nutrient input or shallow mixed layers. Using the rate of change of DIC and nitrate, we observed Redfieldian carbon consumption during the spring bloom at a C:N ratio of 6.2 ± 1.6. A comparison between SOO and PAP sustained observatory data revealed a strong agreement for pCO2 and DIC. This work demonstrates that the study area has continued to absorb atmospheric CO2 in recent years with this sink enhancing over time. Furthermore, the change in pCO2 per unit nitrate became larger as surface buffer capacity changed.

Did Late Cretaceous cooling trigger the Campanian–Maastrichtian Boundary Event?

The Campanian–Maastrichtian (83–66 Ma) was a period of global climate cooling, featuring significant negative carbon-isotope (δ13C) anomalies, such as the Late Campanian Event (LCE) and the Campanian–Maastrichtian Boundary Event (CMBE). A variety of factors, including changes in temperature, oceanic circulation and gateway opening, have been invoked to explain these δ13C perturbations, but no precise mechanism has yet been well constrained. In order to improve our understanding of these events, we measured stable carbon and oxygen isotopes of hemipelagic sediments from the Shuqualak-Evans cored borehole (Mississippi, USA) and compared the data with previously published sea-surface temperature (SST) estimates from the same core. We found that the CMBE can be recognised, unambiguously, in the ShuqualakEvans core, and that it is associated with an interval of cooler SSTs suggesting a possible mechanistic link between palaeotemperature change and this event. Determining the precise position of the LCE in the Shuqualak-Evans core is more problematic, but it may also be associated with cooler SSTs. Our combined records of carbon cycling and SSTs compare well with other studies and provide evidence that cooling during the CMBE (and possibly LCE) was global in nature and affected surface waters, in addition to the deep-ocean. We suggest that short-term cooling drove intensification of high-latitude deep-water formation, which in turn led to changes in the ratio of carbonate to organic carbon burial that led to a negative δ13C excursion. Critically, the absence of warming during these intervals implies that the Late Cretaceous events must not have been associated with an appreciable increase in atmospheric pCO2, and was likely associated with decreased pCO2.

Episodic release of CO2 from the high-latitude North Atlantic Ocean during the last 135\u2009kyr

Antarctic ice cores document glacial-interglacial and millennial-scale variability in atmospheric pCO2 over the past 800 kyr. The ocean, as the largest active carbon reservoir on this timescale, is thought to have played a dominant role in these pCO2 fluctuations, but it remains unclear how and where in the ocean CO2 was stored during glaciations and released during (de)glacial millennial-scale climate events. The evolution of surface ocean pCO2 in key locations can therefore provide important clues for understanding the ocean’s role in Pleistocene carbon cycling. Here we present a 135-kyr record of shallow subsurface pCO2 and nutrient levels from the Norwegian Sea, an area of intense CO2 uptake from the atmosphere today. Our results suggest that the Norwegian Sea probably acted as a CO2 source towards the end of Heinrich stadials HS1, HS4 and HS11, and may have contributed to the increase in atmospheric pCO2 at these times.

The effects of pH and pCO2 on photosynthesis and respiration in the diatom Thalassiosira weissflogii.

The response of marine phytoplankton to the ongoing increase in atmospheric pCO2 reflects the consequences of both increased CO2 concentration and decreased pH in surface seawater. In the model diatom Thalassiosira weissflogii, we explored the effects of varying pCO2 and pH, independently and in concert, on photosynthesis and respiration by incubating samples in water enriched in H218O. In long-term experiments (~6-h) at saturating light intensity, we observed no effects of pH or pCO2 on growth rate, photosynthesis or respiration. This absence of a measurable response reflects the very small change in energy used by the carbon concentrating mechanism (CCM) compared to the energy used in carbon fixation. In short-term experiments (~3min), we also observed no effects of pCO2 or pH, even under limiting light intensity. We surmise that in T. weissflogii, it is the photosynthetic production of NADPH and ATP, rather than the CO2-saturation of Rubisco that controls the rate of photosynthesis at low irradiance. In short-term experiments, we observed a slightly higher respiration rate at low pH at the onset of the dark period, possibly reflecting the energy used for exporting H+ and maintaining pH homeostasis. Based on what is known of the biochemistry of marine phytoplankton, our results are likely generalizable to other diatoms and a number of other eukaryotic species. The direct effects of ocean acidification on growth, photosynthesis and respiration in these organisms should be small over the range of atmospheric pCO2 predicted for the twenty-first century.

Linking biogeochemistry to hydro-geometrical variability in tidal estuaries: a generic modeling approach

Abstract. This study applies the Carbon-Generic Estuary Model (C-GEM) modeling platform to simulate the estuarine biogeochemical dynamics – in particular the air–water CO2 exchange – in three idealized tidal estuaries characterized by increasing riverine influence, from a so-called "marine estuary" to a "riverine estuary". An intermediate case called "mixed estuary" is also considered. C-GEM uses a generic biogeochemical reaction network and a unique set of model parameters extracted from a comprehensive literature survey to perform steady-state simulations representing average conditions for temperate estuaries worldwide. Climate and boundary conditions are extracted from published global databases (e.g., World Ocean Atlas, GLORICH) and catchment model outputs (GlobalNEWS2). The whole-system biogeochemical indicators net ecosystem metabolism (NEM), C and N filtering capacities (FCTC and FCTN, respectively) and CO2 gas exchanges (FCO2) are calculated across the three idealized systems and are related to their main hydrodynamic and transport characteristics. A sensitivity analysis, which propagates the parameter uncertainties, is also carried out, followed by projections of changes in the biogeochemical indicators for the year 2050. Results show that the average C filtering capacities for baseline conditions are 40, 30 and 22 % for the marine, mixed and riverine estuary, respectively, while N filtering capacities, calculated in a similar fashion, range from 22 % for the marine estuary to 18 and 15 % for the mixed and the riverine estuaries. Sensitivity analysis performed by varying the rate constants for aerobic degradation, denitrification and nitrification over the range of values reported in the literature significantly widens these ranges for both C and N. Simulations for the year 2050 suggest that all estuaries will remain largely heterotrophic, although a slight improvement of the estuarine trophic status is predicted. In addition, our results suggest that, while the riverine and mixed systems will only marginally be affected by an increase in atmospheric pCO2, the marine estuary is likely to become a significant CO2 sink in its downstream section. In the decades to come, such a change in behavior might strengthen the overall CO2 sink of the estuary–coastal ocean continuum.

Global increase in plant carbon isotope fractionation following the Last Glacial Maximum caused by increase in atmospheric pCO2

Changes in the carbon isotope composition of terrestrial plant tissue (δ13C) are widely cited for evidence of shifts in climate, vegetation, or atmospheric chemistry across a wide range of time scales. A global compilation of δ13C data from fossil leaves and bulk terrestrial organic matter (TOM) spanning the past 30 k.y., however, shows wide variability and no discernable trend. Here we analyze these data in terms of a relative change in net carbon isotope fractionation between the δ13C value of plant tissue and that of atmospheric CO2 [Δ13C = (δ13CCO2 – δ13C)/(1 + δ13C/1000)] and identify a global 2.1‰ shift in leaf and TOM Δ13C that is synchronous with a global rise in p CO2 documented from ice core data. We apply a relationship describing the effect of p CO2 on Δ13C to the global record of Δ13C change documented here to reconstruct p CO2 levels across the past 30 k.y. Our reconstructed p CO2 levels are in excellent agreement with the ice core data and underscore the potential of the global terrestrial δ13C record to serve as an accurate p CO2 proxy.

Positive feedback drives carbon release from soils to atmosphere during Paleocene/Eocene warming

The Paleocene-Eocene Thermal Maximum (PETM) is the most rapid climatic warming event in the Cenozoic and informs us how the Earth system responds to large-scale changes to the carbon cycle. Warming was triggered by a massive release of 13C depleted carbon to the atmosphere, evidenced by negative carbon isotope excursions (CIE) in nearly every carbon pool on Earth. Differences in these CIEs can give insight into the response of different ecosystems to perturbations in the carbon cycle. Here we present records of δ13Ccc of pedogenic carbonates and δ13Corg from preserved soil organic matter in corresponding paleosols to understand changes to soil carbon during the PETM. CIEs during the event are larger in pedogenic carbonates than preserved organic matter for corresponding paleosols at three sites across two continents. The difference in the CIEs within soil carbon pools can be explained by increased respiration and carbon turnover rates of near-surface labile soil carbon. Increased rates of labile carbon cycling combined with decreases in the amount of preserved organic carbon in soils during the PETM suggests a decrease in the size of the soil carbon pool, resulting in a potential increase in atmospheric pCO2 and a positive feedback with warming. The PETM is a model for how the earth system responds to warming, and this mechanism would suggest that soils might serve as a large source for atmospheric CO2 during warming events.

The impact of fluctuating light on the dinoflagellate Prorocentrum micans depends on NO3− and CO2 availability

Increasing atmospheric pCO2 and its dissolution into oceans leads to ocean acidification and warming, which reduces the thickness of upper mixing layer (UML) and upward nutrient supply from deeper layers. These events may alter the nutritional conditions and the light regime to which primary producers are exposed in the UML. In order to better understand the physiology behind the responses to the concomitant climate changes factors, we examined the impact of light fluctuation on the dinoflagellate Prorocentrum micans grown at low (1μmolL−1) or high (800μmolL−1) [NO3−] and at high (1000μatm) or low (390μatm, ambient) pCO2. The light regimes to which the algal cells were subjected were (1) constant light at a photon flux density (PFD) of either 100 (C100) or 500 (C500) μmolm−2s−1 or (2) fluctuating light between 100 or 500μmolphotonsm−2s−1 with a frequency of either 15 (F15) or 60 (F60) min. Under continuous light, the initial portion of the light phase required the concomitant presence of high CO2 and NO3− concentrations for maximum growth. After exposure to light for 3h, high CO2 exerted a negative effect on growth and effective quantum yield of photosystem II (F′v/F′m). Fluctuating light ameliorated growth in the first period of illumination. In the second 3h of treatment, higher frequency (F15) of fluctuations afforded high growth rates, whereas the F60 treatment had detrimental consequences, especially when NO3− concentration was lower. F′v/F′m responded differently from growth to fluctuating light: the fluorescence yield was always lower than at continuous light at 100μmolm−2s−1, and always higher at 500μmolm−2s−1. Our data show that the impact of atmospheric pCO2 increase on primary production of dinoflagellate depends on the availability of nitrate and the irradiance (intensity and the frequency of irradiance fluctuations) to which the cells are exposed. The impact of global change on oceanic primary producers would therefore be different in waters with different chemical and physical (mixing) properties.

Climatological distributions of pH, pCO2, total CO2, alkalinity, and CaCO3 saturation in the global surface ocean, and temporal changes at selected locations

Climatological mean monthly distributions of pH in the total H+ scale, total CO2 concentration (TCO2), and the degree of CaCO3 saturation for the global surface ocean waters (excluding coastal areas) are calculated using a data set for pCO2, alkalinity and nutrient concentrations in surface waters (depths <50m), which is built upon the GLODAP, CARINA and LDEO databases. The mutual consistency among these measured parameters is demonstrated using the inorganic carbon chemistry model with the dissociation constants for carbonic acid by Lueker et al. (2000) and for boric acid by Dickson (1990). Linear potential alkalinity-salinity relationships are established for 24 regions of the global ocean. The mean monthly distributions of pH and carbon chemistry parameters for the reference year 2005 are computed using the climatological mean monthly pCO2 data adjusted to a reference year 2005 and the alkalinity estimated from the potential alkalinity-salinity relationships. The equatorial zone (4°N-4°S) of the Pacific is excluded from the analysis because of the large interannual changes associated with ENSO events. The pH thus calculated ranges from 7.9 to 8.2. Lower values are located in the upwelling regions in the tropical Pacific and in the Arabian and Bering Seas; higher values are found in the subpolar and polar waters during the spring-summer months of intense photosynthetic production. The vast areas of subtropical oceans have seasonally varying pH values ranging from 8.05 during warmer months to 8.15 during colder months. The warm tropical and subtropical waters are supersaturated by a factor of as much as 4.2 with respect to aragonite and 6.3 for calcite, whereas the cold subpolar and polar waters are supersaturated by 1.2 for aragonite and 2.0 for calcite because of the lower pH values resulting from greater TCO2 concentrations. In the western Arctic Ocean, aragonite undersaturation is observed. The time-series data from the Bermuda (BATS), Hawaii (HOT), Canary (ESTOC) and the Drake Passage show that pH has been declining at a mean rate of about -0.02 pH per decade, and that pCO2 has been increasing at about 19 μatm per decade tracking the atmospheric pCO2 increase rate. This suggests that the ocean acidification is caused primarily by the uptake of atmospheric CO2. The relative importance of the four environmental drivers (temperature, salinity, alkalinity and total CO2 concentration) controlling the seasonal variability of carbonate chemistry at these sites is quantitatively assessed. The ocean carbon chemistry is governed sensitively by the TA/TCO2 ratio, and the rate of change in TA is equally important for the future ocean environment as is the TCO2 in ocean waters increases in the future.

Seasonal variability of the carbon cycle in subantarctic surface water in the South West Pacific

Few Southern Hemisphere time series measurements of biogeochemical tracers are available, and this scarcity is a major impediment in understanding the biological and physical processes underlying the oceanic carbon and nutrient cycles in vast parts of the global oceans. We make use of bi‐monthly measurements of carbonate parameters from 1998 to 2010 in upper Subantarctic Surface Water east of New Zealand's South Island at 45.85°S 171.50°E to investigate seasonal cycles and trends in these species and processes controlling their variability. This time series reveals positive trends in salinity normalized dissolved inorganic carbon (sDIC) and the partial pressure of carbon dioxide (pCO2) that are smaller than would be expected from the anthropogenic increase in atmospheric pCO2 alone, possibly due to a decrease of the average temperature over the observational period. The seasonal cycle of pCO2 is dominated by that of DIC, but is substantially modified by the influence of the annual cycle of sea surface temperature. Investigations with a δ13COC‐constrained diagnostic box model suggest that net community production (NCP) is the dominant process controlling the observed seasonal variability in sDIC by removing 1.2 ± 0.7 mol C m−2 yr−1 from the mixed layer. This carbon drawdown, aided by an additional carbon removal due to horizontal transport, is balanced by vertical diffusion, entrainment, and air‐sea gas exchange of CO2. Oceanic pCO2 is below atmospheric pCO2 for nearly the entire year, leading to an annual mean surface ocean pCO2 undersaturation of about 12 µatm and an annual oceanic uptake of CO2 from the atmosphere of 0.9 ± 0.1 mol C m−2 yr−1.

CO2 drawdown following the middle Miocene expansion of the Antarctic Ice Sheet

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the “greenhouse” of the early Eocene to the “icehouse” of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive δ13C excursion known as carbon maximum 6 (“CM6”), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the δ13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high‐resolution multi‐proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

CO2-induced ocean acidification impairs calcification in the tropical urchin Echinometra viridis

Atmospheric carbon dioxide (pCO2) has risen from approximately 280 to 400ppm since the Industrial Revolution, due mainly to the combustion of fossil fuels, deforestation, and cement production. It is predicted to reach as high as 900ppm by the end of this century. Ocean acidification resulting from the release of anthropogenic CO2 has been shown to impair the ability of some marine calcifiers to build their shells and skeletons. Here, we present the results of ocean acidification experiments designed to assess the effects of an increase in atmospheric pCO2 from ca. 448 to 827ppm on calcification rates of the tropical urchin Echinometra viridis. Experiments were conducted under the urchin's winter (20°C) and summer (30°C) water temperatures in order to identify seasonal differences in the urchin's response to ocean acidification. The experiments reveal that calcification rates decreased for urchins reared under elevated pCO2, with the decline being more pronounced under wintertime temperatures than under summertime temperatures. These results indicate that the urchin E. viridis will be negatively impacted by CO2-induced ocean acidification that is predicted to occur by the end of this century. These results also suggest that impact of CO2-induced ocean acidification on urchin calcification will be more severe in the winter and in cooler waters.