Revelle Factor Research Articles

Generalised expressions for the response of pH to changes in ocean chemistry

The extent to which oceans are capable of buffering chemical changes resulting from the uptake of carbon dioxide (CO2) or other acidifying processes can be quantified using buffer factors. Here, we present general expressions describing the sensitivity of pH and concentrations of CO2 and other acid–base species to a change in ocean chemistry. These expressions can include as many acid–base systems as desirable, making them suitable for application to, e.g., upwelling regions or nutrient-rich coastal waters. We show that these expressions are fully consistent with previously derived expressions for the Revelle factor and other buffer factors, which only included the carbonate and borate acid–base systems, and provide more accurate values.We apply our general expressions to contemporary global ocean surface water and possible changes therein by the end of the 21st century. These results show that most sensitivities describing a change in pH are of greater magnitude in a warmer, high-CO2 ocean, indicating a decreased seawater buffering capacity. This trend is driven by the increase in CO2 and slightly moderated by the warming. Respiration-derived carbon dioxide may amplify or attenuate ocean acidification due to rising atmospheric CO2, depending on their relative importance. Our work highlights that, to gain further insight into current and future pH dynamics, it is crucial to properly quantify the various concurrently acting buffering mechanisms.

Preliminary Studies on Impacts of Ocean Acidification on Diversity of Fish Species Landed By Artisanal and Semi-Industrial Fisheries in Ghana

Increased absorbance of carbon dioxide from the atmosphere has led to the changing of the chemistry of the oceans. In addition to already existing stressors, the resultant ocean acidification poses multiple threats to marine species biodiversity; and goods, services and livelihoods that depend on them. This study set out to determine possible impacts of globally occurring ocean acidification on the abundance and diversity of fin- and shellfish species and ichthyoplankton in the artisanal and semi-industrial fisheries of Ghana. Physico-chemical parameters of the sites where fishing by artisanal and semi-industrial vessels were carried out were collected in the lean and peak fishing seasons. Fish samples were collected, species identified, counted and diversity indices calculated for each fishery and fishing season. A Canonical Correspondence Analysis (CCA) was used to identify which of the principal factors influenced the fish species. Four ocean acidification parameters (pH, carbonate ion concentration, total alkalinity, Revelle factor) out of six principal components were identified to contribute significantly (RELATE, r = 0.955, P < 0.05) to biological variations observed in the two fisheries. A decreasing trend in ocean acidification indicators was observed for both fisheries and variations observed in species abundance between seasons and fisheries, which provide evidence of the possible occurrence of ocean acidification in Ghanaian waters and likelihood of impacts on fish diversity. Continuous long term monitoring of the studied parameters and inclusion of adaptive and mitigative strategies for impacts of ocean acidification in marine fisheries management plans is recommended.

Drivers of the carbonate system seasonal variations in a Mediterranean gulf

The effects of different physical and biogeochemical drivers on the carbonate system were investigated in a semi-enclosed coastal area characterized by high alkalinity riverine discharge (Gulf of Trieste, Northern Adriatic Sea, Mediterranean Sea). Our 2-year time-series showed that a large part of the seasonal carbonate chemistry variation was controlled by the large seasonal change of seawater temperature, though air-sea CO2 exchange, biological activity (primary production-respiration), and riverine inputs also exerted a significant influence.With the exception of summer, the Gulf of Trieste was a sink of atmospheric carbon dioxide, showing a very strong CO2 fluxes from atmosphere into the sea (−16.10 mmol m−2 day−1) during high wind speed event of north easterly Bora wind. The CO2 influx was particularly evident in winter, when the biological activity was at minimum and the low seawater temperature enhanced CO2 solubility. During spring, the drawdown of CO2 by primary production overwhelmed the CO2 physical pump, driving a significant decrease of dissolved inorganic carbon (DIC), [CO2], and increase of pHT25 °C. In summer the primary production in surface waters occurred with the same intensity as respiration in the bottom layer, so the net biological effect on the carbonate system was very low and the further reduction of seawater CO2 concentration observed was mainly due to carbon dioxide degassing induced by high seawater temperature. Finally, during autumn the respiration was the predominant process, which determined an overall increase of DIC, [CO2], and decrease of pHT25 °C. This was particularly evident when the breakdown of summer stratification occurred and a large amount of CO2, generated by respiration and segregated below the pycnocline, was released back to the whole water column. Local rivers also significantly affected the carbonate system by direct input of total alkalinity (AT) coming from the chemical weathering of carbonate rocks, which dominate the river watershed. Our finding clearly demonstrates a high AT concentration in low salinity surface waters (AT max = 2742.8 μmol kg−1) and a negative AT-salinity correlation. As a result the Gulf of Trieste revealed a low Revelle factor (10.1) and one of the highest buffer capacities of the Mediterranean Sea (ßDIC = 0.31 mmol kg−1), which allows the system to store a significant amount of atmospheric CO2 with a small decrease of seawater pH.

On the Southern Ocean CO2 uptake and the role of the biological carbon pump in the 21st century

AbstractWe use a suite of eight ocean biogeochemical/ecological general circulation models from the Marine Ecosystem Model Intercomparison Project and Coupled Model Intercomparison Project Phase 5 archives to explore the relative roles of changes in winds (positive trend of Southern Annular Mode, SAM) and in warming‐ and freshening‐driven trends of upper ocean stratification in altering export production and CO2 uptake in the Southern Ocean at the end of the 21st century. The investigated models simulate a broad range of responses to climate change, with no agreement on a dominance of either the SAM or the warming signal south of 44°S. In the southernmost zone, i.e., south of 58°S, they concur on an increase of biological export production, while between 44 and 58°S the models lack consensus on the sign of change in export. Yet in both regions, the models show an enhanced CO2 uptake during spring and summer. This is due to a larger CO2(aq) drawdown by the same amount of summer export production at a higher Revelle factor at the end of the 21st century. This strongly increases the importance of the biological carbon pump in the entire Southern Ocean. In the temperate zone, between 30 and 44°S, all models show a predominance of the warming signal and a nutrient‐driven reduction of export production. As a consequence, the share of the regions south of 44°S to the total uptake of the Southern Ocean south of 30°S is projected to increase at the end of the 21st century from 47 to 66% with a commensurable decrease to the north. Despite this major reorganization of the meridional distribution of the major regions of uptake, the total uptake increases largely in line with the rising atmospheric CO2. Simulations with the MITgcm‐REcoM2 model show that this is mostly driven by the strong increase of atmospheric CO2, with the climate‐driven changes of natural CO2 exchange offsetting that trend only to a limited degree (∼10%) and with negligible impact of climate effects on anthropogenic CO2 uptake when integrated over a full annual cycle south of 30°S.

Rising atmospheric CO2 leads to large impact of biology on Southern Ocean CO2 uptake via changes of the Revelle factor

The Southern Ocean is a key region for global carbon uptake and is characterized by a strong seasonality with the annual CO2 uptake being mediated by biological carbon drawdown in summer. Here we show that the contribution of biology to CO2 uptake will become even more important until 2100. This is the case even if biological production remains unaltered and can be explained by the decreasing buffer capacity of the ocean as its carbon content increases. The same amount of biological carbon drawdown leads to a more than twice as large reduction in CO2(aq) concentration and hence to a larger CO2 gradient between ocean and atmosphere that drives the gas exchange. While the winter uptake south of 44°S changes little, the summer uptake increases largely and is responsible for the annual mean response. The combination of decreasing buffer capacity and strong seasonality of biological carbon drawdown introduces a strong and increasing seasonality in the anthropogenic carbon uptake.Key PointsDecrease of buffer capacity leads to stronger summer CO2 uptake in the futureBiology will contribute more to future CO2 uptake in Southern OceanSeasonality affects anthropogenic carbon uptake strongly

Spring carbonate chemistry dynamics of surface waters in the northern East China Sea: Water mixing, biological uptake of CO2, and chemical buffering capacity

AbstractWe investigated sea surface total alkalinity (TAlk), dissolved inorganic carbon (DIC), dissolved oxygen (DO), and satellite‐derived chlorophyll‐a in the connection between the Yellow Sea and the East China Sea (ECS) during April to early May 2007. In spring, Changjiang dilution water (CDW), ECS offshore water, and together with Yellow Sea water (YSW) occupied the northern ECS. Using 16 day composite satellite‐derived chlorophyll‐a images, several algal blooms were identified in the CDW and ECS offshore water. Correspondingly, biological DIC drawdown of 73 ± 20 μmol kg−1, oversaturated DO of 10–110 μmol O2 kg−1, and low fugacity of CO2 of 181–304 μatm were revealed in these two waters. YSW also showed CO2 uptake in spring, due to the very low temperature. However, its intrusion virtually counteracted CO2 uptake in the northern ECS. In the CDW and the ECS offshore water, Revelle factor was 9.3–11.7 and 8.9–10.6, respectively, while relatively high Revelle factor values of 11.4–13.0 were revealed in YSW. In the ECS offshore water, the observed relationship between DIC drawdown and oversaturated DO departed from the Redfield ratio, indicating an effect of chemical buffering capacity on the carbonate system during air‐sea reequilibration. Given the fact that the chemical buffering capacity slows down the air‐sea reequilibration of CO2, the early spring DIC drawdown may have durative effects on the sea surface carbonate system until early summer. Although our study is subject to limited temporal and spatial coverage of sampling, these insights are fundamental to understanding sea surface carbonate chemistry dynamics in this important ocean margin.

Detecting anthropogenic carbon dioxide uptake and ocean acidification in the North Atlantic Ocean

Abstract. Fossil fuel use, cement manufacture and land-use changes are the primary sources of anthropogenic carbon dioxide (CO2) to the atmosphere, with the ocean absorbing approximately 30% (Sabine et al., 2004). Ocean uptake and chemical equilibration of anthropogenic CO2 with seawater results in a gradual reduction in seawater pH and saturation states (Ω) for calcium carbonate (CaCO3) minerals in a process termed ocean acidification. Assessing the present and future impact of ocean acidification on marine ecosystems requires detection of the multi-decadal rate of change across ocean basins and at ocean time-series sites. Here, we show the longest continuous record of ocean CO2 changes and ocean acidification in the North Atlantic subtropical gyre near Bermuda from 1983–2011. Dissolved inorganic carbon (DIC) and partial pressure of CO2 (pCO2) increased in surface seawater by ~40 μmol kg−1 and ~50 μatm (~20%), respectively. Increasing Revelle factor (β) values imply that the capacity of North Atlantic surface waters to absorb CO2 has also diminished. As indicators of ocean acidification, seawater pH decreased by ~0.05 (0.0017 yr−1) and ω values by ~7–8%. Such data provide critically needed multi-decadal information for assessing the North Atlantic Ocean CO2 sink and the pH changes that determine marine ecosystem responses to ocean acidification.

Uptake and storage of anthropogenic CO2 in the pacific ocean estimated using two modeling approaches

A basin-wide ocean general circulation model (OGCM) of the Pacific Ocean is employed to estimate the uptake and storage of anthropogenic CO2 using two different simulation approaches. The simulation (named BIO) makes use of a carbon model with biological processes and full thermodynamic equations to calculate surface water partial pressure of CO2, whereas the other simulation (named PTB) makes use of a perturbation approach to calculate surface water partial pressure of anthropogenic CO2. The results from the two simulations agree well with the estimates based on observation data in most important aspects of the vertical distribution as well as the total inventory of anthropogenic carbon. The storage of anthropogenic carbon from BIO is closer to the observation-based estimate than that from PTB. The Revelle factor in 1994 obtained in BIO is generally larger than that obtained in PTB in the whole Pacific, except for the subtropical South Pacific. This, to large extent, leads to the difference in the surface anthropogenic CO2 concentration between the two runs. The relative difference in the annual uptake between the two runs is almost constant during the integration processes after 1850. This is probably not caused by dissolved inorganic carbon (DIC), but rather by a factor independent of time. In both runs, the rate of change in anthropogenic CO2 fluxes with time is consistent with the rate of change in the growth rate of atmospheric partial pressure of CO2.

Multiple regimes of air‐sea carbon partitioning identified from constant‐alkalinity buffer factors

Numerical studies have indicated that the steady‐state ocean‐atmosphere partitioning of carbon will change profoundly as emissions continue. In particular, the globally averaged Revelle buffer factor will first increase and then decrease at higher emissions. Furthermore, atmospheric carbon will initially grow exponentially with emission size, after which it will depend linearly on emissions at higher emission totals. In this article, we explain this behavior by means of an analytical theory based on simple carbonate chemistry. A cornerstone of the theory is a newly defined dimensionless factor, O. We show that the qualitative changes are connected with different regimes in ocean chemistry: if the air‐sea partitioning of carbon is determined by the carbonate ion, then the Revelle factor increases with emissions, whereas the buffer factor decreases with emission size, when dissolved carbon dioxide determines the partitioning. Currently, the ocean carbonate chemistry is dominated by the carbonate ion response, but at high total emissions, the response of dissolved carbon dioxide takes on this role.

Uncoupled transport of chlorofluorocarbons and anthropogenic carbon in the subpolar North Atlantic

Chlorofluorocarbon (CFC) 11 and 12 transports across the transoceanic World Ocean Circulation Experiment (WOCE) A25 section in the subpolar North Atlantic are derived from an inverse model using hydrographic and ADCP data ( Lherminier et al., 2007). CFC and anthropogenic carbon ( C ANT) advective transports contrary to expected are uncoupled: C ANT is transported northeastwards (82±39 kmol s −1) mainly within the overturning circulation, while CFC-11 and CFC-12 are transported southwestwards (−24±4 and −11±2 mol s −1, respectively) as part of the large-scale horizontal circulation. The main reason for this uncoupled behaviour is the complex CFC vs. C ANT relation in the ocean, which stems from the contrasting temperature relation for both tracers: more C ANT dissolves in warmer waters with a low Revelle factor, while CFC’s solubility is higher in cold waters. These results point to C ANT and CFC having different routes of uptake, accumulation and transport within the ocean, and hence: C ANT transport would be more sensitive to changes in the overturning circulation strength, while CFC to changes in the East Greenland Current and Labrador Sea Water formation in the Irminger Sea. Additionally, C ANT and CFCs would have different sensitivities to circulation and climate changes derived from global warming as the slowdown of the overturning circulation, increase stratification due to warming and changes in wind stress.

Bergen Earth system model (BCM-C): model description and regional climate-carbon cycle feedbacks assessment

Abstract. We developed a complex Earth system model by coupling terrestrial and oceanic carbon cycle components into the Bergen Climate Model. For this study, we have generated two model simulations (one with climate change inclusions and the other without) to study the large scale climate and carbon cycle variability as well as its feedback for the period 1850–2100. The simulations are performed based on historical and future IPCC CO2 emission scenarios. Globally, a pronounced positive climate-carbon cycle feedback is simulated by the terrestrial carbon cycle model, but smaller signals are shown by the oceanic counterpart. Over land, the regional climate-carbon cycle feedback is highlighted by increased soil respiration, which exceeds the enhanced production due to the atmospheric CO2 fertilization effect, in the equatorial and northern hemisphere mid-latitude regions. For the ocean, our analysis indicates that there are substantial temporal and spatial variations in climate impact on the air-sea CO2 fluxes. This implies feedback mechanisms act inhomogeneously in different ocean regions. In the North Atlantic subpolar gyre, the simulated future cooling of SST improves the CO2 gas solubility in seawater and, hence, reduces the strength of positive climate carbon cycle feedback in this region. In most ocean regions, the changes in the Revelle factor is dominated by changes in surface pCO2, and not by the warming of SST. Therefore, the solubility-associated positive feedback is more prominent than the buffer capacity feedback. In our climate change simulation, the retreat of Southern Ocean sea ice due to melting allows an additional ~20 Pg C uptake as compared to the simulation without climate change.

Revelle revisited: Buffer factors that quantify the response of ocean chemistry to changes in DIC and alkalinity

We derive explicit expressions of the Revelle factor and several other buffer factors of interest to climate change scientists and those studying ocean acidification. These buffer factors quantify the sensitivity of CO2 and H+ concentrations ([CO2] and [H+]) and CaCO3 saturation (Ω) to changes in dissolved inorganic carbon concentration (DIC) and alkalinity (Alk). The explicit expressions of these buffer factors provide a convenient means to compare the degree of buffering of [CO2], [H+], and Ω in different regions of the oceans and at different times in the future and to gain insight into the buffering mechanisms. All six buffer factors have roughly similar values, and all reach an absolute minimum when DIC = Alk (pH ∼ 7.5). Surface maps of the buffer factors generally show stronger buffering capacity in the subtropical gyres relative to the polar regions. As the dissolution of anthropogenic CO2 increases the DIC of surface seawater over the next century, all the buffer factors will decrease, resulting in a much greater sensitivity to local variations in DIC and Alk. For example, diurnal and seasonal variations in pH and Ω caused by photosynthesis and respiration will be greatly amplified. Buffer factors provide convenient means to quantify the effect that changes in DIC and Alk have on seawater chemistry. They should also help illuminate the role that various physical and biological processes have in determining the oceanic response to an increase in atmospheric CO2.

Coupling of surface &amp;lt;i&amp;gt;p&amp;lt;/i&amp;gt;CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and dissolved oxygen in the northern South China Sea: impacts of contrasting coastal processes

Abstract. We examined the relationship between CO2 partial pressure (pCO2) and dissolved oxygen (DO) based on a cruise conducted in July 2004 to the northern South China Sea (111°–118° E 18°–23° N), spanning from estuarine plume, coastal upwelling and deep basin areas. Distinct relationships between pCO2 and DO saturation were identified in different regimes. In coastal upwelling areas and the Pearl River estuary, biological drawdown of pCO2 and production of O2 were simultaneously observed. The two properties were coupled with each other primarily via photosynthesis and respiration. The stoichiometric relationship of the two properties however, was quite different in these two environments due to different values of the Revelle factor. In the offshore areas, apart from the estuary and upwelling, the dynamics of pCO2 and DO were mainly influenced by air-sea exchange during water mixing. Given the fact that air-sea re-equilibration of O2 is much faster than that of CO2, the observed pCO2-DO relationship deviated from that of the theoretical prediction based on the Redfield relationship in the offshore areas. Although this study is subject to the limited temporal and spatial coverage of sampling, we have demonstrated a simple procedure to evaluate the community metabolic status based on a combination of high-resolution surface pCO2 and DO measurements, which may have applicability in many coastal systems with a large gradient of changes in their physical and biogeochemical conditions.

Riding over the Kuroshio from the South to the East China Sea: Mixing and transport of DIC

Export of dissolved inorganic carbon (DIC) to adjoining oceans enhances the potential of CO2 sequestration in marginal seas. By using a series of measured DIC depth profiles and reported flow transports, we estimated that the intermediate outflow (100–600 m) from the South China Sea is capable of transporting 6.5 ± 4.1 Tg (1 Tg = 1012g) of biologically mediated carbon (DICbio) annually to the East China Sea (ECS) via the northwardly flowing Kuroshio current. The mixing and transport of these DIC‐rich waters would raise 3% and 16% of DIC/TA ratio and the Revelle factor of the adjoining seawaters, respectively. Upon upwelling onto the ECS shelf, these DIC‐rich waters would counteract the potential of CO2 uptake of shelf waters that might have been enhanced by the accompanying increase in nutrient inputs, thus complicating assessment of the ECS as a net CO2 source or sink.

Rapid decline of the CO2 buffering capacity in the North Sea and implications for the North Atlantic Ocean

New observations from the North Sea, a NW European shelf sea, show that between 2001 and 2005 the CO2 partial pressure (pCO2) in surface waters rose by 22 μatm, thus faster than atmospheric pCO2, which in the same period rose approximately 11 μatm. The surprisingly rapid decline in air‐sea partial pressure difference (ΔpCO2) is primarily a response to an elevated water column inventory of dissolved inorganic carbon (DIC), which, in turn, reflects mostly anthropogenic CO2 input rather than natural interannual variability. The resulting decline in the buffering capacity of the inorganic carbonate system (increasing Revelle factor) sets up a theoretically predicted feedback loop whereby the invasion of anthropogenic CO2 reduces the ocean's ability to uptake additional CO2. Model simulations for the North Atlantic Ocean and thermodynamic principles reveal that this feedback should be stronger, at present, in colder midlatitude and subpolar waters because of the lower present‐day buffer capacity and elevated DIC levels driven either by northward advected surface water and/or excess local air‐sea CO2 uptake. This buffer capacity feedback mechanism helps to explain at least part of the observed trend of decreasing air‐sea ΔpCO2 over time as reported in several other recent North Atlantic studies.

Anthropogenic CO2 and CFCs in the North Atlantic Ocean ‐ A comparison of man‐made tracers

We compare estimates of the anthropogenic CO2 content of seawater samples from the subpolar North Atlantic Ocean calculated on the basis of a back‐calculation technique with measurements of the chlorofluorocarbon CFC‐11. Estimated anthropogenic CO2 concentrations are in the range 10–80 µmol kg‐1, while CFC‐11 concentrations cover the full range from below detection limit to &gt; 5 pmol kg‐1 in waters at atmospheric equilibrium. The majority of the data points show a linear correlation between anthropogenic CO2 concentrations and CFC‐11 saturation, which can only be explained by the strongly advective nature of the North Atlantic Ocean. Only deep eastern basin samples deviate from this general observation in that they show still significant concentrations of anthropogenic CO2 where CFC‐11 is no longer detectable. In order to remove the influence of the Revelle factor reflected in the anthropogenic CO2 concentrations we have calculated 'excess' pCO2, showing an even tighter linear correlation with atmospheric equilibrium concentrations of CFC‐11.

A complete set of buffer factors for acid/base CO 2 system in seawater

A set of buffer factors is proposed which allows to compute changes of pH and pCO 2 resulting from an input or an output of bicarbonate, carbonate and proton ions in seawater. Results are compared to the well-known buffer factors that describe a dissolved CO 2 change (among which the Revelle factor β =dln(pCO 2)/dln| ΣCO 2|). It is pointed out that the actual β value can be quite different from the usual one (about 10) when other processes than air-sea exchanges are involved. Two examples of application are discussed: (1) A relationship is proposed to estimate β = dln(pCO 2)/dln| ΣCO 2| by taking into account simultaneous organic and inorganic carbon metabolism: β = −7.02 + 0.186%C org ( r 2 = 0.9994), where %C org is the percentage of carbon uptake for organic metabolism, (2) A relationship is proposed to calculate the amount of CO 2 that has to be exchanged with the atmosphere when adding strong acid to an equilibrated open seawater system.