Revelle Factor Research Articles

Climatological distribution of ocean acidification variables along the North American ocean margins

Abstract. Climatologies, which depict mean fields of oceanographic variables on a regular geographic grid, and atlases, which provide graphical depictions of specific areas, play pivotal roles in comprehending the societal vulnerabilities linked to ocean acidification (OA). This significance is particularly pronounced in coastal regions where most economic activities, such as commercial and recreational fisheries and aquaculture industries, occur. In this paper, we unveil a comprehensive data product featuring coastal ocean acidification climatologies and atlases, encompassing the fugacity of carbon dioxide, pH on the total scale, total hydrogen ion content, free hydrogen ion content, carbonate ion content, aragonite saturation state, calcite saturation state, Revelle factor, total dissolved inorganic carbon content, and total alkalinity content. These variables are provided on 1° × 1° spatial grids at 14 standardized depth levels, ranging from the surface to a depth of 500 m, along the North American ocean margins, defined as the region between the coastline and a distance of 200 nautical miles (∼370 km) offshore. The climatologies and atlases were developed using the World Ocean Atlas (WOA) gridding methods of the NOAA National Centers for Environmental Information (NCEI) based on the recently released Coastal Ocean Data Analysis Product in North America (CODAP-NA), along with the 2021 update to the Global Ocean Data Analysis Project version 2 (GLODAPv2.2021) data product. The relevant variables were adjusted to the index year of 2010. The data product is available in NetCDF (https://doi.org/10.25921/g8pb-zy76, Jiang et al., 2022b) on the NOAA Ocean Carbon and Acidification Data System: https://www.ncei.noaa.gov/data/oceans/ncei/ocads/metadata/0270962.html (last access: 15 July 2024). It is recommended to use the objectively analyzed mean fields (with “_an” suffix) for each variable. The atlases can be accessed at https://www.ncei.noaa.gov/access/ocean-carbon-acidification-data-system/synthesis/nacoastal.html (last access: 15 July 2024).

Projected poleward migration of the Southern Ocean CO2 sink region under high emissions

The Southern Ocean is a major region of ocean carbon uptake, but its future changes remain uncertain under climate change. Here we show the projected shift in the Southern Ocean CO2 sink using a suite of Earth System Models, revealing changes in the mechanism, position and seasonality of the carbon uptake. The region of dominant CO2 uptake shifts from the Subtropical to the Antarctic region under the high-emission scenario. The warming-driven sea-ice melt, increased ocean stratification, mixed layer shoaling, and a weaker vertical carbon gradient is projected to together reduce the winter de-gassing in the future, which will trigger the switch from mixing-driven outgassing to solubility-driven uptake in the Antarctic region during the winter season. The future Southern Ocean carbon sink will be poleward-shifted, operating in a hybrid mode between biologically-driven summertime and solubility-driven wintertime uptake with further amplification of biologically-driven uptake due to the increasing Revelle Factor.

Unraveling the factors influencing CO2 emissions from hydroelectric reservoirs in karst and non-karst regions: A comparative analysis

Carbon migration, transformation, and emissions as CO2 in reservoir and lake systems have been extensively studied. However, uncertainties persist regarding carbon cycling variations in both karst and non-karst regions within large thermal stratified river-reservoir systems. To address this knowledge gap, we combined measurements of water chemistry, isotopic compositions (δ13C), partial pressure of CO2 (pCO2), and CO2 fluxes (FCO2) to elucidate the differences, control mechanisms, and environmental effects of various carbon biogeochemical processes in the Hongjiadu reservoir (HJD, karst reservoir) and Shangyoujiang reservoir (SYJ, non-karst reservoir), Yangtze River basin, China. Our results demonstrate that key biogeochemical processes are associated with CO2 production and emissions. The stronger biological carbon pump (BCP) effect in the lentic area of the HJD reservoir limited CO2 emission (0.9 ± 5.0 mmol m−2 d−1) compared to the SYJ reservoir (50.9 ± 33.4 mmol m−2 d−1), leading to low dissolved inorganic carbon (DIC) and high saturation state of carbonate minerals in the lentic epilimnion. Although the released water from both reservoirs acted as hotspots for CO2 emissions, the results of higher Revelle factor (RF) in the HJD reservoir than SYJ reservoir suggest the greater buffer capacity and lower sensitivity of OC degradation changes in DIC. Despite the shorter hydraulic retention time (HRT) of SYJ reservoir (120 d) compared to HJD reservoir (368 d), FCO2 was 3.5 times higher than that of the HJD reservoir (652.9 mmol m−2 d−1). Moreover, upon analyzing selected reservoirs worldwide, it becomes apparent that karst reservoirs demonstrate a reduced potential for CO2 emissions. Our results indicate that the impact of varying geologic settings should be considered to minimize errors in regional and global CO2 emission estimates.

Alkalinity biases in CMIP6 Earth system models and implications for simulated CO2 drawdown via artificial alkalinity enhancement

Abstract. The partitioning of CO2 between atmosphere and ocean depends to a large degree not only on the amount of dissolved inorganic carbon (DIC) but also on alkalinity in the surface ocean. That is also why ocean alkalinity enhancement (OAE) is discussed as one potential approach in the context of negative emission technologies. Although alkalinity is thus an important variable of the marine carbonate system, little knowledge exists on how its representation in models compares with measurements. We evaluated the large-scale alkalinity distribution in 14 CMIP6 Earth system models (ESMs) against the observational data set GLODAPv2 and show that most models, as well as the multi-model mean, underestimate alkalinity at the surface and in the upper ocean and overestimate it in the deeper ocean. The decomposition of the global mean alkalinity biases into contributions from (i) physical processes (preformed alkalinity), which include the physical redistribution of biased alkalinity originating from the soft tissue and carbonates pumps; (ii) remineralization; and (iii) carbonate formation and dissolution showed that the bias stemming from the physical redistribution of alkalinity is dominant. However, below the upper few hundred meters the bias from carbonate dissolution can gain similar importance to physical biases, while the contribution from remineralization processes is negligible. This highlights the critical need for better understanding and quantification of processes driving calcium carbonate dissolution in microenvironments above the saturation horizons and implementation of these processes into biogeochemical models. For the application of the models to assess the potential of OAE to increase ocean carbon uptake, a back-of-the-envelope calculation was conducted with each model's global mean surface alkalinity, DIC, and partial pressure of CO2 in seawater (pCO2) as input parameters. We evaluate the following two metrics: (1) the initial pCO2 reduction at the surface ocean after alkalinity addition and (2) the uptake efficiency (ηCO2) after air–sea equilibration is reached. The relative biases of alkalinity versus DIC at the surface affect the Revelle factor and therefore the initial pCO2 reduction after alkalinity addition. The global mean surface alkalinity bias relative to GLODAPv2 in the different models ranges from −85 mmol m−3 (−3.6 %) to +50 mmol m−3 (+2.1 %) (mean: −25 mmol m−3 or −1.1 %). For DIC the relative bias ranges from −55 mmol m−3 (−2.6 %) to 53 mmol m−3 (+2.5 %) (mean: −13 mmol m−3 or −0.6 %). All but two of the CMIP6 models evaluated here overestimate the Revelle factor at the surface by up to 3.4 % and thus overestimate the initial pCO2 reduction after alkalinity addition by up to 13 %. The uptake efficiency, ηCO2, then takes into account that a higher Revelle factor and a higher initial pCO2 reduction after alkalinity addition and equilibration mostly compensate for each other, meaning that resulting DIC differences in the models are small (−0.1 % to 1.1 %). The overestimation of the initial pCO2 reduction has to be taken into account when reporting on efficiencies of ocean alkalinity enhancement experiments using CMIP6 models, especially as long as the CO2 equilibrium is not reached.

Global Surface Ocean Acidification Indicators From 1750 to 2100

AbstractAccurately predicting future ocean acidification (OA) conditions is crucial for advancing OA research at regional and global scales, and guiding society's mitigation and adaptation efforts. This study presents a new model‐data fusion product covering 10 global surface OA indicators based on 14 Earth System Models (ESMs) from the Coupled Model Intercomparison Project Phase 6 (CMIP6), along with three recent observational ocean carbon data products. The indicators include fugacity of carbon dioxide, pH on total scale, total hydrogen ion content, free hydrogen ion content, carbonate ion content, aragonite saturation state, calcite saturation state, Revelle Factor, total dissolved inorganic carbon content, and total alkalinity content. The evolution of these OA indicators is presented on a global surface ocean 1° × 1° grid as decadal averages every 10 years from preindustrial conditions (1750), through historical conditions (1850–2010), and to five future Shared Socioeconomic Pathways (2020–2100): SSP1‐1.9, SSP1‐2.6, SSP2‐4.5, SSP3‐7.0, and SSP5‐8.5. These OA trajectories represent an improvement over previous OA data products with respect to data quantity, spatial and temporal coverage, diversity of the underlying data and model simulations, and the provided SSPs. The generated data product offers a state‐of‐the‐art research and management tool for the 21st century under the combined stressors of global climate change and ocean acidification. The gridded data product is available in NetCDF at the National Oceanic and Atmospheric Administration (NOAA) National Centers for Environmental Information: https://www.ncei.noaa.gov/data/oceans/ncei/ocads/metadata/0259391.html, and global maps of these indicators are available in jpeg at: https://www.ncei.noaa.gov/access/ocean-carbon-acidification-data-system/synthesis/surface-oa-indicators.html.

Carbonate system data tracing freshwater inflow into the Ross Sea through the eastern gate and along the Ross Ice Shelf (Antarctica)

The eastern Ross Sea is a key area to understand the role of the Amundsen Sea inflow of freshwater that can influence the Ross Sea water properties and salt budget. A survey was carried out in the eastern Ross Sea during the austral summer 2019–20 to evaluate the contribution of the Amundsen Sea Water (ASW) to the salinity variability. A total of 248 seawater samples were collected f\or the analysis of total alkalinity (AT) and pH. The data collected were used together with temperature and salinity to obtain a full description of the carbonate system properties including total inorganic carbon (CT), CO2 partial pressure (pCO2), calcium carbonate saturation state of aragonite and calcite (Ω), and Revelle factor. Moreover, we estimated the anthropogenic carbon (Cant) throughout the TrOCA method to better understand the carbon cycle, also considering the effect of atmospheric CO2 uptake on ocean acidification. We used principal component analysis (PCA) to investigate the major controls on the carbonate system parameters with the aim of defining their sensitivity as chemical tracers. The changes in carbonate chemistry in surface waters were mainly due to the physical properties. AT and pH traced the entry of the ASW showing limited mixing between water masses on the shelf area. Shelf waters were enriched in Cant, which resulted lower than the estimated value for shelf waters produced in western Ross Sea.

The buffering of a riverine carbonate system under the input of acid mine drainage: Example from a small karst watershed, southwest China

In a karstic area affected by acid mine drainage (AMD), hydrochemical conditions, such as temperature, salinity, alkalinity, DIC, dissolved oxygen, and nutrients, may affect the buffering capacity of carbonate systems in freshwater systems. The resulting pH fluctuation is larger than that of a marine system. Therefore, this study focuses on the buffering of a riverine carbonate system under the input of AMD and discusses the variations in a series of buffering factors, including the Revelle factor, γDIC, γAlk βDIC, βAlk, ωDIC, and ωAlk. The results revealed that the Revelle factor could reflect the buffering process effectively; in addition, the maximum value of the Revelle factor appeared at pH = 8.5. The data points for pH greater than this value indicated that the Huatan River had the ability to absorb atmospheric CO2 in spring. Conversely, the data for pH less than this value reflected the buffering of H+ during CO2 degassing in summer and autumn. In winter, the data were around the maximum value, indicating the weakest buffering capacity. As a result, the dynamics of the carbonate system caused the most sensitive response to pH. In addition, the maximum Revelle factor value did not always indicate the carbonate system had reached equilibrium; the presence of strong CO2 degassing was still a possibility. Under acidic conditions, as CO2(aq) increased, the absolute values of γDIC, βDIC, ωDIC, and γAlk increased correspondingly, indicating the enhanced buffering capacity of H+ during CO2 degassing. Under the four Representative Concentration Pathways scenarios (RCPs) included in the IPCC’s fifth assessment report, the degassing rate of the Huatan River would decrease by 5%, 15%, 26%, or 48%, depending on the scenario. Even though the Huatan River revealed CO2 degassing characteristics in winter and spring under current conditions, it will eventually become a sink for atmospheric CO2 as atmospheric CO2 concentration increases. In this light, the carbon sink effect in karst areas will become increasingly important.

Observation-constrained estimates of the global ocean carbon sink from Earth system models

Abstract. The ocean slows global warming by currently taking up around one-quarter of all human-made CO2 emissions. However, estimates of the ocean anthropogenic carbon uptake vary across various observation-based and model-based approaches. Here, we show that the global ocean anthropogenic carbon sink simulated by Earth system models can be constrained by two physical parameters, the present-day sea surface salinity in the subtropical–polar frontal zone in the Southern Ocean and the strength of the Atlantic Meridional Overturning Circulation, and one biogeochemical parameter, the Revelle factor of the global surface ocean. The Revelle factor quantifies the chemical capacity of seawater to take up carbon for a given increase in atmospheric CO2. By exploiting this three-dimensional emergent constraint with observations, we provide a new model- and observation-based estimate of the past, present, and future global ocean anthropogenic carbon sink and show that the ocean carbon sink is 9 %–11 % larger than previously estimated. Furthermore, the constraint reduces uncertainties of the past and present global ocean anthropogenic carbon sink by 42 %–59 % and the future sink by 32 %–62 % depending on the scenario, allowing for a better understanding of the global carbon cycle and better-targeted climate and ocean policies. Our constrained results are in good agreement with the anthropogenic carbon air–sea flux estimates over the last three decades based on observations of the CO2 partial pressure at the ocean surface in the Global Carbon Budget 2021, and they suggest that existing hindcast ocean-only model simulations underestimate the global ocean anthropogenic carbon sink. The key parameters identified here for the ocean anthropogenic carbon sink should be quantified when presenting simulated ocean anthropogenic carbon uptake as in the Global Carbon Budget and be used to adjust these simulated estimates if necessary. The larger ocean carbon sink results in enhanced ocean acidification over the 21st century, which further threatens marine ecosystems by reducing the water volume that is projected to be undersaturated towards aragonite by around 3.7×106–7.4×106 km3 more than originally projected.

Contrasting projections of the ENSO-driven CO2flux variability in the equatorial Pacific under high-warming scenario

Abstract. The El Niño–Southern Oscillation (ENSO) widely modulates the global carbon cycle. More specifically, it alters the net uptake of carbon in the tropical ocean. Indeed, over the tropical Pacific less carbon is released by oceans during El Niño, while the opposite is the case for La Niña. Here, the skill of Earth system models (ESMs) from the latest Coupled Model Intercomparison Project (CMIP6) to simulate the observed tropical Pacific CO2 flux variability in response to ENSO is assessed. The temporal amplitude and spatial extent of CO2 flux anomalies vary considerably among models, while the surface temperature signals of El Niño and La Niña phases are generally well represented. Under historical conditions followed by the high-warming Shared Socio-economic Pathway (SSP5-8.5) scenarios, about half the ESMs simulate a reversal in ENSO–CO2 flux relationship. This gradual shift, which occurs as early as the first half of the 21st century, is associated with a high CO2-induced increase in the Revelle factor that leads to stronger sensitivity of partial pressure of CO2 (pCO2) to changes in surface temperature between ENSO phases. At the same time, uptake of anthropogenic CO2 substantially increases upper-ocean dissolved inorganic carbon (DIC) concentrations (reducing its vertical gradient in the thermocline) and weakens the ENSO-modulated surface DIC variability. The response of the ENSO–CO2 flux relationship to future climate change is sensitive to the contemporary mean state of the carbonate ion concentration in the tropics. We present an emergent constraint between the simulated contemporary carbonate concentration with the projected cumulated CO2 fluxes. Models that simulate shifts in the ENSO–CO2 flux relationship simulate positive bias in surface carbonate concentrations.

Anthropogenic Carbon Analysis in Eastern Sumatra Waters, Indonesia

Avrionesti; Hermawan, W.; Putri, M.R.; Diastomo, H.; Badriana, M.R.; Surya, M.Y.; Abdurrahman, U.; Suprijo, T., and Park, H., 2021. Anthropogenic carbon analysis in eastern Sumatra waters, Indonesia. In: Lee, J.L.; Suh, K.-S.; Lee, B.; Shin, S., and Lee, J. (eds.), Crisis and Integrated Management for Coastal and Marine Safety. Journal of Coastal Research, Special Issue No. 114, pp. 276–280. Coconut Creek (Florida), ISSN 0749-0208. Human activities are increasing the production of released carbon dioxide into the air, land, or waters. The impact of those activities on the ocean was analyzed based on the calculation of anthropogenic carbon using inorganic carbon measurements. To enhance the understanding of carbon anthropogenic in another part of Indonesia, this research aims to get the spatial distribution of oceanic anthropogenic carbon at eastern Sumatra waters. The 2020 anthropogenic carbon is also calculated based on pH, salinity, and temperature trends and then compared with the revelle factor value to assess the carbon saturation of waters in eastern Sumatra. The concentration of anthropogenic carbon, in general, is inversely proportional to the revelle factor.

The role of soils in the regulation of ocean acidification.

Soils play an important role in mediating chemical weathering reactions and carbon transfer from the land to the ocean. Proposals to increase the contribution of alkalinity to the oceans through ‘enhanced weathering’ as a means to help prevent climate change are gaining increasing attention. This would augment the existing connection between the biogeochemical function of soils and alkalinity levels in the ocean. The feasibility of enhanced weathering depends on the combined influence of what minerals are added to soils, the formation of secondary minerals in soils and the drainage regime, and the partial pressure of respired CO2 around the dissolving mineral. Increasing the alkalinity levels in the ocean through enhanced weathering could help to ameliorate the effects of ocean acidification in two ways. First, enhanced weathering would slightly elevate the pH of drainage waters, and the receiving coastal waters. The elevated pH would result in an increase in carbonate mineral saturation states, and a partial reversal in the effects of elevated CO2. Second, the increase in alkalinity would help to replenish the ocean's buffering capacity by maintaining the ‘Revelle Factor’, making the oceans more resilient to further CO2 emissions. However, there is limited research on the downstream and oceanic impacts of enhanced weathering on which to base deployment decisions.This article is part of the theme issue ‘The role of soils in delivering Nature's Contributions to People’.

Surface ocean pH and buffer capacity: past, present and future

The ocean’s chemistry is changing due to the uptake of anthropogenic carbon dioxide (CO2). This phenomenon, commonly referred to as “Ocean Acidification”, is endangering coral reefs and the broader marine ecosystems. In this study, we combine a recent observational seawater CO2 data product, i.e., the 6th version of the Surface Ocean CO2 Atlas (1991–2018, ~23 million observations), with temporal trends at individual locations of the global ocean from a robust Earth System Model to provide a high-resolution regionally varying view of global surface ocean pH and the Revelle Factor. The climatology extends from the pre-Industrial era (1750 C.E.) to the end of this century under historical atmospheric CO2 concentrations (pre-2005) and the Representative Concentrations Pathways (post-2005) of the Intergovernmental Panel on Climate Change (IPCC)’s 5th Assessment Report. By linking the modeled pH trends to the observed modern pH distribution, the climatology benefits from recent improvements in both model design and observational data coverage, and is likely to provide improved regional OA trajectories than the model output could alone, therefore, will help guide the regional OA adaptation strategies. We show that air-sea CO2 disequilibrium is the dominant mode of spatial variability for surface pH, and discuss why pH and calcium carbonate mineral saturation states, two important metrics for OA, show contrasting spatial variability.

Trends in anthropogenic carbon in the Arctic Ocean

This study evaluates the trends in anthropogenic carbon (Cant) in the different sub-basins of the Arctic Ocean between 1987 and 2015. Data were extracted from the GLODAPv2 data product as well as two GEOTRACERS cruises in the Arctic Ocean from 2015 and Cant was evaluated using the transient time distribution (TTD) approach. In the Nansen and Amundsen sub-basins, the Cant trend in the Atlantic Waters (AW, depths: 200–500 m) and dense AW (dAW, depths: 500–800 m) is about +0.7 µmol kg−1 yr−1. As we move into the Makarov and West Canadian sub-basins, the Cant trend in the AW and dAW is smaller. The upper Polar Deep Water (uPDW, depths: 800–1600 m) has a Cant trend of about +0.4–0.5 µmol kg−1 yr−1 in the Nansen, Amundsen and West Canadian sub-basins. The trend is smallest in the South Canadian sub-basin, with a value of about +0.2 µmol kg−1 yr−1. Ventilation primarily governs Cant trends while the influence of the Revelle factor plays a secondary role. The increase in the Cant column inventory is estimated to be 0.7–1.0 mol C m−2 yr−1 in the Nansen, Amundsen and Makarov sub-basins. By extrapolating the results from our defined sub-basins to the full Arctic Ocean, we estimate an Cant accumulation of 25 Tg C yr−1 in the Arctic Ocean and an inventory of about 3.6–3.9 Pg C between 2005 and 2015.

Seasonal Asymmetry in the Evolution of Surface Ocean pCO2 and pH Thermodynamic Drivers and the Influence on Sea‐Air CO2 Flux

AbstractIt has become clear that anthropogenic carbon invasion into the surface ocean drives changes in the seasonal cycles of carbon dioxide partial pressure (pCO2) and pH. However, it is not yet known whether the resulting sea‐air CO2 fluxes are symmetric in their seasonal expression. Here we consider a novel application of observational constraints and modeling inferences to test the hypothesis that changes in the ocean's Revelle factor facilitate a seasonally asymmetric response in pCO2 and the sea‐air CO2 flux. We use an analytical framework that builds on observed sea surface pCO2 variability for the modern era and incorporates transient dissolved inorganic carbon concentrations from an Earth system model. Our findings reveal asymmetric amplification of pCO2 and pH seasonal cycles by a factor of two (or more) above preindustrial levels under Representative Concentration Pathway 8.5. These changes are significantly larger than observed modes of interannual variability and are relevant to climate feedbacks associated with Revelle factor perturbations. Notably, this response occurs in the absence of changes to the seasonal cycle amplitudes of dissolved inorganic carbon, total alkalinity, salinity, and temperature, indicating that significant alteration of surface pCO2 can occur without modifying the physical or biological ocean state. This result challenges the historical paradigm that if the same amount of carbon and nutrients is entrained and subsequently exported, there is no impact on anthropogenic carbon uptake. Anticipation of seasonal asymmetries in the sea surface pCO2 and CO2 flux response to ocean carbon uptake over the 21st century may have important implications for carbon cycle feedbacks.

Carbon dynamics and inconstant porewater input in a mangrove tidal creek over contrasting seasons and tidal amplitudes

Constraining the contribution of mangrove-derived carbon in tidal creeks is fundamental to understanding the fate of mangrove primary production and the role of mangroves as coastal carbon sinks. Porewater measurements and 24-h time series in a mangrove tidal creek were conducted during the dry and wet season, and over contrasting tidal ranges at the Can Gio Biosphere Reserve, Vietnam. Surface water carbon concentrations (dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), partial pressure of carbon dioxide (pCO2)) and their respective δ13C values were correlated with radon, suggesting that porewater input drives mangrove-derived carbon in the tidal creek. Based on three complementary mixing models, porewater input contributed to about 30% of the water volume and 46% to 100% of DOC and DIC pools in the tidal creek at low tide, with variabilities between seasons and tidal amplitudes. The creek carbon pool was 88% DIC, 6% DOC, and 6% particulate organic carbon (POC). The pCO2 values during the wet season (2973–16,495 μatm) were on average 5-fold higher than during the dry season (584–2946 μatm). This was explained by a potential greater mineralization attributed to higher organic matter availability and residual humidity that stimulate bacterial activity, and by a potential tidal dilution changing the pCO2/DIC ratio as suggested by the Revelle factor. Consequently, average CO2 evasion from the creek was estimated at 327–427 mmolC m−2 d−1 during the wet season and 92–213 mmolC m−2 d−1 during the dry season, using two independent approaches. Tidal amplitude seemed to influence porewater input and its carbon loads, with a higher contribution during frequent and high tidal amplitudes (symmetric). However, the highest input occurred in a tidal cycle which was preceded by tidal cycle of low amplitude (asymmetric). We explain this ambiguity by the influence of both, rapid water turnover intensifying porewater exchange, and long water residence time enhancing carbon load in porewater.

An Assessment of Direct Dissolved Inorganic Carbon Injection to the Coastal Region: A Model Result

The amount of carbon dioxide (CO2) in the atmosphere has increased in the past 60 years and the technology of carbon capture and storage (CCS) has recently been extensively studied. One of the strategies of CCS is to directly inject a high dissolved inorganic carbon (DIC) concentration (or high partial pressure of carbon dioxide, pCO2) solution into the ocean. However, the carbonate dynamics and air-sea gas exchange are usually neglected in a CCS strategy. This study assesses the effect of a DIC-solution injection by using a simple two end-member model to simulate the variation of pH, DIC, total alkalinity (TA) and pCO2 between the river and sea mixing process for the Danshuei River estuary and Hoping River in Taiwan. We observed that the DIC-solution injection can contribute to ocean acidification and can also lead the pCO2 value to change from being undersaturated to oversaturated (with respect to the atmospheric CO2 level). Our model result also showed that the maximum Revelle factors (Δ[CO2]/[CO2])/(Δ[DIC]/[DIC]) among varied pH values (6–9) and DIC concentrations (0.5–3.5 mmol kg−1) were between pH 8.3 and 8.5 in fresh water and were between 7.3 and 7.5 in waters with a salinity of 35, reflecting the changing efficiency of dissolving CO2 gas into the DIC solution and the varying stability of this desired DIC solution. Finally, we suggest this uncoupled Revelle factor between fresh and salty water should be considered in the (anthropogenic) carbonate chemical weathering on a decade to century scale.

Seagrass habitat metabolism increases short-term extremes and long-term offset of CO2 under future ocean acidification

The role of rising atmospheric CO2 in modulating estuarine carbonate system dynamics remains poorly characterized, likely due to myriad processes driving the complex chemistry in these habitats. We reconstructed the full carbonate system of an estuarine seagrass habitat for a summer period of 2.5 months utilizing a combination of time-series observations and mechanistic modeling, and quantified the roles of aerobic metabolism, mixing, and gas exchange in the observed dynamics. The anthropogenic CO2 burden in the habitat was estimated for the years 1765-2100 to quantify changes in observed high-frequency carbonate chemistry dynamics. The addition of anthropogenic CO2 alters the thermodynamic buffer factors (e.g., the Revelle factor) of the carbonate system, decreasing the seagrass habitat's ability to buffer natural carbonate system fluctuations. As a result, the most harmful carbonate system indices for many estuarine organisms [minimum pHT, minimum Ωarag, and maximum pCO2(s.w.)] change up to 1.8×, 2.3×, and 1.5× more rapidly than the medians for each parameter, respectively. In this system, the relative benefits of the seagrass habitat in locally mitigating ocean acidification increase with the higher atmospheric CO2 levels predicted toward 2100. Presently, however, these mitigating effects are mixed due to intense diel cycling of CO2 driven by aerobic metabolism. This study provides estimates of how high-frequency pHT, Ωarag, and pCO2(s.w.) dynamics are altered by rising atmospheric CO2 in an estuarine habitat, and highlights nonlinear responses of coastal carbonate parameters to ocean acidification relevant for water quality management.

The combined effects of acidification and hypoxia on pH and aragonite saturation in the coastal waters of the California current ecosystem and the northern Gulf of Mexico

Inorganic carbon chemistry data from the surface and subsurface waters of the West Coast of North America have been compared with similar data from the northern Gulf of Mexico to demonstrate how future changes in CO2 emissions will affect chemical changes in coastal waters affected by respiration-induced hypoxia ([O2] ≤ ~ 60µmolkg−1). In surface waters, the percentage change in the carbon parameters due to increasing CO2 emissions are very similar for both regions even though the absolute decrease in aragonite saturation is much higher in the warmer waters of the Gulf of Mexico. However, in subsurface waters the changes are enhanced due to differences in the initial oxygen concentration and the changes in the buffer capacity (i.e., increasing Revelle Factor) with increasing respiration from the oxidation of organic matter, with the largest impacts on pH and CO2 partial pressure (pCO2) occurring in the colder West Coast waters. As anthropogenic CO2 concentrations begin to build up in subsurface waters, increased atmospheric CO2 will expose organisms to hypercapnic conditions (pCO2 >1000 µatm) within subsurface depths. Since the maintenance of the extracellular pH appears as the first line of defense against external stresses, many biological response studies have been focused on pCO2-induced hypercapnia. The extent of subsurface exposure will occur sooner and be more widespread in colder waters due to their capacity to hold more dissolved oxygen and the accompanying weaker acid-base buffer capacity. Under present conditions, organisms in the West Coast are exposed to hypercapnic conditions when oxygen concentrations are near 100µmolkg−1 but will experience hypercapnia at oxygen concentrations of 260µmolkg−1 by year 2100 under the highest elevated-CO2 conditions. Hypercapnia does not occur at present in the Gulf of Mexico but will occur at oxygen concentrations of 170µmolkg−1 by the end of the century under similar conditions. The aragonite saturation horizon is currently above the hypoxic zone in the West Coast. With increasing atmospheric CO2, it is expected to shoal up close to surface waters under the IPCC Representative Concentration Pathway (RCP) 8.5 in West Coast waters, while aragonite saturation state will exhibit steeper gradients in the Gulf of Mexico. This study demonstrates how different biological thresholds (e.g., hypoxia, CaCO3 undersaturation, hypercapnia) will vary asymmetrically because of local initial conditions that are affected differently with increasing atmospheric CO2. The direction of change in amplitude of hypercapnia will be similar in both ecosystems, exposing both biological communities from the West Coast and Gulf of Mexico to intensification of stressful conditions. However, the region of lower Revelle factors (i.e., the Gulf of Mexico), currently provides an adequate refuge habitat that might no longer be the case under the most severe RCP scenarios.

Large Reemergence of Anthropogenic Carbon into the Ocean’s Surface Mixed Layer Sustained by the Ocean’s Overturning Circulation

We evaluate the output from a widely used ocean carbon cycle model to identify the subduction and obduction (reemergence) rates of anthropogenic carbon (Cant) for climatological conditions during the World Ocean Circulation Experiment (WOCE) era in 1995 using a new set of Lagrangian diagnostic tools. The principal scientific value of the Lagrangian diagnostics is in providing a new means to connect Cant reemergence pathways to the relatively rapid renewal time scales of mode waters through the overturning circulation. Our main finding is that for this model with 2.04 PgC yr−1 of uptake of Cant via gas exchange, the subduction and obduction rates across the base of the mixed layer (MLbase) are 4.96 and 4.50 PgC yr−1, respectively, which are twice as large as the gas exchange at the surface. Given that there is net accumulation of 0.17 PgC yr−1 in the mixed layer itself, this implies the residual downward Cant transport of 1.40 PgC yr−1 across the MLbase is associated with diffusion. Importantly, the net patterns for subduction and obduction transports of Cant mirror the large-scale patterns for transport of water volume, thereby illustrating the processes controlling Cant uptake. Although the net transfer across the MLbase by compensating subduction and obduction is relatively smaller than the diffusion, the localized pattern of Cant subduction and obduction implies significant regional impacts. The median time scale for reemergence of obducting particles is short (<10 yr), indicating that reemergence should contribute to limiting future carbon uptake through its contribution to perturbing the Revelle factor for surface waters.

Slow acidification of the winter mixed layer in the subarctic western North Pacific

AbstractWe used carbon dioxide (CO2) system data collected during 1999–2015 to investigate ocean acidification at time series sites in the western subarctic region of the North Pacific Ocean. The annual mean pH at station K2 decreased at a rate of 0.0025 ± 0.0010 year−1 mostly in response to oceanic uptake of anthropogenic CO2. The Revelle factor increased rapidly (0.046 ± 0.022 year−1), an indication that the buffering capacity of this region of the ocean has declined faster than at other time series sites. In the western subarctic region, the pH during the winter decline at a slower rate of 0.0008 ± 0.0004 year−1. This was attributed to a reduced rate of increase of dissolved inorganic carbon (DIC) and an increase of total alkalinity (TA). The reduction of DIC increase was caused by the decline of surface water density associated with the pycnocline depression and the reduction of vertical diffusion flux from the upper pycnocline. These physical changes were probably caused by northward shrinkage of the western subarctic gyre and global warming. Meanwhile, the contribution of the density decline to the TA increase is canceled out by that of the reduced vertical diffusive flux. We speculated that the winter TA increase is caused mainly by the accumulation of TA due to the weakened calcification by organisms during the winter.