1. Introduction
Announced by the Sixth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC), the global surface temperature has increased by 1.1°C by 2011-2020 compared to 1850-1900, which is unequivocally caused by human activities through emission of greenhouse gases (GHG) [
1]. Climate researches conducted in recent decades find that carbon dioxide (CO
2), the uppermost contributors for GHS, is higher than at any time in the past 200,000 years of human history, which has already break through the concentration of 420 μatm in the end of 2024. And the historical cumulative net emission of CO
2 from 1850 to 2019 is estimated to be as much as 2400 ±240 Gt [
1] (1Gt =10
9 t). Consequently, holding temperatures to well below 2 °C, and ideally 1.5 °C above the pre-industrial levels by the end of the century, exactly as the Paris Agreement’s objectives, requires not only rapid reductions of greenhouse gas emissions but removing billions of tons of CO
2 from the atmosphere [
2].
Marine carbon dioxide removal (mCDR) technologies have recently gained extensive attention because about a quarter of the CO
2 emission have been taken up by the ocean sinks since the Industrial Revolution [
3,
4], and thus the ocean has great influence on the mitigation of climate changes. As a whole, the ocean, serving as the largest pool of reactive carbon, contains about 3800 Gt of dissolved inorganic carbon (DIC), which is imported as a result of the dissolution of atmospheric CO
2 into the seawater. Exchange of CO
2 between the atmosphere and the ocean mixed layer (roughly the top 100 m of the ocean), regulated basically by the concentration gradient, temperature, and wind speed, is pretty rapid. The characteristic time scale for this air-sea exchange process is on the order of one year. Equation 1 describes what CO
2 undergoes after it enters the ocean [
5]. The gaseous CO
2 firstly transforms into its aqueous form and then forms carbonic acid (H
2CO
3) (Actually, the aqueous form of CO
2 and H
2CO
3 are hard to distinguish technically). Carbonic acid rapidly dissociates into free hydrogen ion (H
+) and bicarbonate (HCO
3-). And then, the bicarbonate further dissociates into H
+ and carbonate (CO
32-) with quite a slow rate. The dissolved species in Equation 1, predominantly in the form of HCO
3-, make up the carbonate alkalinity system, the dominant contributor to seawater alkalinity. Alkalinity, roughly refers to the excess of proton acceptors over donors, is a marine chemical parameter that largely determines the buffer capacity for CO
2 in seawater (Equation 2) [
6]. Basing on the above-mentioned ocean carbon chemistry, the concept of artificial ocean alkalinization (AOA) is put forward. AOA is considered as one of the most promising mCDR methods that has a theoretical sequestration potential in the range of 3 to 30 Gt CO
2 yr
−1 ([
7,
8,
9]). Increasing alkalinity drives consumption of protons and production of bicarbonate (HCO
3−) and carbonate (CO
32−), which leads to a corresponding increase of pH and a following decrease of partial pressure of CO
2 (
pCO
2) in seawater. These above changes would finally promote CO
2 uptake from the atmosphere via air–sea gas exchange process.
Previous studies have explored some aspects of AOA. For example, basing on an ocean carbon cycle model, Ilyina et al. [
10] confirmed that intensive enhancement of ocean alkalinity had the potential to promote oceanic uptake of fossil fuel CO
2 from the atmosphere and could avoid further ocean acidification indeed. Feng et al. [
11] run AOA simulations in the Great Barrier Reef, Caribbean Sea and South China Sea by an Earth system model of intermediate complexity, and founded alkalinization could counteract the local acidification changes expected in 21st century, in aspects of both oceanic surface
pCO
2 and surface aragonite saturation (Ω). However, Keller at al. [
12] found the effectiveness of AOA was actually limited by the production ability and the transport capacity of alkalinity material. So, the practical AOA induced atmospheric CO
2 reduction under current conditions was relatively small compared with the expected business-as-usual CO
2 emissions, and as a result, the atmospheric CO
2 would continue to increase gradually. Zhou et al. [
13] presented the global maps of AOA efficiency, and found that the equilibration kinetics had two characteristic timescales: rapid surface equilibration followed by a slower second phase. These kinetics vary considerably with latitude and the season of alkalinity release.
At present, there seems to be little consensus about the climate impacts and marine response of AOA, especially under the background of continuous rising carbon emission. Methodologically, the AOA implementation could be obtained by both observation-based estimations [e.g.
14,
15,
16] and model simulation outputs [e.g.
17,
18,
19]. But in a way, model simulation can compensate for the inevitable temporal-spatial limitation of observation-based methods. The Earth System Models (ESMs) are the latest generation of the state-of-the-art climate models, which couple the carbon cycle processes among the atmosphere, land, and ocean, and simulate the real earth systems to the maximum extent. Therefore, the ESMs could serve as a helpful and powerful tool to analyze and diagnose the AOA.
To address this, we apply the up-to-date datasets produced by the new versions of ESM from the 6th Coupled Model Intercomparison Project (CMIP6) to characterize the temporal and spatial variabilities of marine carbon chemistry under the implementation of AOA. This paper will provide the comprehensive fundamental information of the CMIP6 AOA experiment, present the variabilities of the four most important carbonate chemistry parameters (DIC, pH,
pCO
2 and Ω), and estimates the long-term average and future tendency of air-sea CO
2 exchange flux (
FCO
2). The remainder of this paper is organized as following.
Section 2 introduces the model, datasets, and analytical materials. The results and discussions are presented in
Section 3.
Section 4 makes the conclusion.
2. Materials and Methods
We use the NorESM2-LM model in this study, which is the second generation of the fully coupled Earth system model developed by the Norwegian Climate Center [
20]. For details, the atmosphere component of NorESM2-LM is built on the Community Atmosphere Model version 6 (CAM6) but with particulate aerosols and the aerosol-radiation-cloud interaction parameterization, which is referred to as the CAM6-Nor. The ocean component is the Bergen Layered Ocean Model (BLOM), which employs an isopycnic vertical coordinate, with near-isopycnic interior layers and variable density layers in the surface mixed boundary layer [
20]. The ocean biogeochemistry component of NorESM2-LM is adapted from the HAMburg Ocean Carbon Cycle model and was converted to isopycnic coordinate (iHAMOCC) [
21]. The sea ice model component is based upon the Community Ice CodE (CICE) sea ice model [
22]. What’s more, the NorESM2-LM employs the latest version of Community Land Model (CLM5) as the land component [
23].
Data analyzed in this study are derived from the monthly outputs of three CMIP6 experiments: the
esm-hist, the
esm-ssp585, and the
esm-ssp585-ocn-alk [
24,
25]. Briefly, The CMIP6
esm-hist simulation, in which the atmospheric CO
2 concentration is calculated according to the historical anthropogenic CO
2 emissions forcing, is essential for the reliability testing before the ocean alkalinization experiment. This experiment is run from the year of 1850 to 2014. The
esm-ssp585, then, is driven by the SSP5-8.5 high CO
2 emission scenario and run from the end year of
esm-hist simulation until the end of this century (2015 to 2100), and serves as the control run and branching point for the subsequent ocean alkalinization experiment. The
esm-ssp585-ocn-alk simulation, forcing by the SSP5-8.5 high CO
2 emission scenario as well, adds 0.14 Pmol TA (1 Pmol=10
15 mol) to the upper ice-free ocean surface waters between 70°N and 60°S every year during from 2015 to 2100. In general, the average differences between the AOA
esm-ssp585-ocn-alk and the no-AOA
esm-ssp585 of specific parameters are obtained as the net effectiveness of AOA implement. What’s more, the key information about the CMIP6 experiments conducted by the NorESM2-LM is summarized in
Table 1 as below.
Observational dataset employed in this paper is the classic climatological air-sea CO
2 flux from Lamont-Doherty Earth Observatory of Columbia University with the original resolution of 4°×5° [
26], which was widely used in the study of global carbon cycle. We re-gridded it into 1°×1° grid and referred to it as “Takahashi2009” for the comparison of long-term average air-sea CO
2 flux and spatial distributions of model bias.
4. Conclusions
Artificial ocean alkalinization (AOA) is one of the most promising marine carbon dioxide removal (mCDR) technologies, which has an enormous theoretical sequestration potential for atmospheric CO2. In this article, we apply the results of the Earth System Model (ESM) from the 6th Coupled Model Intercomparison Project (CMIP6) to characterize the temporal and spatial variabilities of marine carbon chemistry under the implementation of AOA. Our research shown that the marine carbon chemistry system varied widely under the implement of AOA, but some efficiencies were covered up by the forcing of high carbon emission scenario ssp5-8.5. Basing on the CMIP6 protocols, the AOA experiment adds 0.14 Pmol TA to the upper ice-free ocean surface waters between 70°N and 60°S every year during from 2015 to 2100, and could promote the increase of DIC, delayed the rise of pCO2, and restrained the aggravation of pH and Ω, to different extent actually. The esm-ssp585-ocn-alk experiment of CMIP6 was able to simulate the overall variation pattern of the marine carbon system during AOA. The temperate oceans in both hemispheres were the most significant impacted basins, whereas the Southern Ocean were the less affected region. But the detailed spatial and seasonal variations need further specific modeling. In the present century, the oceanic carbon sink would intensify until the year around 2080, and then slow down. The implementation of AOA merely changed the relative strength of oceanic sink rather than the variation pattern. Our results also suggested that the effectiveness of AOA on the atmospheric CO2 concentration under the high SSP5-8.5 scenario did exist, but was quite little, so the concentrations of atmospheric CO2 increased continuously both for the no-AOA esm-ssp585 and the AOA esm-ssp585-ocn-alk during from 2015 to the end of this century. In a similar way, what’ more, the effectiveness of AOA into the ocean interior did exist, but was quite little for the mitigation of ocean acidification under the high SSP5-8.5 scenario. In the year of 2100, the global ocean deeper than about 3900 m would be undersaturated to aragonite, implying the growing problem of ocean acidification.