Air-sea CO2 flux in an equatorial continental shelf dominated by coral reefs (Southwestern Atlantic Ocean)

Coral reefs are ecosystems highly vulnerable to changes in seawater carbonate chemistry, including those related to the ocean acidification and global warming. Brazilian coral reefs contains the major area of reefs coverage in the Southwestern (SW) Atlantic Ocean, however, studies aimed at investigating the controls of seawater carbonate chemistry in coral reefs are still overlooked in Brazil. This study comprehends the first investigation of complete seawater carbonate chemistry parameters in a section of the equatorial continental shelf dominated by coral reefs in the SW Atlantic Ocean. The sampling included spatial continuous underway measurements of sea surface CO2 fugacity (fCO(2)sw), temperature (SST), salinity (SSS), and discrete investigations of total alkalinity (TA), dissolved inorganic carbon (DIC), bicarbonate (HCO3-), carbonate (CO32-), and saturation state of aragonite (Omega(ara)). The study was conducted during a dry period (July-2019) in the Marine State Park of Pedra da Risca do Meio (PRM), a marine protected area dominated by coral reef communities. Overall, the coral-reef dominated waters presented higher values of fCO(2)sw (475 +/- 28 mu atm), and lower values of pH(T) (7.98 +/- 0.008), CO32- (217 +/- 5 mu mol kg(-1)) and Omega(ara) (3.49 +/- 0.07), compared to nearshore regions without the influence of coral reef waters, where the averages of fCO(2)sw, pH(T), CO32-, and Omega(ara) were, respectively, 458 +/- 21 mu atm, 8.00 +/- 0.007, 224 +/- 4 mu mol kg(-1) , and 3.58 +/- 0.05. The relationship between salinity-normalized TA (nTA) and salinity-normalized DIC (nDIC) showed a slope higher than 1 (1.26) in the coral reef, evidencing the occurrence of calcium carbonate (CaCO3) precipitation and prevalence of inorganic carbon metabolism. The CaCO3 precipitation involves the consumption of TA and DIC in a ratio 2:1, with production of CO2. This mechanism explains the higher values of fCO(2)sw in the coral reef-dominated waters. The values of fCO(2)sw were always higher than the atmospheric values (fCO(2)air), indicating a permanent source of CO2 in the study area during the sampled period. The calculated fluxes of CO2 at the air-sea interface averaged 8.4 +/- 6.5 mmolC m(-2) d(-1) in the coral reef-dominated waters, and these data are higher than those verified in nearshore and offshore locations. These higher emissions of CO2 in coral reef-dominated waters evidence that the carbon budgets calculated for North and Northeastern continental shelf of Brazil must include these environments taking into account the widespread coral reef coverage in the region. This study also confirms that biogeochemical processes occurring in coral reefs are modifying the seawater carbonate chemistry, with implication in the context of the current process of ocean acidification.