CaCO3 dissolution in carbonate-poor shelf sands increases with ocean acidification and porewater residence time

Abstract

Carbonate-poor sandy sediments comprise much of the shelf area, and—despite their low CaCO3 content—contain a significant pool of CaCO3 base available to neutralize ocean acid. Here, we conducted flow-through column experiments on permeable, carbonate-poor sand obtained from Catalina Island, CA, to quantify CaCO3 dissolution across a range of current and future seawater conditions. Using 13C isotope mass balance, we show that dissolution depends both on the CaCO3 saturation state (Ω) of the inflowing seawater, as well as porewater residence time. At current ocean conditions (Ωaragonite = 2.4 and Ωcalcite = 3.7 at our field site), dissolution was negligible for porewater residence times < 1.8 h, but increased thereafter, following sufficient production of CO2 from aerobic respiration. As Ω of inlet water was lowered, simulating future ocean conditions, dissolution began earlier and rates increased. The response to acidification was similar to previously reported observations in carbonate-rich shelf environments, suggesting that carbonate-poor sediments have the potential to support enhanced dissolution in an acidifying ocean, given sufficient CaCO3 substrate. With continued acidification projected to occur this century, these sediments could transition from a net source of acid to the overlying seawater (production of alkalinity to dissolved inorganic carbon, ΔAlk/ΔDIC < 1) to net source of buffering capacity (ΔAlk/ΔDIC > 1) when overlying seawater Ωaragonite reaches 0.96 to 0.69 (Ωcalcite = 1.50 and 1.07), depending on porewater residence time. In some areas with naturally acidic water, this threshold has already been reached.