Review: geological and experimental evidence for secular variation in seawater Mg/Ca (calcite-aragonite seas) and its effects on marine biological calcification

Abstract. Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO₃ precipitates (ooids, marine cements) throughout Phanerozoic time are believed to have been caused by tectonically induced variations in the Mg/Ca ratio of seawater (molar Mg/Ca>2="aragonite seas", <2="calcite seas"). Here, I assess the geological evidence in support of secular variation in seawater Mg/Ca and its effects on marine calcifiers, and review a series of recent experiments that investigate the effects of seawater Mg/Ca (1.0–5.2) on extant representatives of calcifying taxa that have experienced variations in this ionic ratio of seawater throughout the geologic past.

Secular variation in seawater Mg/Ca is supported by synchronized secular variations in (1) the ionic composition of fluid inclusions in primary marine halite, (2) the mineralogies of late stage marine evaporites, abiogenic carbonates, and reef- and sediment-forming marine calcifiers, (3) the Mg/Ca ratios of fossil echinoderms, molluscs, rugose corals, and abiogenic carbonates, (4) global rates of tectonism that drive the exchange of Mg²⁺ and Ca²⁺ along zones of ocean crust production, and (5) additional proxies of seawater Mg/Ca including Sr/Mg ratios of abiogenic carbonates, Sr/Ca ratios of biogenic carbonates, and Br concentrations in marine halite.

Laboratory experiments have revealed that aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibit higher rates of calcification and growth in experimental seawaters formulated with seawater Mg/Ca ratios that favor their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary production increased along with calcification within the bryopsidalean and coccolithophorid algae in mineralogically favorable seawater is consistent with the hypothesis that calcification promotes photosynthesis within some species of these algae through the liberation of CO₂.

The experiments also revealed that aragonite-secreting bryopsidalean algae and scleractinian corals, and bacterial biofilms that secrete a mixture of aragonite and high Mg calcite, began secreting an increased proportion of their calcium carbonate as the calcite polymorph in the lower-Mg/Ca experimental seawaters. Furthermore, the Mg/Ca ratio of calcite secreted by the coccolithophores, coralline red algae, reef-dwelling animals (crustacea, urchins, calcareous tube worms), bacterial biofilms, scleractinian corals, and bryopsidalean algae declined with reductions in seawater Mg/Ca. Notably, Mg fractionation in autotrophic organisms was more strongly influenced by changes in seawater Mg/Ca than in heterotrophic organisms, a probable consequence of autotrophic organisms inducing a less controlled mode of calcification simply through the removal of CO₂ via photosynthesis.

These results indicate that biomineralogical control can be partially overridden by ambient seawater Mg/Ca and suggest that modern aragonite-secreting organisms may have secreted a mixture of aragonite and low Mg calcite, and that modern high Mg calcite-secreting organisms probably secreted low Mg calcite, in calcite seas of the past. These effects of seawater Mg/Ca on the polymorph mineralogy and calcite Mg/Ca ratio of calcareous skeletons should be accounted for in thermal-chemical reconstructions of seawater that are based upon skeletal Mg/Ca.

Lastly, by identifying how marine calcifiers respond to changes in seawater Mg/Ca and absolute Ca²⁺ concentration, this work should enhance our interpretation of parallel studies investigating the effects of anthropogenic CO₂-induced ocean acidification on marine calcification.