Review: the effects of secular variation in seawater Mg/Ca on marine biocalcification

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 is believed to have been caused by tectonically-induced variations in seawater molar Mg/Ca (>2="aragonite seas"; <2="calcite seas"). Here, I review a series of experiments in which extant calcifying taxa were reared in experimental seawater formulated over the range of mMg/Ca ratios (1.0 to 5.2) that occurred throughout their geologic history. Aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibited higher rates of calcification and growth in the experimental seawaters that favored 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 in mineralogically-favorable seawater is consistent with the hypothesis that calcification promotes photosynthesis within autotrophs through the liberation of CO2. The Mg/Ca ratio of calcite secreted by the coccolithophores, coralline algae and reef-dwelling animals (crustacea, urchins, calcareous tube worms) declined with reductions in seawater Mg/Ca. Calcifying microbial biofilms varied their mineral polymorph with seawater Mg/Ca (mMg/Ca<2=low Mg calc; mMg/Ca>2=arag+high Mg calc), suggesting a nearly abiotic mode of calcification. These results indicate that biomineralogical control can be partially overridden by ambient seawater Mg/Ca and suggests that modern high Mg calcite organisms probably secreted low Mg calcite in calcite seas of the past. Notably, Mg fractionation in autotrophic organisms was more strongly influenced by changes in seawater Mg/Ca, a probable consequence of them inducing a less controlled mode of calcification simply through the removal of CO2 via photosynthesis. This body of work also has implications for thermal-chemical reconstructions of seawater that are based upon skeletal Mg/Ca. And by identifying how marine calcifiers respond to changes in seawater Mg/Ca and absolute Ca2+ concentration, this work should enhance our interpretation of the parallel studies investigating the effects of CO2-induced ocean acidification on marine calcification.