δ44/40Ca variability in shallow water carbonates and the impact of submarine groundwater discharge on Ca-cycling in marine environments

In the innermost water circulation restricted region of northeastern Florida Bay, sediments and waters exhibit a 0.7‰ gradient in δ44/40Ca values decreasing towards the Florida Everglades. This lowering of δ44/40Ca is predominantly caused by local-scale Ca-inputs from SGD, which has a high Ca concentration (450 mg/L) and low δ44/40Ca value (−0.96‰). Mixing calculations show that Ca inputs from SGD and surface water runoff from the Florida Everglades contribute between 8% and 60% of the dissolved Ca to the studied waters with salinities between 30 and 14, respectively. Similar degrees of circulation restriction between epeiric seas and oceans in the geological past may have also led to overprinting of sedimentary carbonate δ44/40Ca values in nearshore regions of epeiric seas due to local-scale cycling of seawater through coastal carbonate aquifers. Local Ca-cycling effects may explain some of the scatter in δ44/40Ca values present in the Ca-isotope evolution curve of Phanerozoic oceans.