Determination of in situ dissolved inorganic carbon concentration and alkalinity for marine sedimentary porewater

• Porewater sampling associated CaCO3 precipitation alters the in-situ chemistry.
• We develop a method that corrects for sample recovery and handling artifacts.
• The method accounts for precipitation of CaCO3 during sediment recovery.
• The method enables quantification of in situ carbonate chemistry.
• The method is applicable to approximately 50% of the global oceanic seafloor.

Dissolved inorganic carbon (DIC) concentration and total alkalinity in marine sediment vary with biological activity, mineral diagenesis and past bottom ocean water composition. Reliable interpretation of this data is often compromised due to precipitation of calcium carbonate (CaCO3) during sediment recovery, processing and sample storage.Here we present and test a method that corrects for this precipitation and consequently allows quantification of in situ carbonate system chemistry. Our method relies on the over-determination of the dissolved carbonate system by (i) measuring DIC, alkalinity and calcium, and (ii) explicitly assuming CaCO3 saturation in the sediment. We experimentally tested this method using data from Integrated Ocean Drilling Program (IODP) Site U1368 in the South Pacific Gyre. Our results show that we can accurately reproduce in situ aqueous carbonate system chemistry if DIC, alkalinity and calcium concentration are measured simultaneously. At Site U1368, the correction for sampling associated precipitation is equivalent to 4.5 and 8.9% of the measured DIC and alkalinity, respectively. The method is well suited for any sediment porewater that is saturated with respect to calcium carbonate; consequently, it is applicable for approximately 50% of the global oceanic seafloor.