An automated technique for measuring δD and δ18O values of porewater by direct CO2 and H2 equilibration

The stable-oxygen and -hydrogen isotopic values (deltaD, delta O-18) of porewater in geologic media are commonly determined on water obtained by extraction techniques such as centrifugation, mechanical squeezing, vacuum heating and cryogenic microdistillation, and azeotropic distillation. Each of these techniques may cause isotopic fractionation as part the extraction process and each is laborious. Here we demonstrate a new approach to obtain automated, high-precision deltaD and delta O-18 measurements of porewater in geologic sediments by direct H-2- and CO2-porewater equilibration using a modified commercial CO2-water equilibrator. This technique provides an important and cost-effective improvement over current extraction methods, because many samples can be rapidly analyzed with minimal handling, thereby reducing errors and potential for isotopic fractionation. The precision and accuracy of direct H-2- and CO2-porewater equilibration is comparable to or better than current porewater extraction methods. Finally, the direct equilibration technique allows investigators to obtain high-resolution (cm scale) porewater deltaD and delta O-18 profiles using cores from individual boreholes, eliminating the need for costly piezometers or conventional porewater extractions.