Temperature profiling: Temperature profiles at the sampling site were recorded using Alvin’s external heatflow temperature probe, a 0.6 m titanium tube containing a linear heater and five thermistors (type 44032, Omega Engineering, Inc.) at 10 cm intervals along the length of the tube (McKay et al., 2012). When fully immersed in the sediment, this probe records five in-situ temperatures at the sediment/water interface, and at 10, 20, 30 and 40 cm sediment depth.

Geochemical Analyses: Sulfate concentration measurements were completed shipboard; after centrifuging sediment-filled 15 ml tubes, the overlying porewater was filtered through 0.45 um filters, acidified with 50 ul of 50% HCl and bubbled with nitrogen for 4 minutes to remove sulfide. Sulfate concentrations were then measured shipboard using a 2010i Dionex Ion Chromatograph (Sunnyvale, CA, USA) through Ag exchange columns (Dionex) so as to remove Cl (Martens et al., 1999). For sulfide, 1 ml porewater samples were combined with 0.1M zinc acetate and concentrations were analyzed spectrophotometrically on the ship (Cline 1969).

Headspace methane concentrations were determined onboard by standard gas chromatography with a flame ionization detector (FID), specifically using a HACH Carle Series 100 AGC Gas Chromatograph with a Alltech Molecular Sieve 5A packed column (80/100 mesh, 3.05 m length, 3.2 mm ID) and a 80 degree C isothermal temperature profile. Stable isotopic compositions of the same methane samples (core 4484-3) were measured post-cruise at UNC via gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) on a Finnigan MAT 252 Isotope Ratio Mass Spectrometer, using a HP 5890 Series II Gas Chromatograph with a HP Plot Q column (30 m length, 0.32 mm ID, 20 um film thickness) and a 30 degree C isothermal temperature profile. To measure DIC, 2 ml of unamended porewater from each sediment horizon were injected into evacuated serum vials (30 ml) and stored upside down at -20 degrees C. At UNC, the samples were thawed, and DIC was reacted to gaseous CO2 by adding 1 ml of a 30% phosphoric acid solution to each serum vial and shaking vigorously before GC analysis (Kelley et al., 1990). Stable isotopic values and concentrations of DIC were analyzed via coupled GC (Hewlett Packard 5890) and Isotope Ratio Mass Spectrometer (Finnigan MAT 252).

porewater_geochemistry.csv