Samples were collected aboard the R/V Knorr using its long coring system in November of 2014 on cruise KN-223 in the North Atlantic. Samples used in this study came from two sediment coring sites located within 90m of each other at 50°37.25’W, 14°24.05’N, and 4455 m water depth. Porewaters were extracted at approximately 0.5m intervals from two long piston cores (30 and 34 m long) using Rhizon samplers (0.2 mm pore size) and either analyzed shipboard or frozen until analyses were conducted shore side.
Nitrate and nitrite concentrations were determined shipboard using ion chromatography with UV detection (D’Hondt et al., 2015). Isotopes were measured in the Wankel lab (Woods Hole Oceanographic Institution) using an Isoprime 100 isotope ratio mass spectrometer coupled to a modified TraceGas prep system similar to that described previously (McIlvin and Casciotti, 2011), which is used to flush, purify and cryogenically trap sample N2O from converted nitrate or nitrite samples. Nitrate isotopic composition was measured using the denitrifier method to convert nitrate to N2O, normalized to international reference materials (USGS 34, USGS 32, and USGS 35) (Sigman et al., 2001; Casciotti et al., 2002). Nitrite isotope measurements were made separately using the azide method for conversion of nitrite to N2O (McIlvin and Altabet, 2005), normalizing to previously calibrated Wankel isotope lab standards (WILIS 10, 11, and 20) (Buchwald et al., 2016). Where co-occurring nitrite concentrations were less than 5 times as high as nitrate, nitrite was removed by addition of sulfamic acid (Granger and Sigman, 2009) prior to the denitrifier method. In the deepest samples having measurable nitrate, where concentrations were very low, the N and O isotopic composition of nitrate was calculated by mass balance using analyses of the combined nitrate + nitrite pools by the denitrifier method, in which both nitrate and nitrite standards were also analyzed, together with nitrite isotope values from the azide-only measurements described previously (Casciotti and McIlvin, 2007).
