Using ammonium pore water profiles to assess stoichiometry of deep remineralization processes in methanogenic continental margin sediments

Abstract

AbstractIn many continental margin sediments, a deep reaction zone exists which is separated from remineralization processes near the sediment surface. Here, methane diffuses upward to a depth where it is oxidized by downwardly diffusing sulfate. However, the methane sources that drive this anaerobic oxidation of methane (AOM) in the sulfate‐methane transition zone (SMT) may vary among sites. In particular, these sources can be thought of as either (i) “internal” sources from in situ methanogenesis (regardless of where it occurs in the sediment column) that are ultimately coupled to organic matter deposition and burial, or (ii) “external” sources such as hydrocarbon reservoirs derived from ancient source rocks, or deeply buried gas hydrates, both of which are decoupled from contemporaneous organic carbon deposition at the sediment surface. Using a modeling approach, we examine the relationship between different methane sources and pore water sulfate, methane, dissolved inorganic carbon (DIC), and ammonium profiles. We show that pore water ammonium profiles through the SMT represent an independent “tracer” of remineralization processes occurring in deep sediments that complement information obtained from profiles of solutes directly associated with AOM and carbonate precipitation, i.e., DIC, methane, and sulfate. Pore water DIC profiles also show an inflection point in the SMT based on the type of deep methane source and the presence/absence of accompanying upward DIC fluxes. With these results, we present a conceptual framework which illustrates how shallow pore water profiles from continental margin settings can be used to obtain important information about remineralization processes and methane sources in deep sediments.