Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation

Dissolved inorganic nitrogen, largely in reduced form (NH₄(T)≈NH_4(aq)⁺+NH_3(aq)^o), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH₄(T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH₄(T) concentration and δ¹⁸O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH₄(T) and other solutes in some areas. The isotopic composition of dissolved NH₄(T) is highly variable (δ¹⁵N = −6‰ to +30‰) and is positively correlated with pH values. In comparison to likely δ¹⁵N values of nitrogen source materials (+1‰ to +7‰), high δ¹⁵N values in hot springs with pH >5 are attributed to isotope fractionation associated with NH_3(aq)^o loss by volatilization. NH₄(T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative δ¹⁵N values that are attributed to NH_3(g)^o condensation. NH₄(T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH₄(T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.