Abstract

An instrument was developed for the measurement of gaseous ammonia concentration, NH(3(sw,eq)), in equilibrium with surface waters, notably ocean water. The instrument measures the ammonia flux from a flowing water surface under defined conditions and allows the calculation of NH(3(sw,eq)) from the principles of Fickian diffusion. The flux collector resembles a wetted parallel plate denuder previously developed for air sampling. The sample under study runs on one plate of the device; the ammonia released from the sample is collected by a slow flow of a receptor liquid on the other plate. The NH(3) + NH(4)(+) (hereinafter called N(T)) in the effluent receptor liquid is preconcentrated on a silica gel column and subsequently measured by a fluorometric flow injection analysis (FIA) system. With a 6-min cycle (4-min load, 2-min inject), the analytical system can measure down to 0.3 nM N(T) in the receptor liquid. Coupled with the flux collector, it is sufficiently sensitive to measure the ammonia flux from seawater. The instrument design is such that it is little affected by ambient ammonia. In both laboratory (N(T) 0.2-50 μM), and field investigations (N(T) 0.18-1.7 μM) good linearity between the ammonia flux and the N(T) concentration in seawater (spiked, synthetic, natural) was observed, although aged seawater, with depleted N(T) content, behaves in an unusual fashion upon N(T) addition, showing the existence of an "ammonia demand". NH(3(sw,eq)) levels from ocean water measured in the Coconut Island Laboratory, HI, ranged from 6.6 to 33 nmol/m(3) with an average of 17.4 ± 6.9 nmol/m(3), in comparison to 2.8-21 nmol/m(3) (average 10 ± 7 nmol/m(3)) NH(3(sw,eq)) values previously reported for the Central Pacific Ocean (Quinn, P. K.; et al. J. Geophys. Res. 1990, 95, 16405-16416).

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