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An inter-comparison of techniques for long-term sampling of atmospheric ammonia (NH3) was conducted with a view to establishing a national network with >50 sites. Key requirements were for: a low cost system, simplicity and durability to enable a postal exchange with local site operators, a precision of <±20% for monthly sampling at expected NH3 concentrations of 1–2 µg m–3, a detection limit sufficient to resolve the small NH3 concentrations (<0.2 µg m–3) expected in remote parts of the UK, and a quantitative means to establish quality control. Five sampling methods were compared: A, a commercially available membrane diffusion tube (exposed in triplicate), with membranes removed immediately after sampling; B, the above method, with the membranes left in place until analysis; C, open-ended diffusion tubes (exposed with 4 replicates); D, a new active sampling diffusion denuder system; and E, an active sampling bubbler system. Method D consisted of two 0.1 m acid coated glass denuders in series with sampling at 0.3 l min–1. These methods were deployed at 6 locations in the UK and the Netherlands and compared against reference estimates. Method D was the most precise and sensitive of the techniques compared, with a detection limit of <0.1 µg m–3. The bubbler provided a less precise estimate of NH3 concentration, and also suffered several practical drawbacks. The diffusion tubes were found to correlate with the reference at high concentrations (>3 µg m–3), but were less precise and overestimated NH3 at smaller concentrations. Of the passive methods, A was the most precise and C the least precise. On the basis of the results, method D has been implemented in the national network, together with application of method A to explore spatial variability in regions with expected high NH3 concentrations.

Fluxes of NO, NO2 and O3 were determined over a drained marshland pasture in south-east England by using flux-gradient techniques. Nitric oxide was found to be emitted at rates of up to 40 ng m−2 s−1, the rate of emission being related to the magnitude of the eddy diffusivity. Nitrogen dioxide deposited at rates of up to 90 ng m−2 s−1 under the control of stomatal resistance, a clear diurnal cycle being observed. Minimum canopy resistance was of the order of 80 s m−1. Ozone deposition was also controlled by stomatal resistance, the minimum canopy resistance being around 100 s m−1 and fluxes reaching a maximum of 220 ng m−2 s−1. Corrections made to NO and NO2 fluxes to compensate for chemical reactions showed flux divergences of the order of 30% for NO and NO2, but these were not statistically significantly different from the measured fluxes. The pasture was found to be a net sink for nitrogen in the form of NOx.