Foliage surface ozone deposition: a role for surface moisture?

Abstract. This paper addresses the potential role of surface wetness in ozone deposition to plant foliage. We studied Scots pine foliage in field conditions at the SMEARII field measurement station in Finland. We used a combination of data from flux measurement at the shoot (enclosure) and canopy scale (eddy covariance), information from foliage surface wetness sensors, and a broad array of ancillary measurements such as radiation, precipitation, temperature, and relative humidity. Environmental conditions were defined as moist during rain or high relative humidity and during the subsequent twelve hours from such events, circumstances that were frequent at this boreal site. From the measured fluxes we estimated the ozone conductance using it as the expression of the strength of ozone removal surface sink or total deposition. Further, we estimated the stomatal contribution and the remaining deposition was interpreted and analysed as the non-stomatal sink.

The combined time series of measurements showed that both shoot and canopy-scale ozone total deposition were enhanced when moist conditions occurred. On average, the estimated stomatal deposition accounted for half of the measured removal at the shoot scale and one third at the canopy scale. However, during dry conditions the estimated stomatal uptake predicted the behaviour of the measured deposition, but during moist conditions there was disagreement. The estimated non-stomatal sink was analysed against several environmental factors and the clearest connection was found with ambient relative humidity. The relationship disappeared under 70% relative humidity, a threshold that coincides with the value at which surface moisture gathers at the foliage surface according to the leaf surface wetness measurements. This suggests the non-stomatal ozone sink on the foliage to be modulated by the surface films. We attempted to extract such potential modulation with the estimated film formation via the theoretical expression of adsorption. Whereas this procedure could predict the behaviour of the non-stomatal sink, it implied a chemical sink that was not accountable as simple ozone decomposition. We discuss the existence of other mechanisms whose relevance in the removal of ozone needs to be clarified, in particular: a significant nocturnal stomatal aperture neglected in the estimations, and a potentially large chemical sink offered by reactive biogenic organic volatile compounds.