Ozone deposition impact assessments for forest canopies require accurate ozone flux partitioning on diurnal timescales

Dry deposition is an important sink of tropospheric ozone that affects surface concentrations and impacts crop yields, the land carbon sink, and the terrestrial water cycle. Dry deposition pathways include plant uptake via stomata and non-stomatal removal by soils, leaf surfaces, and chemical reactions. Observational studies indicate that ozone deposition exhibits substantial temporal variability that is not reproduced by atmospheric chemistry models due to a simplified representation of vegetation uptake processes in these models. In this study, we explore the importance of stomatal and non-stomatal uptake processes in driving ozone dry deposition variability on diurnal to seasonal timescales. Specifically, we compare two land surface ozone uptake parameterizations – a commonly applied big leaf parameterization (W89; Wesely, 1989) and a multi-layer model (MLC-CHEM) constrained with observations – to multi-year ozone flux observations at two European measurement sites (Ispra, Italy, and Hyytiälä, Finland). We find that W89 cannot reproduce the diurnal cycle in ozone deposition due to a misrepresentation of stomatal and non-stomatal sinks at our two study sites, while MLC-CHEM accurately reproduces the different sink pathways. Evaluation of non-stomatal uptake further corroborates the previously found important roles of wet leaf uptake in the morning under humid conditions and soil uptake during warm conditions. The misrepresentation of stomatal versus non-stomatal uptake in W89 results in an overestimation of growing season cumulative ozone uptake (CUO), a metric for assessments of vegetation ozone damage, by 18 % (Ispra) and 28 % (Hyytiälä), while MLC-CHEM reproduces CUO within 7 % of the observation-inferred values. Our results indicate the need to accurately describe the partitioning of the ozone atmosphere–biosphere flux over the in-canopy stomatal and non-stomatal loss pathways to provide more confidence in atmospheric chemistry model simulations of surface ozone mixing ratios and deposition fluxes for large-scale vegetation ozone impact assessments.

Ozone deposition impact assessments for forest canopies require accurate ozone flux partitioning on diurnal timescales

Dry deposition is an important sink of tropospheric ozone that affects surface concentrations, and impacts crop yields, the land carbon sink and the terrestrial water cycle. Dry deposition pathways include plant uptake via stomata and nonstomatal removal by soils, leaf surfaces and chemical reactions. Observational studies indicate that ozone deposition exhibits substantial temporal variability that is not reproduced by atmospheric chemistry models due to a simplified representation of vegetation uptake processes in these models. In this study, we explore the importance of stomatal and non-stomatal uptake processes in driving ozone dry deposition variability on diurnal to seasonal timescales. Specifically, we compare two land surface ozone uptake parameterizations – a commonly applied ’big leaf’ parameterization (W89; Wesely, 1989) and a multi-layer model (MLC-CHEM) constrained with observations – to multi-year ozone flux observations at two European measurement sites (Ispra, Italy, and Hyytiälä, Finland). We find that W89 cannot reproduce the diurnal cycle in ozone deposition due to a mis-representation of stomatal and non-stomatal sinks at our two study sites, while MLC-CHEM accurately reproduces the different sink pathways. Evaluation of non-stomatal uptake further corroborates the previously found important roles of wet leaf uptake in the morning under humid conditions, and soil uptake during warm conditions. The misrepresentation of stomatal versus non-stomatal uptake in W89 results in an overestimation of growing-season cumulative ozone uptake (CUO), a metric for assessments of vegetation ozone damage, by 18 % (Ispra) and 28 % (Hyytiälä), while MLC-CHEM reproduces CUO within 7 % of the observation-inferred values. Our results indicate the need to accurately describe the partitioning of the ozone atmosphere-biosphere flux over the in-canopy stomatal and non-stomatal loss pathways to provide more confidence in atmospheric chemistry model simulations of surface ozone mixing ratios and deposition fluxes for large-scale vegetation ozone impact assessments.

Ozone deposition to a coastal sea: comparison of eddy covariance observations with reactive air–sea exchange models

A fast-response (10 Hz) chemiluminescence detector for ozone (O3) was used to determine O3 fluxes using the eddy covariance technique at the Penlee Point Atmospheric Observatory (PPAO) on the south coast of the UK during April and May 2018. The median O3 flux was −0.132 mg m−2 h−1 (0.018 ppbv m s−1), corresponding to a deposition velocity of 0.037 cm s−1 (interquartile range 0.017–0.065 cm s−1) – similar to the higher values previously reported for open-ocean flux measurements but not as high as some other coastal results. We demonstrate that a typical single flux observation was above the 2σ limit of detection but had considerable uncertainty. The median 2σ uncertainty of deposition velocity was 0.031 cm s−1 for each 20 min period, which reduces with the square root of the sample size. Eddy covariance footprint analysis of the site indicates that the flux footprint was predominantly over water (> 96 %), varying with atmospheric stability and, to a lesser extent, with the tide. At very low wind speeds when the atmosphere was typically unstable, the observed ozone deposition velocity was elevated, most likely because the footprint contracted to include a greater land contribution in these conditions. At moderate to high wind speeds when atmospheric stability was near-neutral, the ozone deposition velocity increased with wind speed and showed a linear dependence with friction velocity. This observed dependence on friction velocity (and therefore also wind speed) is consistent with the predictions from the one-layer model of Fairall et al. (2007), which parameterises the oceanic deposition of ozone from the fundamental conservation equation, accounting for both ocean turbulence and near-surface chemical destruction, while assuming that chemical O3 destruction by iodide is distributed over depth. In contrast to our observations, the deposition velocity predicted by the recently developed two-layer model of Luhar et al. (2018) (which considers iodide reactivity in both layers but with molecular diffusivity dominating over turbulent diffusivity in the first layer) shows no major dependence of deposition velocity on wind speed and underestimates the measured deposition velocities. These results call for further investigation into the mechanisms and control of oceanic O3 deposition.

Ozone Deposition on Free-Running Indoor Materials and the Corresponding Volatile Organic Compound Emissions: Implications for Ventilation Requirements

Recently, tropospheric ozone has become a public health concern worldwide, along with the continuous battle against ambient fine particulate matter in countries like China. In this study, we investigate the impact of indoor ozone pollution using seven materials categorized as either wood-based panels or synthetic fibers, which were freely-stored in an office/lab environment. Most materials were considered as used and aged more than 1–2 years. An experimental apparatus was used to study ozone deposition and detect volatile organic compound (VOC) emissions from the specimens when exposed to ozone at three concentration levels: <10, 100, and 300 ppb. A simplified model is proposed to discuss ventilation requirements based on a standard room. We found that the mean ozone deposition velocities from the seven materials ranged from 0.005 to 0.062 cm·s−1. Both the engineering wood and some of the synthetic fibers were, moreover, prone to ozone deposition. Second, 15 VOCs were found in the sampling air from a 24-VOC target list after ozone exposure. The emission rates of the VOCs from all seven materials were then determined. Third, when the ozone concentration in the outdoor air is not severely high, it is possible to use ventilation to maintain acceptable indoor air quality.