Tropospheric ozone reduces carbon assimilation in trees: estimates from analysis of continuous flux measurements.

High ground-level ozone concentrations are typical of Mediterranean climates. Plant exposure to this oxidant is known to reduce carbon assimilation. Ozone damage has been traditionally measured through manipulative experiments that do not consider long-term exposure and propagate large uncertainty by up-scaling leaf-level observations to ecosystem-level interpretations. We analyzed long-term continuous measurements (>9 site-years at 30 min resolution) of environmental and eco-physiological parameters at three Mediterranean ecosystems: (i) forest site dominated by Pinus ponderosa in the Sierra Mountains in California, USA; (ii) forest site composed of a mixture of Quercus spp. and P. pinea in the Tyrrhenian sea coast near Rome, Italy; and (iii) orchard site of Citrus sinensis cultivated in the California Central Valley, USA. We hypothesized that higher levels of ozone concentration in the atmosphere result in a decrease in carbon assimilation by trees under field conditions. This hypothesis was tested using time series analysis such as wavelet coherence and spectral Granger causality, and complemented with multivariate linear and nonlinear statistical analyses. We found that reduction in carbon assimilation was more related to stomatal ozone deposition than to ozone concentration. The negative effects of ozone occurred within a day of exposure/uptake. Decoupling between carbon assimilation and stomatal aperture increased with the amount of ozone pollution. Up to 12-19% of the carbon assimilation reduction in P. ponderosa and in the Citrus plantation was explained by higher stomatal ozone deposition. In contrast, the Italian site did not show reductions in gross primary productivity either by ozone concentration or stomatal ozone deposition, mainly due to the lower ozone concentrations in the periurban site over the shorter period of investigation. These results highlight the importance of plant adaptation/sensitivity under field conditions, and the importance of continuous long-term measurements to explain ozone damage to real-world forests and calculate metrics for ozone-risk assessment.

Ozone deposition to an orange orchard: Partitioning between stomatal and non-stomatal sinks.

Orange trees are widely cultivated in regions with high concentrations of tropospheric ozone. Citrus absorb ozone through their stomata and emit volatile organic compounds (VOC), which, together with soil emissions of NO, contribute to non-stomatal ozone removal. In a Valencia orange orchard in Exeter, California, we used fast sensors and eddy covariance to characterize water and ozone fluxes. We also measured meteorological parameters necessary to model other important sinks of ozone deposition. We present changes in magnitude of these ozone deposition sinks over the year in response to environmental parameters. Within the plant canopy, the orchard constitutes a sink for ozone, with non-stomatal ozone deposition larger than stomatal uptake. In particular, soil deposition and reactions between ozone, VOC and NO represented the major sinks of ozone. This research aims to help the development of metrics for ozone-risk assessment and advance our understanding of citrus in biosphere-atmosphere exchange.

Sesquiterpenoid emissions from agricultural crops: correlations to monoterpenoid emissions and leaf terpene content.

Emissions of biogenic volatile organic compounds (BVOCs) are important precursors to both ozone and secondary organic aerosol formation. In this study, we identify and quantify volatile (C(10)) and intermediate-volatility (C(15)) BVOCs stored in and emitted from 22 prominent woody and herbaceous crops with a particular focus on sesquiterpenoids (SQTs), which have presented measurement challenges in previous studies. Monoterpenoids (MNTs) and SQTs were simultaneously emitted from all the crops studied; there were significant correlations between emission rates and leaf content for both MNTs and SQTs and additional correlations between MNTs and SQTs in both emissions and leaf content. Our results suggest that species with high concentrations of stored terpenoids in their leaves, such as those grown commercially for their essential oil content, are likely high BVOC emitters. Emissions from agricultural species were dominated by SQTs at low MNT emission rates (on the order of several tens of ng/(g(DM)*h)), while at higher MNT levels (on the order of several hundreds of ng/(g(DM)*h)), SQT emissions were approximately equivalent. Based on our empirical correlations, we estimate that global SQT emissions are similar to MNT emissions and on the order of 100 Tg yr(-1), which justifies the need for better representation of SQTs in both BVOC emission and atmospheric models.