Stomatal uptake of O3 in aspen and aspen-birch forests under free-air CO2 and O3 enrichment

Rising atmospheric carbon dioxide (CO₂) may alleviate the toxicological impacts of concurrently rising tropospheric ozone (O₃) during the present century if higher CO₂ is accompanied by lower stomatal conductance (g_s), as assumed by many models. We investigated how elevated concentrations of CO₂ and O₃, alone and in combination, affected the accumulated stomatal flux of O₃ (AFst) by canopies and sun leaves in closed aspen and aspen-birch forests in the free-air CO₂-O₃ enrichment experiment near Rhinelander, Wisconsin. Stomatal conductance for O₃ was derived from sap flux data and AFst was estimated either neglecting or accounting for the potential influence of non-stomatal leaf surface O₃ deposition. Leaf-level AFst (AFst_l) was not reduced by elevated CO₂. Instead, there was a significant CO₂ × O₃ interaction on AFst_l, as a consequence of lower values of g_s in control plots and the combination treatment than in the two single-gas treatments. In addition, aspen leaves had higher AFst_l than birch leaves, and estimates of AFst_l were not very sensitive to non-stomatal leaf surface O₃ deposition. Our results suggest that model projections of large CO₂-induced reductions in g_s alleviating the adverse effect of rising tropospheric O₃ may not be reasonable for northern hardwood forests.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Gene expression responses of paper birch (Betula papyrifera) to elevated CO2 and O3 during leaf maturation and senescence

Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO₂ and O₃ were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O₃, alone or in combination with CO₂. O₃ induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO₂ reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO₂ + O₃ treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O₃ treatment, indicating that CO₂ cannot totally alleviate the harmful effects of O₃.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Diurnal changes in photosynthetic parameters of Populus tremuloides, modulated by elevated concentrations of CO2 and/or O3 and daily climatic variation

The diurnal changes in light-saturated photosynthesis (Pn) under elevated CO₂ and/or O₃ in relation to stomatal conductance (g_s), water potential, intercellular [CO₂], leaf temperature and vapour-pressure difference between leaf and air (VPD_L) were studied at the Aspen FACE site. Two aspen (Populus tremuloides Michx.) clones differing in their sensitivity to ozone were measured. The depression in Pn was found after 10:00 h. The midday decline in Pn corresponded with both decreased g_s and decreased Rubisco carboxylation efficiency, Vc_max. As a result of increasing VPD_L, g_s decreased. Elevated [CO₂] resulted in more pronounced midday decline in Pn compared to ambient concentrations. Moreover, this decline was more pronounced under combined treatment compared to elevated CO₂ treatment.The positive impact of CO₂ on Pn was relatively more pronounced in days with environmental stress but relatively less pronounced during midday depression. The negative impact of ozone tended to decrease in both cases.     

An integrated tool to assess the role of new planting in PM10 capture and the human health benefits: A case study in London

The role of vegetation in mitigating the effects of PM₁₀ pollution has been highlighted as one potential benefit of urban greenspace. An integrated modelling approach is presented which utilises air dispersion (ADMS-Urban) and particulate interception (UFORE) to predict the PM₁₀ concentrations both before and after greenspace establishment, using a 10 × 10 km area of East London Green Grid (ELGG) as a case study. The corresponding health benefits, in terms of premature mortality and respiratory hospital admissions, as a result of the reduced exposure of the local population are also modelled. PM₁₀ capture from the scenario comprising 75% grassland, 20% sycamore maple (Acer pseudoplatanus L.) and 5% Douglas fir (Pseudotsuga menziesii (Mirb.) Franco) was estimated to be 90.41 t yr⁻¹, equating to 0.009 t ha⁻¹ yr⁻¹ over the whole study area. The human health modelling estimated that 2 deaths and 2 hospital admissions would be averted per year.