Dynamic-chemical coupling of the upper troposphere and lower stratosphere region

The importance of the interaction between chemistry and dynamics in the upper troposphere and lower stratosphere for chemical species like ozone is investigated using two chemistry-climate models and a Lagrangian trajectory model. Air parcels from the upper troposphere, i.e. regions of lightning and aircraft emissions, are able to be transported into the lowermost stratosphere (LMS). Trajectory calculations suggest that the main transport pathway runs via the inter tropical convergence zone, across the tropical tropopause and then to higher latitudes, i.e. into the LMS. NOx from aircraft emissions at mid-latitudes are unlikely to perturb the LMS since they are washed-out while still in the troposphere. In contrast, NOx from tropical lightning has the chance to accumulate in the LMS. Because of the longer residence times of NOx in the LMS, compared to the upper troposphere, this excess NOx from lightning has the potential to form ozone in the LMS, which then is transported back to the troposphere at mid-latitudes. In the models, around 10% of the ozone concentration and 50% of the NOx concentration in the northern hemisphere LMS is produced by lightning NOx At least 5% of the ozone concentration and 35% the NOx concentration at 150 hPa at mid-latitudes originates from tropical lightning in the climate-chemistry simulations.     

The reciprocal relation between lightning and pollution and their impact over Kolkata, India

Aerosol loading in the atmosphere can cause increased lightning flashes, and those lightning flashes produce NO _X , which reacts in sun light to produce surface ozone. The present study deals with the effect of surface pollutants on premonsoon (April–May) lightning activity over the station Kolkata (22.65° N, 88.45° E). Seven-year (2004–2010) premonsoon thunderstorms data are taken for the study. Different parameters like aerosol optical depth and cloud top temperature from the Moderate Resolution Imaging Spectroradiometer satellite products along with lightning flash data from Tropical Rainfall Measuring Mission’s (TRMM) Lightning Imaging Sensor are analyzed. Some surface pollution parameters like suspended particulate matter, particulate matter 10, nitrogen oxides (NO _X ), and surface ozone (O₃) data during the same period are taken account for clear understanding of their association with lightning activity. Heights of convective condensation level and lifting condensation level are collected from radiosonde observations to anticipate about cloud base. It is found that increased surface pollution in a near storm environment is related to increased lightning flash rate, which results in increased surface NO _X and consequently increased surface ozone concentration over the station Kolkata.     

Analysis of carbon monoxide budget in North China

A global chemical transport model (MOZART-2; model of ozone and related tracers, version 2) was used to assess physical and chemical processes that control the budget of tropospheric carbon monoxide (CO) in North China. Satellite observations of CO from the measurements of pollution in the troposphere (MOPITT) instrument are combined with model results for the analysis. The comparison between the model simulations and the satellite observations of total column CO (TCO) shows that the model can reproduce the spatial and temporal distributions. However, the model results underestimate TCO by 23% in North China. This underestimation of TCO may be caused by the uncertainties of emissions. The tropospheric CO budget analysis suggests that in North China, surface emission is the largest source of tropospheric CO. The main sinks of tropospheric CO in this region are chemical reaction and stratosphere_and_troposphere exchange. The analysis also shows that most of inflow CO to Pacific regions comes from the upwind regions of North China. This transport of CO is significant during Winter and Spring time.     

Ozone dynamics and deposition processes at a deforested site in the Amazon basin

The goal of this study is to investigate the impact of deforestation on ozone dynamics and deposition in the Brazilian Amazon basin. This goal is accomplished through i) analyses of ozone levels and deposition rates at a deforested site during the rainy season; and ii) comparisons of these data with similar information derived at a forest. At the pasture site maximum ozone mixing ratios reach 20 parts per billion on a volume basis (ppbv) but about 6 ppbv prevail over the forest. Maximum ozone deposition velocities for pastures can reach 0.7 cm s-1, which is about threefold lower than values derived for forests. Combining ozone abundance and deposition velocities, pasture maximum ozone fluxes reach approximately 0.2 microgram (ozone) m-2 s-1. This flux represents approximately 70% of the deposition rates measured over the forest. Hence, this study suggests that conversion of rainforests to pastures could lead to a net reduction (30%) in the ozone sink in the Amazon.     

Ozonation of Procaine Penicillin G formulation effluent Part I: Process optimization and kinetics

Ozonation characteristics of synthetic Procaine Penicillin G (PPG) formulation effluent were investigated in a semi-batch ozone reactor at different pH (3, 7 and 12), ozone feed rates (600-2600 mg h-1) and COD values (200-600 mg l-1). Ozonation of aqueous PPG effluent resulted in 37 (82)% COD removal after 60 (120) min ozonation when the reaction pH was kept constant at pH=7.900 mg l-1 (corresponding to 50% of the total introduced) ozone was absorbed during a reaction period of 1 h. The effects of increasing the applied ozone dose and the initial COD on the COD abatement rates of PPG effluent were also studied. Results have indicated that increasing the ozone dose and decreasing the COD content both have positive effects on COD removal rates. The significant contribution of the free radical (.OH) reaction pathway to PPG ozonation could be traced using tert-butyl alcohol as the .OH probe compound at varying concentrations. The bimolecular reaction rate constants for the direct reaction of PPG with ozone were found as 152 and 2404 M-1 h-1 at pH=3 and 7, respectively, using the gas phase ozone partial pressures determined from of the outlet gas stream analysis. It could be demonstrated that ozone decomposition to free radicals being triggered by increasing the pH from 3 to 7 is essential for the rate enhancement of PPG effluent ozonation.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

The distinctive isotopic signature of plant-derived chloromethane: possible application in constraining the atmospheric chloromethane budget

Chloromethane (CH(3)Cl) is the most abundant halocarbon in the atmosphere. Although largely of natural origin it is responsible for around 17% of chlorine-catalysed ozone destruction. Sources identified to date include biomass burning, oceanic emissions, wood-rotting fungi, higher plants and most recently tropical ferns. Current estimates reveal a shortfall of around 2 million ty(-1) in sources versus sinks for the halocarbon. It is possible that emissions from green plants have been substantially underestimated. A potentially valuable tool for validating emission flux estimates is comparison of the delta13C value of atmospheric CH(3)Cl with those of CH(3)Cl from the various sources. Here we report delta13C values for CH(3)Cl released by two species of tropical ferns and show that the isotopic signature of CH(3)Cl from pteridophytes like that of CH(3)Cl from higher plants is quite different from that of CH(3)Cl produced by biomass burning, fungi and industry. delta13C values for CH(3)Cl produced by Cyathea smithii and Angiopteris evecta were respectively -72.7 per thousand and -69.3 per thousand representing depletions relative to plant biomass of 42.3 per thousand and 43.4 per thousand. The characteristic isotopic signature of CH(3)Cl released by green plants should help constrain their contribution to the atmospheric burden when reliable delta13C values for all other major sources of CH(3)Cl are obtained and a globally averaged delta13C value for atmospheric CH(3)Cl is available.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

Size-mediated foliar response to ozone in black cherry trees

Local ozone concentration and visible foliar injury were measured over the 1994 growing season on open-grown black cherry (Prunus serotina Ehrh.) trees of varying size (age) within forest stands and adjacent openings at a site in north-central Pennsylvania. Relationships were determined between visible ozone injury and ozone exposure, as well as calculated between injury and ozone uptake expressed as the product of stomatal conductance and ozone concentration. In addition, simultaneous measurements of visible symptoms and leaf gas exchange were also conducted to determine the correlation between visible and physiological injury and ozone exposure. By September, the amount of leaf area affected by visible foliar ozone injury was greatest for seedlings (46%), followed by canopy trees (20%) and saplings (15%). A large amount of variability in foliar ozone symptom expression was observed among trees within a size class. Sum40 and Sum60 (ozone concentration > 40 and > 60 nl liter(-1)) cumulative exposure statistics were the most meaningful indices for interpretation of foliar injury response. Seedlings were apparently more sensitive to ozone injury than larger trees because their higher rates of stomatal conductance resulted in higher rates of ozone uptake. Seedlings also had higher rates of early leaf abscission than larger trees with an average of nearly 30% of the leaves on a shoot abscised by 1 September compared to approximately 5% for larger trees. However, per unit ozone uptake into the leaf, larger trees exhibited larger amounts of foliar injury. The amount of visible foliar injury was negatively correlated (r(2) = 0.82) with net photosynthetic rates, but was not related to stomatal conductance. Net photosynthesis and stomatal conductance thus became uncoupled at high levels of visible foliar injury.     

Simulations of stratospheric to tropospheric transport during the tropical cyclone Marlene event

Enhanced ozone values observed in the upper troposphere near intense tropical cyclones have raised the question of the role of stratospheric–tropospheric exchange. The dynamical mechanisms involved in the enhanced ozone values of 6 April 1995 observed at Reunion and associated with the tropical cyclone Marlene could not be explained by ECMWF meteorological analysis with 1.125° horizontal resolution. A previous study based on the ECHAM model has demonstrated the impact of biomass burning, but of limited amplitude (<60–80 ppbv max). In this paper, the upper tropospheric ozone enhancement on the periphery of Marlene has been studied with a mesoscale model (MESO-NH). This model is able to reproduce a stratospheric PV filament into the troposphere, crossing the isentropes to the 350 K level. The ageostrophic circulation associated with divergence zones that have induced vertical movements has been shown. Further, the influence of vertical wind shear, evident in both the mesoscale analysis and in the idealized HURRICANE tropical cyclone model, also contributes to our understanding of this downward transport process.     

Reduction of stem growth and site dependency of leaf injury in Massachusetts black cherries exhibiting ozone symptoms

Leaf ozone symptoms in natural ecosystems are increasingly reported but ozone effects on tree growth and the mediation of site conditions are still little documented. This study tests two hypotheses: (1) leaf injury in black cherry is associated with decline in radial growth, (2) symptoms are more prevalent on mesic sites. On sites supporting black cherry across Massachusetts, tree growth and leaf ozone injury were surveyed in 1996 using a randomized plot network established in the 1960s. Forty-seven percent of 120 trees sampled for ozone symptoms were symptomatic with generally low levels of injury. Over a 31-year period symptomatic trees had 28% lower stem growth rates than asymptomatic trees. Ozone symptom expression was enhanced in well growing stands on moister, cooler and more elevated sites. Ozone appeared to increase environmental stress and had a more pronounced effect on growth in better growing black cherry stands. This complicates management decisions as thinning increases growth and moisture availability.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Beech (Fagus sylvatica) response to ozone exposure assessed with a chlorophyll a fluorescence performance index

This paper describes a relationship between ozone exposure, biomass, visual symptoms and a chlorophyll a fluorescence performance index for young beech trees (Fagus sylvatica). The plants were exposed to four levels of ozone in open-top fumigation chambers (50, 85, 100% of ambient, and 50% of ambient+30 nl l(-1) ozone) that fluctuated in parallel with ambient ozone during a single growing season. The trees were fumigated in the four treatments with ozone levels corresponding to an AOT40 (accumulated exposure above a threshold of 40 nl l(-1)) of 0.01, 3.35, 7.06 and 19.70 microl l(-1) h, respectively. Highly significant differences were found between the 50% of ambient+30 nl l(-1) ozone treatment and all other treatments, with a 70.5% reduction in primary photosynthetic performance, as measured with the PI index. The reduction of the PI values demonstrated a high correlation with visual symptom development (r(2)=0.98), and by the end of September with biomass loss (r(2)=0.99). A significant ozone exposure-response relationship was found between AOT40 and primary photochemistry (r(2)=0.97). Thus, analysis of PI provides an alternative method for regional monitoring of tree health within the context of the currently employed AOT40.     

Ozone and UV-B variations at Ispra from 1993 to 1997

An analysis of the variability of the total ozone column at Ispra (Italy) has been performed to ascertain if, even in a short-time interval of 5 years (1993–1997), a decline of the monthly mean ozone values could be demonstrated. A linear fit of the data displays a decrease of 0.21% per year with a mean value equal to 319±2 D.U. and an amplitude of the annual cycle of about 10% of the mean. A linear regression of the surface monthly mean ozone values has also been performed showing a decreasing trend (−1% per year) that could contribute, even if for a very small amount, to the decline of the total ozone values. Ispra monthly mean total ozone data have been compared with those of three stations located within 2° latitude and 3° longitude from Ispra (Haute Provence, Hohenpeissenberg and Arosa). A linear fit of the data shows some discrepancies in the ozone changes, which can be attributed to the limited length of the observational period.An analysis has been performed to verify if the variation of ozone at Ispra is in agreement with that of the solar UV measured at a wavelength (305 nm) where the ozone absorption is still remarkable. The results, taken at a fixed solar zenith angle of 68°, show a clear anticorrelation between the monthly mean values of UV and the corresponding values of the total ozone column; the linear fit of the UV data displays an increase of 2.0% per year, much higher than expected from the ozone decrease, and a mean value of 1.4±0.1 mW m^-2 nm^-1.     

A lagrangian approach to analyse the tropospheric ozone climatology in the tropics: Climatology of stratosphere–troposphere exchange at Reunion Island

Sixteen years of ozone measurements (1992–2006) at Reunion Island (21°S, 55.5°E) have been processed to detect stratospheric signatures on each single ozone profile.The characterisation method consists in the advection of the potential vorticity (PV) over two to ten days of backtrajectory with the lagrangian trajectory code LACYTRAJ. LACYTRAJ is a Trajectory-Reverse Domain Filling code using the ERA40 ECMWF database and allowing the reconstruction of high resolution advected PV profiles. Correlation between high values of ozone mixing ratio and high PV is interpreted as a stratospheric signature.A climatology of STE events at Reunion has been derived and reveals that STE events occur more frequently during spring (SON) and summer (DJF). The method is tested for a set of PV threshold values (i.e. 1 PVU, 1.5 PVU and 2 PVU) and for a set of duration of backtrajectories (i.e. 2 days, 5 days and 10 days). The number of detected STE is sensitive to PV threshold values and duration criterions. For instance, the number of stratospheric intrusions detected in October with a 1.5 PVU criterion ranges between 25% (2 days of backtrajectories) and 56% (10 days of backtrajectories). The vertical distributions of STE show intrusions covering the whole free troposphere (between 7 and 15 km) and mainly located in the upper troposphere.Finally, results show that an important number of stratospheric intrusions are detected during spring and in the upper troposphere what points at the contribution of the stratospheric source to the tropospheric ozone spring maximum which is strongly influenced by the biomass burning emissions from South Africa and Madagascar.     

Impact of biogenic emission uncertainties on the simulated response of ozone and fine particulate matter to anthropogenic emission reductions

The role of emissions of volatile organic compounds and nitric oxide from biogenic sources is becoming increasingly important in regulatory air quality modeling as levels of anthropogenic emissions continue to decrease and stricter health-based air quality standards are being adopted. However, considerable uncertainties still exist in the current estimation methodologies for biogenic emissions. The impact of these uncertainties on ozone and fine particulate matter (PM2.5) levels for the eastern United States was studied, focusing on biogenic emissions estimates from two commonly used biogenic emission models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emissions Inventory System (BEIS). Photochemical grid modeling simulations were performed for two scenarios: one reflecting present day conditions and the other reflecting a hypothetical future year with reductions in emissions of anthropogenic oxides of nitrogen (NOx). For ozone, the use of MEGAN emissions resulted in a higher ozone response to hypothetical anthropogenic NOx emission reductions compared with BEIS. Applying the current U.S. Environmental Protection Agency guidance on regulatory air quality modeling in conjunction with typical maximum ozone concentrations, the differences in estimated future year ozone design values (DVF) stemming from differences in biogenic emissions estimates were on the order of 4 parts per billion (ppb), corresponding to approximately 5% of the daily maximum 8-hr ozone National Ambient Air Quality Standard (NAAQS) of 75 ppb. For PM2.5, the differences were 0.1-0.25 microg/m3 in the summer total organic mass component of DVFs, corresponding to approximately 1-2% of the value of the annual PM2.5 NAAQS of 15 microg/m3. Spatial variations in the ozone and PM2.5 differences also reveal that the impacts of different biogenic emission estimates on ozone and PM2.5 levels are dependent on ambient levels of anthropogenic emissions.     

Simulation of trace species production by lightning and corona discharge in moist air

Numerical simulations of chemical processes initiated in moist air by lightning strokes and lightning coronas indicate that the amounts of major new species generated are not very different from the amounts previously found in dry air. Thus, the major new species produced globally in moist air are estimated to be: 2.4 megatonnes NO y⁻¹, 0.28 megatonnes NO₂ y⁻¹ and 220 tonnes N₂O y⁻¹. The minor species, ozone and those containing hydrogen released by lightning from water in moist air are: 1.2 kilotonnes O₃ y⁻¹, 25 kilotonnes HNO₂ y⁻¹, 1.2 kilotonnes HNO₃ y⁻¹, 0.32 kilotonnes H₂O₂ y⁻¹ and 0.32 kilotonnes HO₂ y⁻¹.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

Glaciochemical records from a Mt. Everest ice core: relationship to atmospheric circulation over Asia

Glaciochemical records recovered from an 80.4 m ice core in the East Rongbuk (ER) Glacier (elevation: 6450 m) on the northern slope of Mt. Everest provide a reconstructing of past climate for the period AD 1846–1997. Empirical orthogonal function (EOF) analysis on the eight major ion (SO₄²⁻, Mg²⁺, Ca²⁺, Na⁺, Cl⁻, NH₄⁺, K⁺, and NO₃⁻) time-series reveals inter-species relations and common structure within the ER glaciochemical data. The first two EOF series (EOF1-ions and EOF2-ions) are compared with instrumental data of sea level pressure (SLP) to demonstrate that the EOF-ions series display strong connections to winter (January) and summer (July) SLP over the Mongolian region. The positive relationship between EOF1-ions and the Mongolian High (MongHi) series suggests that enhanced winter MongHi strengthens the transport of dust aerosols southward from arid regions over central Asia to Mt. Everest. The close correspondence between EOF2-ions and the summer Mongolian Low (MongLow) indicates that the deeper MongLow, which is related to the stronger Indian Monsoon, contributes to a decrease in summer dust aerosols. Therefore, the ER ice core record comprises two assemblages of crustal species, each transported from different source regions during different seasons. EOF1-ions represents the majority of the crustal species and is related to winter atmospheric circulation patterns. These species are mainly transported from arid regions of central Asia during the winter dry season. EOF2-ions represents crustal species transported by summer atmospheric circulation from local/regional sources in the northern and southern Himalayas.     

Thermoluminescence as a tool for monitoring ozone-stressed plants

The effect of ozone (6 h, various concentrations from 0 to 350 ppb) on barley (Hordeum vulgare L., cv. Bomi) and tomato (Lycopersicon esculentum L., cv. Yellow Cherry) leaves was investigated in parallel by thermoluminescence (TL) and fluorescence (FL) methods. Several significant changes were found in TL glow curves measured after excitation by one single turnover flash at +2 degree C in the temperature range from 2 to 170 degree C immediately after ozone exposure. Contrary to TL, ozone induced only negligible changes in FL parameters F0, FM and Fv/FM. Measurements done 24 h after ozone exposure showed partial recovery of ozone-induced changes. The extent of recovery was not the same in different parts of TL curves. Fluorescence parameters were not significantly changed. The results demonstrate that TL parameters are more sensitive to ozone than conventially used FL parameters F0, FM and Fv/FM. Moreover, TL measurements seem to give information not only about the PSII electron transport, but also about the extent of oxidative damage and membrane lipid peroxidation. It is concluded, that TL can be a highly informative tool for monitoring the impact of ozone on plants.