A Multi-Trajectory Chemical-Transport Vectorized Gear Model: 3-D Simulations and Model Validation

A new multi-trajectory highly vectorizable Gear chemical-transport model is discussed and tested against measurements from 25 sites in Europe for a two-week summer period. The simulations are compared with measurement data and with results of a Quasi-Steady-State Approximation (QSSA) based Lagrangian model using the EMEP mechanism.The model is developed from the Lagrangian EMEP model. The Regional Atmospheric Chemistry Mechanism (RACM) is used as the models chemical mechanism. To solve the stiff chemical rate equations, a sparse-matrix highly vectorizable Gear algorithm is used. The meteorological data used to run the model are obtained from the HIgh Resolution Limited Area Model (HIRLAM).The vectorized Gear based model improves the accuracy of the numerical solution for the chemistry compared with the QSSA based model. The differences between the two models are explained by alternative approaches of the chemical modules employed in the model: a Gear algorithm versus a QSSA solver, photolysis rate parameters in RACM are calculated from a radiation transfer code versus parameterized photolysis rate parameters used in the Lagrangian EMEP model, the RACM versus the EMEP atmospheric chemical mechanisms and two methods of aggregating the emissions of Volatile Organic Compounds (VOC). Photolysis rate parameters calculated from radiation codes (which are more accurate than simple parameterizations) and the Gear algorithm (which is a benchmark solver compared with the QSSA solver) are recommended for atmospheric chemistry modeling because of the high sensitivity of ozone concentrations to the chemical reaction scheme and to the photolysis rates (Stockwell and Goliff, 2004).     

NOx or VOC Limitation in East German Ozone Plumes?

The ozone forming potential of VOCs and NO_x for plumes observed from several cities and a power plant in eastern Germany was investigated. A closed box model with a gas phase photochemical reaction mechanism was employed to simulate several scenarios based upon aircraft observations. In several of the scenarios, the initial concentrations of NO_x, VOCs, and SO₂, were reduced to study the factors limiting the O₃ production. Ozone production was limited by the initial VOC concentrations for all of the simulated plumes. Higher O₃ concentrations were produced with reduced initial NO_x. In one sample with high SO₂ mixing ratios (>100 ppb), SO₂ was also identified as a significant contributor to the production of O₃.     

Cloud model experiments of the effect of iron and copper on tropospheric ozone under marine and continental conditions

Summary We have used a multi-phase cloud photochemistry model to investigate the influence of dissolved iron (Fe) and copper (Cu) on the in-cloud production and loss of ozone and ozone-related species. Comparison of the results of our simulations with and without Fe and Cu reactions for three different photochemical scenarios (marine, averaged continental and polluted continental) indicate that Fe and Cu reactions, depending upon the scenario considered, can either increase or decrease the predicted rate of loss of ozone and ozone related species. For the marine and averaged continental scenarios the rate of loss of ozone in the aqueous-phase was decreased by as much as 45% and 70%, respectively, when Fe and Cu reactions were considered. For polluted continental conditions, the rate of loss of ozone in the aqueous phase increased with a factor 2 for low metal concentrations up to a factor 20 for high metal concentrations. In all three scenarios inclusion of the Fe and Cu reactions results in cloud droplets becoming more efficient sinks for gas-phase HO₂ and also enhances OH production. The net effect of the decreased losses of ozone from the aqueous phase and the effect of the cloud droplets on HO₂ and OH determine the overall impact on ozone and ozone related species, for each of the situations considered. Overall, when Fe and Cu reactions were included the marine cloud was found to be a less efficient sink for ozone, and averaged continental and polluted continental clouds were more efficient sinks for ozone (O₃ losses doubled in the averaged continental scenario). The higher OH flux in the aqueous phase also enhances the rate at which organic compounds, such as formaldehyde and formic acid, are oxidized in the cloud.With 4 Figures     

NUMERICAL SIMULATION OF THE SEASONAL VARIATION OF TROPOSPHERIC OZONE OVER CHINA

An updated version of the Regional Acid Deposition Model(RADM)driven by meteorologicalfields derived from Chinese Regional Climate Model(CRegCM)is used to simulate seasonal variationof tropospheric ozone over the eastern China.The results show that:(1)Peak O_3 concentration moves from south China to north China responding to the changing ofsolar perpendicular incidence point from south to north.When solar perpendicular incidence pointmoves from north to south,so does the peak O_3 concentration.(2)In the eastern China.the highest O_3 month-average concentration appears in July.thelowest in January and the medium in April and October.The pattern mainly depends on the solarradiation,the concentration of O_3 precursors NO_x and NMHC and the ratio of NMHC/NO_x.(3)Daily variations of O_3 over the eastern China are clear.Namely,O_3 concentrations rise withthe sun rising and the maximums appear at noon.then O_3 concentrations decrease.The highest dailyvariation range of O_3 appears in summer(40×10~(-9) in volume fraction)and the lowest in winter(20×10~(-9) in volume fraction).(4)Daily variations of O_3 over the western China are not clear.The daily variation range of O_3 isless than 10×10~(-9) in volume fraction.     

A Three-Dimensional Simulation of HO x Concentrations Over East Asia During TRACE-P

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is used to simulate three-dimensional concentration distributions of hydroxyl (OH) and hydroperoxyl (HO₂) radicals over the western Pacific Ocean during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign. Modeled values of OH and HO₂ and their closely related chemical species and photolysis rates are compared with observational data collected onboard the DC-8 aircraft. Comparison shows that the model reasonably reproduced these observed values over a broad range of conditions with an overall tendency to overestimate the measured OH and HO₂ by a factor of 1.56 and 1.24, respectively. A case study of OH, HO₂ and their closely related chemical species and photolysis rates along the DC-8 flights 11 and 12 conducted on 17–18 March 2001 shows that the model reproduces the temporal and spatial variations reasonable well, and produces more reliable OH and HO₂ concentrations in the polluted environment than in the clean marine boundary layer.     

Natural and anthropogenic C2 to C6 hydrocarbons in the central-eastern Venezuelan atmosphere during the rainy season

The levels of low molecular weight hydrocarbons were measured at pristine sites and rural locations affected by hydrocarbon emissions from oil and gas producing fields in Venezuela. At the clean sites, lower concentrations of C₂ to C₆ alkanes were observed, whereas, in comparison with remotes sites, very much higher levels were measured at the polluted sites. Alkenes present relatively high concentrations, with isoprene being the most abundant, all over the study region. The main sources of alkenes are likely to be natural, mainly from vegetation. The levels of alkanes recorded at the clean sites and the alkene levels found everywhere in the region are in agreement with the values reported for other clean sites in the tropics. The increase of ozone production capacity due to the anthropogenic emissions of alkanes from oil and gas fields was estimated. Due to the presence in the atmosphere of important amounts of naturally emitted isoprene, ethene and propene, which makes a substantial contribution to the reactivity of the hydrocarbon mixture, a small increase (<5%) was estimated to occur in the capacity of the ozone production at a regional scale during the rainy season.     

Comparison of Measured Ozone Production Efficiencies in the Marine Boundary Layer at Two European Coastal Sites under Different Pollution Regimes

Ozone production efficiencies (E_N), which can be defined as the netnumber of ozone molecules produced per molecule of NO_xoxidised, have been calculated from measurements taken during three intensive field campaigns (one in the spring, EASE 96, and two in the summer, EASE 97 and TIGER 95), at two European coastal sites (Mace Head, Ireland (EASE) and Weybourne, Norfolk (TIGER)) impacted by polluted air masses originating from both the U.K. and continental Europe, as well as relatively clean oceanic air masses from the Arctic and Atlantic. From a detailed wind sector analysis of the EASE 96 and 97 data it is clear that two general types of pollution regime were encountered at Mace Head. The calculated ozone production efficiency in clean oceanic air masses was approximately 65, which contrasted to more polluted air, from the U.K. and the continental European plume, where the efficiency decreased to between 4 and 6. The latter values of E_Nagree well with literature measurements conducted downwind of various urban centres in the U.S. and Europe, which are summarised in a wide-ranging review table. The E_N value calculated for clean oceanic air is effectivelyan upper limit, owing to the relatively rapid deposition of HNO₃ tothe ocean. Consideration of the variation of E_N with NO_x forthe three campaigns suggests that ozone production efficiency is relatively insensitive to both geographical location and season. The measuredE_N values are also compared with values derived from steady-state expressions. An observed anti-correlation between E_N and measured ozone tendencyis briefly discussed.     

东亚区域对流层臭氧及其前体物的季节性关联

利用2010—2012年对流层臭氧（O₃）及其多种前体物的卫星遥感资料和全球水汽再分析资料,研究东亚区域O₃及其前体物的时空分布,以及在中国东部（分为南、北两部分）相关性的季节变化。结果表明:东亚区域NO₂与CO的对流层柱含量均表现为冬季高、夏季低的时空变化形式。O₃对流层柱含量夏季达到峰值,冬季为谷值。中国东部的北部与南部地区O₃与NO₂均在夏秋季呈正相关,冬春季呈负相关。夏季大部分地区NO_x的光化学循环反应对O₃生成有积极的促进作用,冬季大部分地区O₃的光化学循环生成受到抑制。O₃与CO在北部地区夏秋季和南部地区夏季正相关性最大,无论是在北部还是南部地区,O₃与CO的相关性在轻污染情况下最大,而在重污染和背景情况下较小,表明重污染气团向下风方的输送更有利于O₃的光化学生成。O₃与水汽在北部和南部地区的多数时间均呈较显著的正相关性,而在南部地区夏季和北部地区冬季具有较大的负相关性,反映出不同的环流形式、气团来源及伴随的天气条件变化对O₃分布的影响。     

Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

Ozone in the Marine Boundary Layer at Cape Grim: Model Simulation

A photochemical box model has been used to simulate the mixing ratio ofozone under conditions reflecting those encountered in the marine boundarylayer at Cape Grim, Tasmania, where a decade-long record of ozone mixingratio is available. The model is based on the proposition that ozone loss byphotolysis, atmospheric reaction with hydroperoxy and hydroxyl radicals, andsurface deposition is balanced by ozone gain via entrainment from the lowerfree troposphere with a small additional source in summer from photolysis ofnitrogen dioxide. This model simulates very well the observed ozone records,reproducing both the small diurnal cycle in ozone mixing ratio observedduring the summer months, and the factor of two seasonal ozone cycle showinga distinct winter maximum and summer minimum. The model result confirms thatunder the low-NO_x conditions of the clean marine boundarylayer net photochemical loss of ozone occurs at all times of year.     

NUMERICAL SIMULATION OF OZONE DISTRIBUTIONS AND ITS VARIATION MECHANISM*

A 2-D global chemistry-transport model is set up in this paper.The model simulates the atmospheric ozone distributions well with specified dynamical conditions.The analysis of ozone variation mechanism shows that ozone is chemically in quasi-equilibrium except for the polar night region where the variation of ozone concentration is under the control of dynamical processes,that the oxygen atoms which produce ozone are mainly provided by the photolysis of O₂ in the upper stratosphere and by the photolysis of NO₂ in the lower stratosphere and the troposphere.and that the ozone is destroyed mainly by NO_x:the reactions between NO_x and O₃ and the odd oxygen cycle contribute 80% to more than 90% of the ozone destruction.     

Regionally Representative Ozone Monitoring at Cape Arkona

Long Path Different Optical Absorption measurements of theconcentrations of O₃, NO₂, NO₃ andSO₂ were carried out at Cape Arkona, Island Rügen, nearthe well-known long-term ozone registration. A statistical analysis ofdifferent trace gas concentrations for all seasons is presented. Daytimedata, wind speed and sector-classified results are used to estimaterepresentative ozone concentrations. Comparison of the long path ozonemeasurements with point measurements at Cape Arkona shows ozoneconcentration differences.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Segregation and Interpretation of Ozone and Carbon Monoxide Measurements by Air Mass Origin at the TOR Station Mace Head, Ireland from 1987 to 1995

Three independent methods have been used to sort the ozone, carbonmonoxide, and other radiatively important trace gases measured at Mace Head,Ireland, and thereby distinguish clean air masses transported over the NorthAtlantic from the more polluted air masses which have recently travelledfrom the European continent. Over the period April 1987–June 1995 theNorthern Hemisphere surface ozone baseline concentrations exhibited a meanconcentration of 34.8 ppb, with a small positive trend (+0.19 ppbyr^-1), while the corresponding trend in air originating fromthe polluted European areas was negative (–0.39 ppbyr^-1). Carbon monoxide measurements from March 1990 toDecember 1994 showed negative trends for both the unpolluted (–0.17ppb yr^-1) and polluted data (–13.6 ppbyr^-1). Overall the continent of Europe was shown to be a smallnet sink of 2.6 ppb for all occasions when European air was transported tothe North Atlantic.     

Model analysis of seasonal variations in tropospheric ozone and carbon monoxide over East Asia

Temporal-spatial variations in tropospheric ozone concentrations over East Asia in the period from 1 January 2000 to 31 December 2004 were simulated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the Regional Atmospheric Modeling System (RAMS). The simulated concentrations of ozone and carbon monoxide were compared with ground level observations at two remote sites, Ryori (39.03°N, 141.82°E) and Yonagunijima (24.47°N, 123.02°E). The co...     

The role of precursor emissions on ground level ozone concentration during summer season in Poland

Three online coupled chemical transport model simulations were analyzed for three summer months of 2015 in Poland. One of them was run with default emission inventory, the other two with NO_x and VOC emissions reduced by 30%, respectively. Obtained ozone concentrations were evaluated with data from air quality measurement stations and ozone sensitivity to precursor emissions was estimated by ozone concentration differences between simulations and with the use of indicator ratios. They were calculated based on modeled mixing ratios of ozone, total reactive nitrogen and its components, nitric acid and hydrogen peroxide. The results show that the model overestimates ozone concentrations with the largest errors in the morning and evening, which is primarily related to the way vertical mixing is resolved by the model. Better model performance for ozone is achieved in rural than urban environment, as PBL and mixing mechanisms play more significant role in urban areas. Modeled ozone shows mixed sensitivity to precursor concentrations, similarly to other European regions, but indicator ratios have different values than are found in literature, particularly H₂O₂/HNO₃ is larger than in southern Europe. However, indicator ratios often differ between locations and transition values need to be established individually for a given region.     

Chemistry–Climate Interactions of Stratospheric and Mesospheric Ozone in EMAC Long-Term Simulations with Different Boundary Conditions for CO2, CH4, N2O,and ODS

Abstract

To evaluate future climate change in the middle atmosphere and the chemistry–climate interaction of stratospheric ozone, we performed a long-term simulation from 1960 to 2050 with boundary conditions from the Intergovernmental Panel on Climate Change A1B greenhouse gas scenario and the World Meteorological Organization Ab halogen scenario using the chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). In addition to this standard simulation we performed five sensitivity simulations from 2000 to 2050 using the rerun files of the simulation mentioned above. For these sensitivity simulations we used the same model setup as in the standard simulation but changed the boundary conditions for carbon dioxide (CO₂), methane (CH₄), nitrous oxide (N₂O), and ozone-depleting substances (ODS). In the first sensitivity simulation we fixed the mixing ratios of CO₂, CH₄, and N₂O in the boundary conditions to the amounts for 2000. In each of the four other sensitivity simulations we fixed the boundary conditions of only one of CO₂, CH₄, N₂O, or ODS to the year 2000.

In our model simulations the future evolution of greenhouse gases leads to significant cooling in the stratosphere and mesosphere. Increasing CO₂ mixing ratios make the largest contributions to this radiative cooling, followed by increasing stratospheric CH₄, which also forms additional H₂O in the upper stratosphere and mesosphere. Increasing N₂O mixing ratios makes the smallest contributions to the cooling. The simulated ozone recovery leads to warming of the middle atmosphere.

In the EMAC model the future development of ozone is influenced by several factors. 1) Cooler temperatures lead to an increase in ozone in the upper stratosphere. The strongest contribution to this ozone production is cooling due to increasing CO₂ mixing ratios, followed by increasing CH₄. 2) Decreasing ODS mixing ratios lead to ozone recovery, but the contribution to the total ozone increase in the upper stratosphere is only slightly higher than the contribution of the cooling by greenhouse gases. In the polar lower stratosphere a decrease in ODS is mainly responsible for ozone recovery. 3) Higher NO_x and HO_x mixing ratios due to increased N₂O and CH₄ lead to intensified ozone destruction, primarily in the middle and upper stratosphere, from additional NO_x; in the mesosphere the intensified ozone destruction is caused by additional HO_x. In comparison to the increase in ozone due to decreasing ODS, ozone destruction caused by increased NO_x is of similar importance in some regions, especially in the middle stratosphere. 4) In the stratosphere the enhancement of the Brewer-Dobson circulation leads to a change in ozone transport. In the polar stratosphere increased downwelling leads to additional ozone in the future, especially at high northern latitudes. The dynamical impact on ozone development is higher at some altitudes in the polar stratosphere than the ozone increase due to cooler temperatures. In the tropical lower stratosphere increased residual vertical upward transport leads to a decrease in ozone.     

The annual cycle of peroxides and ozone in marine air at Cape Grim, Tasmania

The concentration of gas-phase peroxides has been measured almost continuously at the Cape Grim baseline station (41° S) over a period of 393 days (7702 h of on-line measurements) between February 1991 and March 1992. In unpolluted marine air a distinct seasonal cycle in concentration was evident, from a monthly mean value of>1.4 ppbv in summer (December) to <0.2 ppbv in winter (July). In the summer months a distinct diurnal cycle in peroxides was also observed in clean marine air, with a daytime build-up in concentration and decay overnight. Both the seasonal and diurnal cycles of peroxides concentration were anticorrelated with ozone concentration, and were largely explicable using a simple photochemical box model of the marine boundary layer in which the central processes were daytime photolytic destruction of ozone, transfer of reactive oxygen into the peroxides under the low-NO_x ambient conditions that favour self-reaction between peroxy radicals, and continuous heterogeneous removal of peroxides at the ocean surface. Additional factors affecting peroxides concentrations at intermediate timescales (days to a week) were a dependence on air mass origin, with air masses arriving at Cape Grim from higher latitudes having lower peroxides concentrations, a dependence on local wind speed, with higher peroxides concentrations at lower wind speeds, and a systematic decrease in peroxides concentration during periods of rainfall. Possible physical mechanisms for these synoptic scale dependencies are discussed.     

Studies of Oxidant Production at the Weybourne Atmospheric Observatory in Summer and Winter Conditions

Detailed studies have been made of the behaviour of gases and radicals involved in the production of oxidants at the Weybourne Atmospheric Observatory in both summertime and wintertime conditions. In June 1995 the range of meteorological conditions experienced varied such that ozone destruction was observed in clean northerly air flows reaching Weybourne down the North Sea from the Arctic, and ozone production was observed in varying degrees in air with different loadings of nitrogen oxides and other precursors. The transition point for ozone destruction to ozone production occurred at a nitric oxide concentration of the order of 50 pptv. Plumes of polluted air from various urban areas in the U.K. were experienced in the June campaign at Weybourne. Quantitative studies of ozone production in a plume from the Birmingham conurbation on 18 June 1995 showed that the measurement of ozone production agreed well with calculated production rates from the product of the nitric oxide and peroxy radical concentrations (r2=0.9). In wintertime conditions (October–November 1994) evidence was also found for oxidant production, defined as the sum of O3+NO2. At this time of year the peroxy radical concentrations (RO2) were much lower than observed in the summertime and the nitric oxide (NO) was much higher. There was still sufficient RO2 during the day, however, for a slow accumulation of oxidant. Confirmatory evidence for this comes from the diurnal co-variance of (O3+NO2) with PAN, an excellent tracer of tropospheric photochemistry. The same type of covariance occurs in summer between PAN and ozone. The results obtained in these series of measurements are pertinent to understanding the measures necessary to control production of regional photochemical air pollution, and to the production of ozone throughout the northern hemisphere in winter.     

Temporal variations in surface ozone and its precursors and meteorological effects at an urban site in China

Continuous measurements of ozone and its precursors including NO, NO₂, and CO at an urban site (32°03′N, 118°44′E) in Nanjing, China during the period from January 2000 to February 2003 are presented. The effects of local meteorological conditions and distant transports associated with seasonal changed Asian monsoons on the temporal variations of O₃ and its precursors are studied by statistical, backward trajectory, and episode analyses. The diurnal variation in O₃ shows high concentrations during daytime and low concentrations during late night and early morning, while the precursors show high concentrations during night and early morning and low concentrations during daytime. The diurnal variations in air pollutants are closely related to those in local meteorological conditions. Both temperature and wind speed have significant positive correlations with O₃ and significant negative correlations with the precursors. Relative humidity has a significant negative correlation with O₃ and significant positive correlations with the precursors. The seasonal variation in O₃ shows low concentrations in late autumn and winter and high concentrations in late spring and early summer, while the precursors show high concentrations in late autumn and winter and low concentrations in summer. Local mobile and stationary sources make a great contribution to the precursors, but distant transports also play a very important role in the seasonal variations of the air pollutants. The distant transport associated with the southeastern maritime monsoon contributes substantially to the O₃ because the originally clean maritime air mass is polluted when passing over the highly industrialized and urbanized areas in the Yangtze River Delta. The high frequency of this type of air mass in summer causes the fact that a common seasonal characteristic of surface O₃ in East Asia, summer minimum, is not observed at this site. The distant transports associated with the northern continental monsoons that dominate in autumn and winter are related to the high concentrations of the precursors in these two seasons. This study can contribute to a better understanding of the O₃ pollution in vast inland of China affected by meteorological conditions and the rapid urbanization and industrialization.