Global financial crisis making a V-shaped fluctuation in NO<Subscript>2</Subscript> pollution over the Yangtze River Delta

The Yangtze River Delta (YRD), China’s main cultural and economic center, has become one of the most seriously polluted areas in the world with respect to nitrogen oxides (NO_x), owing to its rapid industrialization and urbanization, as well as substantial coal consumption. On the basis of nitrogen dioxide (NO₂) density data from ozone monitoring instrument (OMI) and ground-based observations, the effects of industrial fluctuations due to the financial crisis on local NO₂ pollution were quantitatively assessed. The results were as follows. (1) A distinct V-shaped fluctuation of major industrial products, thermal generating capacity, electricity consumption, and tropospheric NO₂ densities was associated with the global financial crisis from May 2007 to December 2009, with the largest anomalies 1.5 times more than standard deviations at the height of the crisis period from November 2008 to February 2009. (2) Among all industrial sectors, thermal power plants were mainly responsible for fluctuations in local NO₂ pollution during the crisis period. Thermal generating capacity had its greatest decrease of 12.10% at the height of the crisis compared with that during November 2007–February 2008, leading to local tropospheric NO₂ density decreasing by 16.97%. As the crisis appeased, thermal generating capacity increased by 29.63% from November 2009 to February 2010, and tropospheric NO₂ densities correspondingly increased by 30.07%. (3) Among all industrial sectors in the YRD, the thermal power sector has the greatest coal consumption of about 65.96%. A decline in thermal power of about 10% can induce a decrease of about 30% in NO_x emissions and NO₂ densities, meaning that a relative small fluctuation in industrial production can lead to a large decrease in tropospheric NO₂ densities over industrially developed areas like the YRD region. Since electricity is mainly obtained from local coal-burning thermal plants without NO_x-processing equipment, installing NO_x-removal devices for all thermal power plants is an important and feasible way of controlling local NO_x pollution at present.     

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.     

An ozone depletion event in the sub-arctic surface layer over Hudson Bay,Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrO _x remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO₂ ratio.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

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.     

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.     

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。     

Sensitivity Analysis of Photochemical Indicators for O<Subscript>3</Subscript> Chemistry Using Automatic Differentiation

Photochemical indicators for determination of O₃–NO_x–ROG sensitivity and their sensitivity to model parameters are studied for a variety of polluted conditions using a comprehensive mixed-phase chemistry box model and the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect the indicators are identified and analyzed. Condensed mixed-phase chemical mechanisms are derived from the sensitivity analysis.Our results show that cloud chemistry has a significant impact on the indicators and their sensitivities, particularly on those involving H₂O₂, HNO₃, HCHO, and NO_z. Caution should be taken when applying the established threshold values of indicators in regions with large cloud coverage. Among the commonly used indicators, NO_y and O₃/NO_y are relatively insensitive to most model parameters, whereas indicators involving H₂O₂, HNO₃, HCHO, and NO_z are highly sensitive to changes in initial species concentrations, reaction rate constants, equilibrium constants, temperature, relative humidity, cloud droplet size, and cloud water content.     

The Heterogeneous Reaction of NO<Subscript>2</Subscript> with NH<Subscript>4</Subscript>Cl: A Molecular Diffusion Tube Study

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with NO<Subscript>2</Subscript>

The kinetics of heterogeneous reactions of NO₂ with 17 polycyclic aromatic hydrocarbons (PAHs) adsorbed on laboratory generated kerosene soot surface was studied over the temperature range (255–330) K in a low pressure flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption due to their desorption and reaction with NO₂ were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of reaction time, NO₂ concentrations in the gas phase being analyzed by mass spectrometer. No measurable decay of PAHs due to the reaction with NO₂ was observed under experimental conditions of the study (maximum NO₂ concentration of 5.5 × 10¹⁴ molecule cm⁻³ and reaction time of 45 min), which allowed to determine the upper limits of the first-order rate constants for the heterogeneous reactions of 17 soot-bound PAHs with NO₂: k < 5.0 × 10⁻⁵ s⁻¹ (for most PAHs studied). Comparison of these results to previous studies carried on different carbonaceous substrates, showed that heterogeneous reactivity of PAHs towards NO₂ is, probably, dependent on the substrate nature even for resembling, although different carbonaceous materials. Results show that particulate PAHs degradation by NO₂ alone is of minor importance in the atmosphere     

青藏高原闪电与NO_2的分析及中国内陆地区LNO_x产量的估算

为了进一步认识闪电活动与对流层氮氧化物的关系及更准确地估算中国地区闪电产生的氮氧化物(LNOx)总量,选取人口稀疏,工业生产水平较低的青藏高原地区作为研究区域,基于LIS(Lightning Imaging Sensor)和GOME-2(The Global Ozone Monitoring Experiment-2)卫星探测仪资料,分析了青藏高原中部区域2009年1月至2012年2月闪电与对流层NO2垂直浓度(VCD)月均值资料的时空分布特性和相关性。在此基础上,结合Beirle et al.(2004)的LNOx估算方法,估算了中国内陆地区的LNOx产量。结果表明:青藏高原地区对流层NO2与闪电与在年际趋势、空间分布及季节变化上保持很好的一致性,闪电密度与NO2VCD的线性拟合相关系数为0.84,这表明青藏高原地区NOx受人为源影响小,是研究LNOx的理想区域。基于拟合结果,估算得到中国内陆地区LNOx的年均产量为0.15(0.03~0.38)Tg(N)a-1。这一结论进一步缩小了以往研究中中国地区LNOx产量估算的不确定范围,有助于更清楚地认识闪电在中国气候变化中的重要作用。     

A method for the selective measurement of HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript> radical concentrations using a Nafion-PERCA system

An instrument is developed for the measurement of peroxy radical using chemical amplification coupled with NO₂-luminol chemiluminescence detection. The chain length of 147 ± 10 (1σ) is determined by an HO₂ source that uses the photolysis of water vapor under 184.9 nm in air. A Nafion system equipped with a Nafion tube of ~2.2 mm external diameter and 350 mm length is employed in the PERCA instrument (Nafion-PERCA system). When flowing an air sample containing HO₂ through the Nafion system, it is found that - 94.6 % of HO₂ is removed. In contrast, only 17.8 % of RO₂ radicals (a mixtures of CH₃O₂ and CH₃C(O)O₂ with a ratio of 1.1:0.9) are removed. The results indicate the Nafion system has a good selective removing performance of HO₂ radical during the PERCA measurement. Therefore, the method could be applied to ambient and laboratory measurements of absolute concentrations of RO₂ as well as the sum of HO₂ and RO₂.     

A numerical model for one‐dimensional simulation of stratospheric chemistry

Abstract

We describe a one‐dimensional (1‐D) numerical model developed to simulate the chemistry of minor constituents in the stratosphere. The model incorporates most of the chemical species presently found in the upper atmosphere and has been used to investigate the effect of increasing chlorofluorocarbon (CFC) emissions on ozone (O₃).

Our calculations confirm previous results that O₃ depletions in the 20–25 km region, the region of the O₃ maximum, are very sensitive to the relative abundances of Cl_x and NO_y in the lower stratosphere for high Cl_x amounts. The individual abundances of lower stratospheric Cl_x and NO_y amounts are very sensitive to upper tropospheric mixing ratios, which, in turn, are determined largely by surface input fluxes and heterogeneous loss processes. Thus the behaviour of column O₃ depletions at high Cl_x levels is greatly affected, albeit indirectly, by tropospheric processes. For high Cl_x levels the O_x flux from the stratosphere to the troposphere is dramatically reduced, leading to a large reduction in tropospheric O₃. Some of the variation between different published 1‐D model results is most likely due to this critical dependence of O₃ depletion on NO_y‐Cl_x ratios.

Model simulations of time‐dependent CFC effects on ozone indicate that if CFCs were to remain at constant 1980 emission rates while N₂O increased at 0.25% a^?1 and CH₄ increased at 1% a^?1, we could expect a 2.2% decrease in total column O₃ (relative to the 1980 atmosphere) by the year 2000. However, if CFC emission rates were to increase by 3% a^?1 (current estimates are 5–6% a^?1), we would predict a depletion of 2.7% by the year 2000. The calculations for times beyond the year 2000 suggest that the effects on total O₃ will begin to accelerate. If methyl chloroform emissions are added at 7% a^?1 (current estimates are 7–9% a^?1) to the above CFC‐N₂O‐CH₄ scenario we calculate total O₃ depletions by the year 2000 that are 41% larger than those calculated without. This suggests that if the emissions of methyl chloroform continue to increase at their present rate then methyl chloroform could have a significant effect upon total O₃.     

Chemical characterization and multivariate analysis of atmospheric PM<Subscript>2.5</Subscript> particles

The new European Council Directive (PE-CONS 3696/07) frames the inhalable (PM₁₀) and fine particles (PM_2.5) on priority to chemically characterize these fractions in order to understand their possible relation with health effects. Considering this, PM_2.5 was collected during four different seasons to evaluate the relative abundance of bulk elements (Cl, S, Si, Al, Br, Cu, Fe, Ti, Ca, K, Pb, Zn, Ni, Mn, Cr and V) and water soluble ions (F⁻, Cl⁻, NO₂ ⁻, NO₃ ⁻, SO₄ ²⁻, Na⁺, NH₄ ⁺, Ca²⁺ and Mg²⁺) over Menen, a Belgian city near the French border. The air quality over Menen is influenced by industrialized regions on both sides of the border. The most abundant ionic species were NO₃ ⁻, SO₄ ²⁻ and NH₄ ⁺, and they showed distinct seasonal variation. The elevated levels of NO₃ ⁻ during spring and summer were found to be related to the larger availability of the NO_x precursor. The various elemental species analyzed were distinguished into crustal and anthropogenic source categories. The dominating elements were S and Cl in the PM_2.5 particles. The anthropogenic fraction (e.g. Zn, Pb, and Cu) shows a more scattered abundance. Furthermore, the ions and elemental data were also processed using principal component analysis and cluster analysis to identify their sources and chemistry. These approach identifies anthropogenic (traffic and industrial) emissions as a major source for fine particles. The variations in the natural/anthropogenic fractions of PM_2.5 were also found to be a function of meteorological conditions as well as of long-range transport of air masses from the industrialized regions of the continent. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Analysis of Air Quality in Eastern China and its Interaction with Other Regions of the World

In this study, we used satellite data (GOME and MOPITT) together with a global chemical-transport-model of atmosphere (MOZART-2) to characterize the chemical/aerosol composition over eastern China. We then estimated the effects of local emissions in China on the chemical budgets in other regions of the world. Likewise, we also investigated the effects of air pollution from other regions on the chemical budget over eastern China. The study shows that the column CO and NO _x concentrations are also high in eastern China. The high CO and NO _x concentrations produce modest levels of O₃ concentrations during summer (about 40 to 50 ppbv) and very low O₃ during winter (about 10 to 20 ppbv) in eastern China. The calculated NO₂ column is fairly consistent from the GOME measurement. The calculated CO column is underestimated from the MOPITT measurement. One of the reasons of the underestimation of the predicted CO is due to a fact that the CO emissions were taken without considering the rapid increase of emissions from 1990 to 2000. The calculated surface O₃ is consistent with the measured values, with strong seasonal variations. However, the measurement is very limited, and more measurements in eastern China will be needed. The column NO₂ has a very strong seasonal variation in eastern China, with the highest concentrations during winter and the lowest concentrations during summer. The cause of this seasonal variability is mainly due to the seasonal changes in the chemical loss of NO _x , which is very high in summer and very low during winter. The effects of the local emissions in China and long-range transport from other regions on the chemical distributions in eastern China are studied. The results show that NO _x concentrations in eastern China are mostly caused by the local emissions in China, especially during the winter. The CO concentration over eastern China is from both the local emissions (30% to 40%) and the transport from other regions. Likewise, the CO emissions in China have an important effect on the other regions of the world, but the effect is limited in the northern hemisphere. The local emissions in China also have an important effect on surface O₃ concentrations. During winter, the local emissions reduce the surface O₃ concentrations by 30 to 50%. During summer, the local emissions produce about 50 to 70% of the O₃ concentration in eastern China.     

A budget analysis of NO x column losses over the Korean peninsula

In this study, the chemical and physical losses of nitrogen oxides (NO_x) over the Korean peninsula were discussed in order to better understand the effects of the NO_x losses on the tropospheric NO₂ columns. Initially, it was found that the physical loss processes due to dry and wet depositions had almost negligible impacts on the NO_x loss processes over the Korean peninsula. In contrast, the hourly NO_x chemical column losses were large at ??10¹⁴ molecules cm^?2 h^?1. The amounts of NO_x removed for 1 hour account for approximately 33?C35% of the episode-averaged tropospheric NO₂ columns during summer over the Korean peninsula. The NO_x chemical column loss rates were 24.1?C70.9 times larger than the NO_x physical column loss rates. In a budget analysis of the NO_x chemical column losses, HNO₃ formation via the reaction of OH + NO₂ had the largest contribution toward the NO_x chemical losses (42?C55% during fall and winter seasons; 76?C77% during spring; 92?C93% during summer). Large amounts of NO_x were also removed by heterogeneous nitrate formation via N₂O₅ condensation during the cold seasons (42?C56%) over the Korean peninsula. The columnar NO_x chemical losses took place mainly due to the two chemico-physical reaction processes, and also showed seasonal variations. PAN (Peroxyacetyl Nitrate) is another NO₂ reservoir of potential importance. If the influence of the PAN-related chemistry on the NO_x budget is considered, it can result in an approximate 69% increase in the NO_x chemical column loss during summer. Such increases in the amounts of NO_x removed for 1 hour due to the formation of PAN were equivalent to 56?C58% of the episode-averaged tropospheric NO₂ columns during summer over the Korean peninsula. Such active NO_x chemical losses during summer are another main factor for the tropospheric NO₂ columns exhibiting their smallest values during summer.     

长三角地区典型城市臭氧及其前体物时空分布特征

基于美国宇航局NASA/AURA卫星臭氧监测仪OMI数据,分析了2005—2014年长三角地区及其典型城市对流层O_3、NO_2柱浓度和HCHO大气总柱浓度的时空分布特征。结果表明:10 a间,长三角地区对流层O_3柱浓度和HCHO总柱浓度呈现增长趋势,O_3增量为0.23ppbv/10 a,HCHO增量为0.07×10~(16) mol/(cm~2·10 a),对流层NO_2柱浓度呈现降低趋势,减量为0.06×10~(15)mol/(cm~2·10 a);长三角地区对流层O_3柱浓度最大值出现在3、4、5月,而对流层NO_2柱浓度最大值出现在1、12月,HCHO总柱浓度最大值出现在6、7月;对流层O_3柱浓度的高值区分布在长三角中部、北部区域,对流层NO_2柱浓度高值区分布于长三角中部,HCHO总柱浓度高值区相对分散,且四季的分布各不相同。O_3与NO_2和HCHO在时间和空间上呈现一定的相关性。     

Variations in CO,O<Subscript>3</Subscript> and black carbon aerosol mass concentrations associated with planetary boundary layer (PBL) over tropical urban environment in India

Carbon monoxide (CO), Ozone (O₃) and Black Carbon (BC) aerosol mass concentrations in relation to planetary boundary layer (PBL) height measurements were analyzed from January–December, 2008 over tropical urban environment of Hyderabad, India. DMSP-OLS night-time satellite data were analyzed for fire occurrence over the region and its correlation with pollution concentrations over the urban region. Results of the study suggested considerable increase in CO and BC concentrations during early morning hours. Higher concentration of BC, CO and ozone was observed during pre-monsoon, post-monsoon and winter and lowest concentrations exhibited during monsoon season. NCEP/NCAR reanalysis winds suggested long range transport of aerosols and trace gases from forest fires are enhancing the pollutant concentrations over the study area.     

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.