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.     

Long-term measurements of atmospheric PM<Subscript>2.5</Subscript> and its chemical composition in rural Korea

Long-term measurements of ambient particulate matter less than 2.5 μm in diameter (PM_2.5) and its chemical compositions were performed at a rural site in Korea from December 2005 to August 2009. The average PM_2.5 concentration was 31 μg m⁻³ for the whole sampling period, and showed a slightly downward annual trend. The major components of PM_2.5 were organic carbon, SO₄²⁻, NO₃⁻, and NH₄⁺, which accounted for 55 % of total PM_2.5 mass on average. For the top 10 % of PM_2.5 samples, anionic constituents and trace elements clearly increased while carbonaceous constituents and NH₄⁺ remained relatively constant. Both Asian dust and fog events clearly increased PM_2.5 concentrations, but affected its chemical composition differently. While trace elements significantly increased during Asian dust events, NO₃⁻, NH₄⁺ and Cl were dramatically enhanced during fog events due to the formation of saturated or supersaturated salt solution. The back-trajectory based model, PSCF (Potential Source Contribution Function) identified the major industrial areas in Eastern China as the possible source areas for the high PM_2.5 concentrations at the sampling site. Using factor analysis, soil, combustion processes, non-metal manufacture, and secondary PM_2.5 sources accounted for 77 % of the total explained variance.     

Analysis of chemical characteristics of PM<Subscript>2.5</Subscript> in Beijing over a 1-year period

Beijing is one of the largest and most densely populated cities in China. PM_2.5 (fine particulates with aerodynamic diameters less than 2.5 μm) pollution has been a serious problem in Beijing in recent years. To study the temporal and spatial variations in the chemical components of PM_2.5 and to discuss the formation mechanisms of secondary particles, SO₂, NO₂, PM_2.5, and chemical components of PM_2.5 were measured at four sites in Beijing, Dingling (DL), Chegongzhuang (CG), Fangshan (FS), and Yufa (YF), over four seasons from 2012 to 2013. Fifteen chemical components, including organic carbon (OC), elemental carbon (EC), K⁺, NH₄ ⁺, NO₃ ^?, SO₄ ^2?, Cl^?, Al, Ca, Fe, Mg, Na, Pb, Si, and Zn, were selected for analysis. Overall, OC, SO₄ ^2?, NO₃ ^?, and NH₄ ⁺ were dominant among 15 components, the annual average concentrations of which were 22.62 ± 21.86, 19.39 ± 21.06, 18.89 ± 19.82, and 13.20 ± 12.80 μg·m^?3, respectively. Compared with previous studies, the concentrations of NH₄ ⁺ were significantly higher in this study. In winter, the average concentrations of OC and EC were, respectively, 3 and 2.5 times higher than in summer, a result of coal combustion during winter. The average OC/EC ratios over the four sites were 4.9, 7.0, 8.1, and 8.4 in spring, summer, autumn, and winter, respectively. The annual average [NO₃ ^?]/[SO₄ ^2?] ratios in DL, CG, FS, and YF were 1.01, 1.25, 1.08, and 1.12, respectively, which were significantly higher than previous studies in Beijing, indicating that the contribution ratio of mobile source increased in recent years in Beijing. Analysis of correlations between temperature and relative humidity and between SOR ([SO₄ ^2?]/([SO₄ ^2?] + [SO₂])) and NOR ([NO₃ ^?]/([NO₃ ^?] + [NO₂])) indicated that gas-phase oxidation reactions were the major formation mechanism of SO₄ ^2? in spring and summer in urban Beijing, whereas slow gas-phase oxidation reactions and heterogeneous reactions both occurred in autumn and winter. NO₃ ^? was mainly formed through year-round heterogeneous reactions in urban Beijing.     

Black carbon and chemical characteristics of PM<Subscript>10</Subscript> and PM<Subscript>2.5</Subscript> at an urban site of North India

The concentrations of PM₁₀, PM_2.5 and their water-soluble ionic species were determined for the samples collected during January to December, 2007 at New Delhi (28.63° N, 77.18° E), India. The annual mean PM₁₀ and PM_2.5 concentrations (± standard deviation) were about 219 (± 84) and 97 (±56) μgm⁻³ respectively, about twice the prescribed Indian National Ambient Air Quality Standards values. The monthly average ratio of PM_2.5/PM₁₀ varied between 0.18 (June) and 0.86 (February) with an annual mean of ∼0.48 (±0.2), suggesting the dominance of coarser in summer and fine size particles in winter. The difference between the concentrations of PM₁₀ and PM_2.5, is deemed as the contribution of the coarse fraction (PM_10−2.5). The analyzed coarse fractions mainly composed of secondary inorganic aerosols species (16.0 μgm⁻³, 13.07%), mineral matter (12.32 μgm⁻³, 10.06%) and salt particles (4.92 μgm⁻³, 4.02%). PM_2.5 are mainly made up of undetermined fractions (39.46 μgm⁻³, 40.9%), secondary inorganic aerosols (26.15 μgm⁻³, 27.1%), salt aerosols (22.48 μgm⁻³, 23.3%) and mineral matter (8.41 μgm⁻³, 8.7%). The black carbon aerosols concentrations measured at a nearby (∼300 m) location to aerosol sampling site, registered an annual mean of ∼14 (±12) μgm⁻³, which is significantly large compared to those observed at other locations in India. The source identifications are made for the ionic species in PM₁₀ and PM_2.5. The results are discussed by way of correlations and factor analyses. The significant correlations of Cl⁻, SO₄²⁻, K⁺, Na⁺, Ca²⁺, NO₃⁻ and Mg²⁺ with PM_2.5 on one hand and Mg²⁺ with PM₁₀ on the other suggest the dominance of anthropogenic and soil origin aerosols in Delhi.     

Sources,transport, and sinks of SO<Subscript>2</Subscript> over the equatorial Pacific during the Pacific Atmospheric Sulfur Experiment

The Pacific Atmospheric Sulfur Experiment (PASE) is the first sulfur-budget field experiment to feature simultaneous flux measurements of DMS marine emissions and SO₂ deposition to the ocean surface. We make use of these data to constrain a 1-D chemical transport model to study the production and loss pathways for DMS and SO₂ over the equatorial Pacific. Model results suggest that OH is the main sink for DMS in the boundary layer (BL), and the average DMS-to-SO₂ conversion efficiency is ~73%. In an exploratory run involving the addition of 1 pptv of BrO as a second oxidant, a 14% increase in the DMS flux is needed beyond that based on OH oxidation alone. This BrO addition also reduces the DMS-to-SO₂ conversion efficiency from 73% to 60%. The possibility of non-DMS sources of marine sulfur influencing the estimated conversion efficiency was explored and found to be unconvincing. For BL conditions, SO₂ losses consist of 48% dry deposition, while transport loss to the BuL and aerosol scavenging each account for another 19%. The conversion of SO₂ to H₂SO₄ consumes the final 14%. In the BuL, cloud scavenging removes 85% of the SO₂, thus resulting in a decreasing vertical profile for SO₂. The average SO₂ dry deposition velocity from direct measurements (i.e., 0.36 cm sec⁻¹) is approximately 50% of what is calculated from the 1-D model and the global GEOS-Chem model. This suggests that the current generation of global models may be significantly overestimating SO₂ deposition rates over some tropical marine areas. Although the specific mechanism cannot be determined, speculation here is that the dry deposition anomalous results may point to the presence of a micro-surface chemical phenomenon involving partial saturation with either S(IV) and/or S(VI) DMS oxidation products. This could also appear as a pH drop in the ocean’s surface microfilm layer in this region. Finally, we propose that the enhanced SO₂ level observed in the lower free troposphere versus that in the upper BuL during PASE is most likely the result of transported DMS/SO₂-rich free-tropospheric air parcels from the east of the PASE sampling area, rather than an inadequate representation in the model of local convection.     

DOAS observations of formaldehyde and its impact on the HO<Subscript>x</Subscript> balance in the tropical Atlantic marine boundary layer

Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO₂ production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HO_x (HO₂+OH) balance of the remote marine boundary layer.     

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.     

Urban Atmospheric Chemistry During the PUMA Campaign 1: Comparison of Modelled OH and HO<Subscript>2</Subscript> Concentrations with Measurements

Photochemical box modelling was undertaken to investigate OH and HO₂ radical chemistry during summer and winter field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism (v3.1) and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The model was used to predict OH and HO₂ concentrations for comparison with measurements made by the fluorescence assay by gas expansion technique. Whilst there was generally good agreement between the modelled and measured OH concentrations, particularly during summer, there was sometimes a significant model under-prediction during daylight hours, which significantly skews the overall model: measured agreement. There were less measured data available for HO₂, but the agreement between model and measurement for the days where measurements existed were less good than for OH, with one or two exceptions. The modelled:measured ratios between the hours of 11:00–15:00 h for OH were 0.58 and 0.50 for summer and winter respectively. For HO₂, the same ratios were 0.56 in the summer and 0.49 in the winter. Sensitivity studies were conducted to attempt to understand the model-measurement discrepancy. The predicted radical concentrations were particularly sensitive to changes in NO_X concentrations. Constraining the model to the observed HO₂ concentrations made the OH predictions worse. These results highlight the fact that there are many complexities in urban areas and that more highly-instrumented campaigns are required in the future to further our understanding.     

CO<Subscript>2</Subscript> and non-CO<Subscript>2</Subscript> radiative forcings in climate projections for twenty-first century mitigation scenarios

Climate is simulated for reference and mitigation emissions scenarios from Integrated Assessment Models using the Bern2.5CC carbon cycle–climate model. Mitigation options encompass all major radiative forcing agents. Temperature change is attributed to forcings using an impulse–response substitute of Bern2.5CC. The contribution of CO₂ to global warming increases over the century in all scenarios. Non-CO₂ mitigation measures add to the abatement of global warming. The share of mitigation carried by CO₂, however, increases when radiative forcing targets are lowered, and increases after 2000 in all mitigation scenarios. Thus, non-CO₂ mitigation is limited and net CO₂ emissions must eventually subside. Mitigation rapidly reduces the sulfate aerosol loading and associated cooling, partly masking Greenhouse Gas mitigation over the coming decades. A profound effect of mitigation on CO₂ concentration, radiative forcing, temperatures and the rate of climate change emerges in the second half of the century.     

Carbonaceous and inorganic species in PM<Subscript>10</Subscript> during wintertime over Giridih,Jharkhand (India)

Ambient concentrations of organic carbon (OC), elemental carbon (EC) and water soluble inorganic ionic components (WSIC) of PM₁₀ were studied at Giridih, Jharkhand, a sub-urban site near the Indo Gangatic Plain (IGP) of India during two consecutive winter seasons (November 2011–February 2012 and November 2012–February 2013). The abundance of carbonaceous and water soluble inorganic species of PM₁₀ was recorded at the study site of Giridih. During winter 2011–12, the average concentrations of PM₁₀, OC, EC and WSIC were 180.2?±?46.4; 37.2?±?6.2; 15.2?±?5.4 and 18.0?±?5.1 μg m^?3, respectively. Similar concentrations of PM₁₀, OC, EC and WSIC were also recorded during winter 2012–13. In the present case, a positive linear trend is observed between OC and EC at sampling site of Giridih indicates the coal burning, as well as dispersed coal powder and vehicular emissions may be the source of carbonaceous aerosols. The principal components analysis (PCA) also identifies the contribution of coal burning? +?soil dust, vehicular emissions?+?biomass burning and seconday aerosol to PM₁₀ mass concentration at the study site. Backward trajectoy and potential source contributing function (PSCF) analysis indicated that the aerosols being transported to Giridih from upwind IGP (Punjab, Haryana, Uttar Pradesh and Bihar) and surrounding region.     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.     

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.     

A nocturnal atmospheric loss of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> in the remote marine boundary layer

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH₂I₂) and chloro-iodomethane (CH₂ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH₂I₂ and CH₂ICl in air and of CH₂I₂ in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH₂I₂ was lower in amplitude than that of CH₂ICl, despite its faster photolysis rate. We speculate that night-time loss of CH₂I₂ occurs due to reaction with NO₃ radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k _CH2I2+NO3 of ≤4 × 10^?13 cm³ molecule^?1 s^?1; a previous kinetic study carried out at ≤100 Torr found k _CH2I2+NO3 of 4 × 10^?13 cm³ molecule^?1 s^?1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m^?2 d^?1 for CH₂I₂ and 3.7 +/? 0.8 nmol m^?2 d^?1 for CH₂ICl), we show that the model overestimates night-time CH₂I₂ by >60 % but reaches good agreement with the measurements when the CH₂I₂ + NO₃ reaction is included at 2–4 × 10^?13 cm³ molecule^?1 s^?1. We conclude that the reaction has a significant effect on CH₂I₂ and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.     

Spectra of CO<Subscript>2</Subscript> and Water Vapour in the Marine Atmospheric Surface Layer

Spectra of CO₂ and water vapour fluctuations from measurements made in the marine atmospheric surface layer have been analyzed. A normalization of spectra based on Monin–Obukhov similarity theory, originally developed for wind speed and temperature, has been successfully extended also to CO₂ and humidity spectra. The normalized CO₂ spectra were observed to have somewhat larger contributions from low frequencies compared to humidity spectra during unstable stratification. However, overall, the CO₂ and humidity spectra showed good agreement as did the cospectra of vertical velocity with water vapour and CO₂ respectively. During stable stratification the spectra and cospectra displayed a well-defined spectral gap separating the mesoscale and small-scale turbulent fluctuations. Two-dimensional turbulence was suggested as a possible source for the mesoscale fluctuations, which in combination with wave activity in the vertical wind is likely to explain the increase in the cospectral energy for the corresponding frequency range. Prior to the analysis the turbulence time series of the density measurements were converted to time series of mixing ratios relative to dry air. Some differences were observed when the spectra based on the original density measurements were compared to the spectra based on the mixing ratio time series. It is thus recommended to always convert the density time series to mixing ratio before performing spectral analysis.     

The millennial atmospheric lifetime of anthropogenic CO<Subscript>2</Subscript>

The notion is pervasive in the climate science community and in the public at large that the climate impacts of fossil fuel CO₂ release will only persist for a few centuries. This conclusion has no basis in theory or models of the atmosphere/ocean carbon cycle, which we review here. The largest fraction of the CO₂ recovery will take place on time scales of centuries, as CO₂ invades the ocean, but a significant fraction of the fossil fuel CO₂, ranging in published models in the literature from 20–60%, remains airborne for a thousand years or longer. Ultimate recovery takes place on time scales of hundreds of thousands of years, a geologic longevity typically associated in public perceptions with nuclear waste. The glacial/interglacial climate cycles demonstrate that ice sheets and sea level respond dramatically to millennial-timescale changes in climate forcing. There are also potential positive feedbacks in the carbon cycle, including methane hydrates in the ocean, and peat frozen in permafrost, that are most sensitive to the long tail of the fossil fuel CO₂ in the atmosphere.     

Choosing a Stabilization Target for CO<Subscript>2</Subscript>

The choice of stabilization target for CO₂ concentration depends on the following: what is considered to be dangerous anthropogenic interference with the climate system; the forcings that might arise from non-CO₂ gases; and the climate sensitivity. These three factors are specified here probabilistically, as probability density functions (pdfs), and combined to produce a pdf for the CO₂ concentration target. There is a probability of 17% that the stabilization target should be less than the present level, and the median target is 536 ppm. The effects of reducing the emissions of non-CO₂ gases and/or implementing adaptation strategies are considered probabilistically and shown to alter these figures significantly.     

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.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

A semi-continuous measurement of gaseous ammonia and particulate ammonium concentrations in PM<Subscript>2.5</Subscript> in the ambient atmosphere

Ammonia has a short residence time in the atmosphere and rapidly neutralizes acid gases that occur near its source, requiring a rapid measurement system for ammonia and particulate ammonium concentrations to better understand their sources, temporal variation of ammonia emissions, and the formation of secondary ammonium aerosols. A semi-continuous measurement system, consisting of a diffusion scrubber, a particle growth chamber, an air-liquid separator, and a fluorescent detector, was developed to determine both gaseous ammonia (NH₃) and particulate ammonium (NH ₄ ⁺ ) in PM_2.5 in the ambient atmosphere of Gwangju, South Korea, during the months of March, April, July, and September of 2007. During the sampling periods, the average concentrations of ammonia and ammonium were found to be 2.33?±?1.29 μg/m³ and 1.89?±?0.99 μg/m³, respectively. Although the average gaseous ammonia concentration was highest in March, the particulate ammonium concentration was higher during the warmer season, reaching 2.08?±?1.07 μg/m³ and 2.32?±?0.94 μg/m³ in April and July, respectively, while only 1.68?±?0.61 μg/m³ in March and 1.24?±?0.99 μg/m³ in September. It is proposed that the higher availability of acid species during the warmer months produced a significant amount of particulate ammonium sulfate. Diurnal fluctuation of ammonia and ammonium during the warmer months showed that their peak time occurred at approximately 10:00 am. Both ammonia and ammonium concentrations were better correlated during the warmer months than during the cooler months. Further, the data suggest that the ammonia and ammonium were measured under well dispersed conditions, and multiple sources contributed to the ammonia at the sampling site.     

Effect of Data Assimilation Parameters on The Optimized Surface CO<Subscript>2</Subscript> Flux in Asia

In this study, CarbonTracker, an inverse modeling system based on the ensemble Kalman filter, was used to evaluate the effects of data assimilation parameters (assimilation window length and ensemble size) on the estimation of surface CO₂ fluxes in Asia. Several experiments with different parameters were conducted, and the results were verified using CO₂ concentration observations. The assimilation window lengths tested were 3, 5, 7, and 10 weeks, and the ensemble sizes were 100, 150, and 300. Therefore, a total of 12 experiments using combinations of these parameters were conducted. The experimental period was from January 2006 to December 2009. Differences between the optimized surface CO₂ fluxes of the experiments were largest in the Eurasian Boreal (EB) area, followed by Eurasian Temperate (ET) and Tropical Asia (TA), and were larger in boreal summer than in boreal winter. The effect of ensemble size on the optimized biosphere flux is larger than the effect of the assimilation window length in Asia, but the importance of them varies in specific regions in Asia. The optimized biosphere flux was more sensitive to the assimilation window length in EB, whereas it was sensitive to the ensemble size as well as the assimilation window length in ET. The larger the ensemble size and the shorter the assimilation window length, the larger the uncertainty (i.e., spread of ensemble) of optimized surface CO₂ fluxes. The 10-week assimilation window and 300 ensemble size were the optimal configuration for CarbonTracker in the Asian region based on several verifications using CO₂ concentration measurements.