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.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

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.     

Long-term characterization of major water-soluble inorganic ions in PM<Subscript>10</Subscript> in coastal site on the Japan Sea

PM₁₀ samples were collected over three years at Monzenmachi, the Japan Sea coast, the Noto Peninsula, Ishikawa, Japan from January 17, 2001 to December 18, 2003, using a high volume air sampler with quartz filters. The concentrations of the water-soluble inorganic ions in PM₁₀ were determined with using ion chromatography. By analyzing the characteristics of these, the evidences were found that the Asian outflow had an obviously influence on the air quality at our study site. The results were as follows: the secondary pollutants SO₄²⁻, NO₃⁻ and NH₄⁺ were the primary water-soluble inorganic ions at our study site. The monthly mean concentrations of SO₄²⁻, NH₄⁺, NO₃⁻ and Ca²⁺ have prominent peak in spring due to the strong influence of the Asian continent outflow—these according to backward air trajectory analysis, the maximum of which were 6.09 for nss-SO₄²⁻ in May, 2.87 for NO₃⁻ and 0.68 μg m⁻³ for nss-Ca²⁺ in April, respectively. Comparable to similar data reported from various points around East Asia, it had the characteristics of a polluted coastal area at our study site. The concentration of nss-Ca²⁺ in PM₁₀ drastically increased when the Asian dust invaded, the mean value during the Asian dust days(AD) was 0.86 μg m⁻³, about 4 times higher than those of normal days (NAD). Meanwhile, the mean concentrations of nss-SO₄²⁻, NO₃⁻ and NH₄⁺ in AD periods were higher than those in NAD periods which were 5.87, 1.76 and 1.82 μg m⁻³, respectively, it is due to the interaction between dust and secondary particles during the long-range transport of dust storms. Finally, according to the source apportionment with positive matrix factorization (PMF) method in this study, the major source profiles of PM₁₀ at our study site were categorized as (1) marine salt, (2) secondary sulfate, (3) secondary nitrate and (4) crustal source.     

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     

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.     

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.     

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.     

Reconstructed light extinction coefficients using chemical compositions of PM<Subscript>2.5</Subscript> in winter in Urban Guangzhou,China

The objective of this study was to reconstruct light extinction coefficients (b ext ) according to chemical composition components of particulate matter up to 2.5 μm in size (PM 2.5 ). PM 2.5 samples were collected at the monitoring station of the South China of Institute of Environmental Science (SCIES, Guangzhou, China) during January 2010, and the online absorbing and scattering coefficients were obtained using an aethalometer and a nephelometer. The measured values of light absorption coefficient by particle (b ap ) and light scattering coefficient by particle (b sp ) significantly correlated (R 2 > 0.95) with values of b ap and b sp that were reconstructed using the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula when RH was <70%. The measured b ext had a good correlation (R 2 > 0.83) with the calculated b ext under ambient RH conditions. The result of source apportionment of b ext showed that ammonium sulfate [(NH 4 ) 2 SO 4 ] was the largest contributor (35.0%) to b ext , followed by ammonium nitrate (NH 4 NO 3 , 22.9%), organic matter (16.1%), elemental carbon (11.8%), sea salt (4.7%), and nitrogen dioxide (NO 2 , 9.6%). To improve visibility in Guangzhou, the effective control of secondary particles like sulfates, nitrates, and ammonia should be given more attention in urban environmental management.     

Uptake of nitrogen dioxide (NO<Subscript>2</Subscript>) on acidic aqueous humic acid (HA) solutions as a missing daytime nitrous acid (HONO) surface source

A comprehensive kinetic study of a potential daytime nitrous acid (HONO) source reaction, the photoenhanced reduction reaction of the nitrogen dioxide (NO₂) on acidic humic acid (HA), was completed using a wetted-wall flow tube (WWFT) (Fickert et al.: J. Phys. Chem. A. 102, 10689, 1998) photoreactor integrated with a high sensitivity HONO analyser (Wall et al.: J. Atmos. Chem. 55, 31–54, 2006; Huang et al.: Atmos. Environ. 36, 2225–2235, 2002). The nature of this reaction, is of great interest since recently observed, unpredictably high HONO daytime concentrations demand its ordinarily proposed heterogeneous source to proceed 60 times more rapidly at noon than during the night (Kleffmann et al.: ChemPhysChem 8, 1137–1144, 2007). This study investigated the nature of the reduction reaction with simulated colloidal HA aqueous solutions characteristic of anaerobic environmental conditions, varying in acidity, concentration and composition. Typical urban NO₂ levels were investigated. Increasing photoenhanced HONO production with weakening solution acidity was detected due to increased deprotonation of the carboxyl groups within the humic acid. It was deduced that the acidic HA substrate contains numerous feasible chromophoric sensitizer units capable of photochemically reducing NO₂ to HONO, owing to its ‘biofilm’ (Donlan, 2002) function under UV exposure. The mechanism was found to be more effective for HA standards with higher levels of ‘bioactivity’ (refractivity). Using a complex mathematical model developed, incorporating both chemistry and diffusion, reaction probability datasets were produced from the experimental data, providing evidence that this is, indeed, an environmentally important daytime HONO surface source reaction. The parameters required to scale up the data of the photoreactor to that of a regional rural/urban scale were assessed.     

Factors Influencing Nitrogen Speciation in Coastal Rainwater

Rainwater was collected from 129 rain events between February 2002 and August 2003 and analyzed for ammonium (NH₄⁺), nitrate (NO₃⁻), organic nitrogen (ON) and free amino acids (AA). Inorganic nitrogen (NO₃⁻ + NH₄⁺) was the dominant form of N representing 85% of total nitrogen based on volume-weighted averages. The remainder of the N occurred as organic nitrogen species of which free amino acids contribute approximately 17%. A significant, and in some cases the majority (> 75%), of the remaining ON could be accounted for by macromolecular uncharacterized humic like substances. This has important ramifications with respect to the long range transport of atmospheric ON because humic materials are recalcitrant and therefore may travel long distances from their source. There was a distinct seasonality to the N speciation data with maximum concentrations of NH₄⁺, ON and AA occurring in the spring. Air-mass back trajectory analysis indicates there is a strong anthropogenic component to the NO₃⁻, NH₄⁺ and AA signal but not ON. There was a strong positive correlation between amino acid concentrations and ammonium which suggests they have similar sources and sinks in rainwater. Finally, large episodic additions of NH₄⁺ and AA during tropical events could significantly impact short term bioavailable N budgets in estuaries impacted by these storms. Approximately three times as much NH₄⁺ and AA were deposited during Hurricane Isabel (317 μ moles ⋅ m⁻² and 84 μ moles ⋅ m⁻² respectively) compared to the mean impact of average summertime rain events at this location.     

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.     

Measurement and investigation of chamber radical sources in the European Photoreactor (EUPHORE)

It is essential to quantify the background reactivity of smog-chambers, since this might be the major limitation of experiments carried out at low pollutant concentrations typical of the polluted atmosphere. Detailed investigation of three chamber experiments at zero-NO _x in the European Photoreactor (EUPHORE) were carried out by means of rate-of-production analysis and two uncertainty analysis tools: local uncertainty analysis and Monte Carlo simulations with Latin hypercube sampling. The chemical mechanism employed was that for methane plus the inorganic subset of the Master Chemical Mechanism (MCMv3.1). Newly installed instruments in EUPHORE allowed the measurement of nitrous acid and formaldehyde at sub-ppb concentrations with high sensitivity. The presence of HONO and HCHO during the experiments could be explained only by processes taking place on the FEP Teflon walls. The HONO production rate can be described by the empirical equation W(HONO)_EUPHORE ^dry = a × j _{NO 2}× exp (− T ₀/T) in the low relative humidity region (RH < 2%, a = 7.3×10²¹ cm⁻³, T ₀ = 8945K), and by the equation W(HONO)_EUPHORE ^humid = W(HONO)_EUPHORE ^dry+ j _{NO 2}× b × RH ^q in the higher relative humidity region (2% < RH < 15%, b = 5.8×10⁸ cm⁻³ and q = 0.36, and RH is the relative humidity in percentages). For HCHO the expression W(HCHO)_EUPHORE = c × j _{NO 2}exp (− T′₀/T) is applicable (c = 3.1×10¹⁷ cm⁻³ and T′₀ = 5686 K). In the 0–15% relative humidity range OH production from HONO generated at the wall is about a factor of two higher than that from the photolysis of 100 ppb ozone. Effect of added NO₂ was found to be consistent with the dark HONO formation rate coefficient of MCMv3.1.     

Measurements of Reaction Coefficients of NO2 and HONO on Aerosol Particles

The reaction coefficients of nitrogen dioxide and nitrous acid with monodisperse sodium chloride and ammonium sulphate aerosols have been measured in a flow reactor at atmospheric pressure. These experiments were performed at relative humidities above and below the deliquescence points of both aerosols (r.h. 50 and 85%) at 279 K. The results for NO₂ afford a reaction coefficient in the range (2.8–10) × 10^-4 and for HONO, (2.8–4.6) × 10^-3. For both species, there appears to be an enhancement of the reaction coefficient on sodium chloride aerosol at 50% r.h. The results are compared with reaction coefficients determined by other experimental methods. A good agreement is found for both gases between this method and the coated denuder method previously developed in our research laboratories (Msibi et al., 1993) and with the majority of other published data for NO₂. In the case of HONO, our estimate of reaction coefficient is smaller than, or at the lower limits of the ranges reported by other published studies.     

Secondary aerosol formation and identification of regional source locations by PSCF analysis in the Indo-Gangetic region of India

Secondary aerosol formation was studied at Allahabad in the Indo-Gangetic region during a field campaign called Land Campaign-II in December 2004 (northern winter). Regional source locations of the ionic species in PM₁₀ were identified by using Potential Source Contribution Function (PSCF analysis). On an average, the concentration of water soluble inorganic ions (sum of anions and cations) was 63.2 μgm⁻³. Amongst the water soluble ions, average NO₃⁻ concentration was the highest (25.0 μgm⁻³) followed by SO₄²⁻ (15.8 μgm⁻³) and NH₄⁺ (13.8 μgm⁻³) concentrations. These species, contributed 87% of the total mass of water soluble species, indicating that most of the water soluble PM₁₀ was composed of NH₄NO₃ and (NH₄)₂SO₄/NH₄HSO₄ or (NH₄)₃H(SO₄)₂ particles. Further, the concentrations of SO₄²⁻, NO₃⁻, and NH4⁺ aerosols increased at high relative humidity levels up to the deliquescence point (∼63% RH) for salts of these species suggesting that high humidity levels favor the conversion and partitioning of gaseous SO₂, NO_x, and NH₃ to their aerosol phase. Additionally, lowering of ambient temperature as the winter progressed also resulted in an increase of NO₃⁻ and NH₄⁺ concentrations, probably due to the semi volatile nature of ammonium nitrate. PSCF analysis identified regions along the Indo-Gangetic Plain (IGP) including Northern and Central Uttar Pradesh, Punjab, Haryana, Northern Pakistan, and parts of Rajasthan as source regions of airborne nitrate. Similar source regions, along with Northeastern Madhya Pradesh were identified for sulfate.     

Consequences of Uncertainties in CO<Subscript>2</Subscript> Density for Estimating Net Ecosystem CO<Subscript>2</Subscript> Exchange by Open-path Eddy Covariance

Errors in the estimation of CO₂ surface exchange by open-path eddy covariance, introduced during the removal of density terms [Webb et al. Quart J Roy Meteorol Soc 106:85–100, (1980) - WPL], can happen both because of errors in energy fluxes [Liu et al. Boundary-Layer Meteorol 120:65–85, (2006)] but also because of inaccuracies in other terms included in the density corrections, most notably due to measurements of absolute CO₂ density (ρ _c ). Equations are derived to examine the propagation of all errors through the WPL algorithm. For an open-path eddy covariance system operating in the Sierra de Gádor in south-east Spain, examples are presented of the inability of an unattended, open-path infrared gas analyzer (IRGA) to reliably report ρ _c and the need for additional instrumentation to determine calibration corrections. A sensitivity analysis shows that relatively large and systematic errors in net ecosystem exchange (NEE) can result from uncertainties in ρ _c in a semi-arid climate with large sensible heat fluxes (H _s ) and (wet) mineral deposition. When ρ_c is underestimated by 5% due to lens contamination, this implies a 13% overestimation of monthly CO₂ uptake.     

Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Chemical Composition and Association of Size-Differentiated Aerosols at a Suburban Site in a Semi-Arid Tract of India

Size-differentiated concentrations of SPM, F, Cl, NO₃, SO₄, Na, K, Ca, Mg and NH₄ in atmospheric aerosols were measured in a suburban area of Agra city during December 1992 to March 1993. Except for NH₄, Cl and Na, all components were found to have a bimodal distribution. The fine fraction was dominated by NH₄, K, NO₃ and SO₄, while Na, Ca, Mg, F and Cl contributed to the coarse fraction. Fifty-eight percent of SO₄ and 67% of NO₃ were found in the fine mode and the coarse mode comprised 42 and 33% of SO₄ and NO₃, respectively. SO₄ was found to have a peak above the submicron range at 1.1 µm which has been attributed to secondary sulphate formation by heterogeneous oxidation of SO₂ on alkaline particles of Ca and Mg. The total aerosol was basic in nature and dominated by the soil-derived acid neutralising components (Ca, Mg and Na).