Role of atmospheric ammonia in the formation of inorganic secondary particulate matter: A study at Kanpur,India

Levels of fine Particulate Matter (PM_fine), SO₂ and NO_x are interlinked through atmospheric reactions to a large extent. NO_x, NH₃, SO₂, temperature and humidity are the important atmospheric constituents/conditions governing formation of fine particulate sulfates and nitrates. To understand the formation of inorganic secondary particles (nitrates and sulfates) in the atmosphere, a study was undertaken in Kanpur, India. Specifically, the study was designed to measure the atmospheric levels of covering winter and summer seasons and day and night samplings to capture the diurnal variations. Results showed are found to be significantly high in winter season compared to the summer season. In winter, the molar ratio of to was found to be greater than 2:1. This higher molar ratio suggests that in addition to (NH₄)₂SO₄, NH₄NO₃ will be formed because of excess quantity of present. In summer, the molar ratio was less than 2:1 indicating deficit of to produce NH₄NO₃. The nitrogen conversion ratio (NO₂ to NO₃) was found to be nearly 50% in the study area that suggested quick conversion of NO₂ into nitric acid. As an overall conclusion, this study finds that NH₃ plays a vital role in the formation of fine inorganic secondary particles particularly so in winter months and there is a need to identify and assess sources of ammonia emissions in India.     

Chemical characterization of wet precipitation events and deposition of pollutants in coal mining region,India

The present study investigated the chemical composition of wet atmospheric precipitation in India’s richest coal mining belt. Total 418 samples were collected on event basis at six sites from July to October in 2003 and May to October in 2004 and analysed for pH, EC, F⁻, Cl⁻, , , Ca²⁺, Mg²⁺, Na⁺, K⁺ and . The average pH value (5.7) of the rainwater of the investigated area is alkaline in nature. However, the temporal pH variation showed the alkaline nature during the early phase of monsoonal rainfall but it trends towards acidic during the late and high rainfall periods. The rainwater chemistry of the region showed high contribution of Ca²⁺ (47%) and (21%) in cations and (55%) and Cl⁻ (23%) in anionic abundance. The high non seas salt fraction (nss) of Ca²⁺ (99%) and Mg²⁺ (96%) suggests crustal source of the ions, while the high nss (96%) and high ratio signifying the impact of anthropogenic sources and the source of the acidity. The ratio of varies from 0.03 to 3.23 with the average value of 0.84 suggesting that Ca²⁺ and play a major role in neutralization processes. The assessment of the wet ionic deposition rates shows no any specific trend, however Ca²⁺ deposition rate was highest followed by and _.     

Chemistry of Precipitation Events and Inter-Relationship with Ambient Aerosols over a Semi-Arid Region in Western India

The precipitation events (n = 91), collected for 3 years (2000–2002) during the period of SW-monsoon (Jun–Aug) from an urban site (Ahmedabad, 23.0°N, 72.6°E) of a semi-arid region in western India, are found to exhibit characteristic differences in terms of their solute contents. The low solute (<700 μeq L⁻¹) events are either marked by heavy precipitation amount or successive events collected during an extended rain spell; whereas light precipitation events occurring after antecedent dry period are characterized by high solutes (>700 μeq L⁻¹). The ionic composition of low solute events show large variability due to varying contribution of anthropogenic species (: 1%–74%; : 1%–25%; and : 8%–68%) to the respective ion balance. In high solute events, ionic abundances are dominated by mineral dust (Ca²⁺ and ) and sea-salts (Na⁺ and Cl⁻). These differences are also reflected in the pH of low solute events (range: 5.2–7.4, VWM: 6.4) and high solute events (range: 6.6–8.2, VWM: 7.3). The comparison of Ca²⁺/Na⁺ and nss- ratios (on equivalent basis) in rain and aerosols suggests that the ionic composition of high solute events is influenced by below-cloud scavenging; whereas evidence for in-cloud scavenging is significantly reflected in low solute events. The annual wet-deposition fluxes of and are 330 and 480 mg m⁻² y⁻¹, respectively, in contrast to their corresponding dry-deposition fluxes (14 and 160 mg m⁻² y⁻¹); whereas wet and dry removal of Ca²⁺, Mg²⁺ and are comparable.     

Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature

The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions , , (in units of cm³ molecule⁻¹ s⁻¹). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO₃, O₃ and Cl have been calculated.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

Chemical composition of wet deposition in a Mediterranean site Athens,Greece related to the origin of air masses

The goal of this study is to determine the chemical composition of rain, in the wider region of Athens, Greece for the time period 1st September 2001 to 31st August 2002. Two model automatic rain samplers were installed in the Meteorological Station of Laboratory of Climatology (latitude: 37° 58′ N, longitude: 23° 47′ E) inside the Athens University Campus and in a site at Heraklio Attica, a northern suburb of Athens (latitude: 38° 03′ N, longitude: 23° 45′ E). The concentrations (μeq l⁻¹) of the major cations (H⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (Cl⁻, , και ), as well as pH and conductivity of rain in 39 total samples were determined. The figures of pH range from 6.4 to 8.4 and conductivity from 8 to 207 μS cm⁻¹. The analysis showed that Ca²⁺ ions are abundant within all examined samples, while and present the highest concentrations from the anions. In order to find out the origin of the air masses, the air mass back trajectories were calculated. Five sectors of the origin of air masses were revealed: the North, the South, the Local, the West and the East sector. Multivariate methods included Factor Analysis and Discriminant Analysis were applied to the examined ion concentrations and three main factors were extracted, which discriminated the ions according to their origin. The first group of ions is interpreted as the result of the anthropogenic activity, the second group represents the acidity–alkalinity independently of their source and the third one the marine influence.     

Oligomerization of levoglucosan by Fenton chemistry in proxies of biomass burning aerosols

Reactions of levoglucosan with produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by , forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).     

A dual site study of the rainwater chemistry within the Western Pacific region

The two-year (1999–2000) rainwater chemistry at two monitoring sites in nearby coastal areas [Taiwan (TW) and Hong Kong (HK)] within the Western Pacific region has been studied. The volume weighted average pH values for the entire sampling period in TW and HK were 4.6 and 4.2, respectively. Sea salt Na⁺ and Cl⁻ were the most abundant species in the TW samples but and H⁺ were the most abundant in the HK samples. The sea salt and concentrations at TW were higher than those at HK both in the cold and warm seasons. Chloride depletion was minimal in the rainwater samples at both sites. Non seasalt- was associated with . Under the influence of the East Asian Winter Monsoon, the back-trajectory studies revealed that elevated anthropogenic species concentrations were associated with trajectories (1) very near to the continental boundary layer of Mainland China; or (2) along the coastline of Eastern China where large cities/industrial areas are located or (3) passing through the region of stagnant air over Northern/Eastern China. The lowest anthropogenic and crustal species concentrations measured in HK are associated with the summer monsoon and are attributed not only to the clean marine air masses but also to the relatively low SO₂, NO _x and NH₃ emissions from the South/ South East Asian countries, as well as infrequent biomass burning activities and wet scavenging at sources during the summer months. Approaching tropical cyclones led to the lowest pH values (4.2 in TW and 3.8 in HK) amongst the other weather categories. The findings here have been compared with other studies within East Asia and elsewhere.     

Modification of Two-Equation Models to Account for Plant Drag

A modification of the most popular two-equation (E–φ) models, taking into account the plant drag, is proposed. Here E is the turbulent kinetic energy (TKE) and φ is any of the following variables: El (product of E and the mixing length l), (dissipation rate of TKE), and ω (specific dissipation of TKE, ). The proposed modification is due to the fact that the model constants estimated experimentally for ‘free-air’ flow do not allow for adequate reconstruction of the ratio between the production and dissipation rates of TKE in the vegetation canopy and have to be adjusted. The modification is universal, i.e. of the same type for all E–φ models considered. The numerical experiments carried out for both homogeneous and heterogeneous plant canopies with E–φ models (and with the E–l model taken as a kind of reference) show that the modification performs well. They also suggest that E– and E–ω schemes are more promising than the E–El scheme for canopy flow simulation since they are not limited by the need to use a wall function.In addition, a new parameterization for enhanced dissipation within the plant canopy is derived. It minimizes the model sensitivity to C _μ, the key parameter for two-equation schemes, and whose estimates unfortunately vary considerably from experiment to experiment. The comparison of results of new modified E– and E –ω models with observations from both field and wind-tunnel experiments shows that the proposed parameterization is quite robust. However, because of uncertainties with the turbulence Prandtl and Schmidt numbers for the E– model within the canopy, the E–ω model is recommended for future implementation, with the suggested modifications.     

Some methodological questions concerning advection measurements: a case study

A dataset from two campaigns conducted at the Vielsalm experimental site in Belgium was used as a basis for discussing some methodological problems and providing intermediate results on estimating CO₂ advection. The analysis focused on the horizontal [CO₂] gradient and on the vertical velocity w, the variables most affected by uncertainty. The sampling error for half-hourly horizontal [CO₂] gradients was estimated to be 1.3 μmol mol⁻¹. Despite this important random error for half-hour estimations of [CO₂], the mean horizontal [CO₂] gradients in advective conditions were shown to be representative at the ecosystem scale and to extend only to the lowest part of a drainage sub-layer, which developed in the trunk space. By contrast, under daytime conditions, this gradient was shown to be more sensitive to local source heterogeneities. The estimation of the short-term averaged vertical velocity ( was the greater source of error when computing advection terms. The traditional correction methods used to obtain are discussed and a (co)sine correction is tested to highlight the instrumental origin of the offset in w. A comparison of measurements by sonic anemometers placed close together above the canopy showed that the uncertainty on was 0.042 m s⁻¹, which is of the same order of magnitude as the velocity itself. In addition, as the drainage sub-layer is limited to the lowest part of the canopy, the representativeness of is questionable. An alternative computation using the divergence of the horizontal wind speed in the trunk space produced a estimation that was four times lower than the single-point measurement. However, this value gives a more realistic estimate of the vertical advection term and improves the CO₂ budget closure at the site.     

An Investigation on Temperature Variance Scaling in the Atmospheric Surface Layer

We present surface-layer measurements of temperature fluctuation variance from a site characterized by small-scale inhomogeneities. Periods of marked radiative forcing are selected. The data characterized by diabatic conditions and vertical heat flux larger than some threshold (here, chosen to be 0.01 K ms⁻¹) agree quite well with the convective scaling in unstable cases, and with the z-less parameterisation (with a large scatter) in stable cases. For near-neutral cases, the similarity function diverges because of the loss of significance of the temperature scale. Departures from similarity are highlighted in cases with smaller thermal fluxes, because horizontal heterogeneity and unsteadiness become important as production terms.     

Probabilistic Model for Concentration Fluctuations in Compact-Source Plumes in an Urban Environment

A comprehensive model for the prediction of concentration fluctuations in plumes dispersing in the complex and highly disturbed wind flows in an urban environment is formulated. The mean flow and turbulence fields in the urban area are obtained using a Reynolds-averaged Navier-Stokes (RANS) flow model, while the standard k-ϵ turbulence model (k is the turbulence kinetic energy and ϵ is the viscous dissipation rate) is used to close the model. The RANS model provides a specification of the velocity statistics of the highly disturbed wind flow in the urban area, required for the solution of the transport equations for the mean concentration and concentration variance (both of which are formulated in the Eulerian framework). A physically-based formulation for the scalar dissipation time scale t _d , required for the closure of the transport equation for , is presented. This formulation relates t _d to an inner time scale corresponding to “internal” concentration fluctuation associated with relative dispersion, rather than an outer time scale associated with the entire portion of the fluctuation spectrum. The two lowest-order moments of concentration ( and ) are used to determine the parameters of a pre-chosen functional form for the concentration probability density function (clipped-gamma distribution). Results of detailed comparisons between a water-channel experiment of flow and dispersion in an idealized obstacle array and the model predictions for mean flow, turbulence kinetic energy, mean concentration, concentration variance, and concentration probability density function are presented.     

Time Scales in the Unstable Atmospheric Surface Layer

Calculation of eddy covariances in the atmospheric surface layer (ASL) requires separating the instantaneous signal into mean and fluctuating components. Since the ASL is not statistically stationary, an inherent ambiguity exists in defining the mean quantities. The present study compares four methods of calculating physically relevant time scales in the unstable ASL that may be used to remove the unsteady mean components of instantaneous time signals, in order to yield local turbulent fluxes that appear to be statistically stationary. The four mean-removal time scales are: (t _c ) based on the location of the maximum in the ogive of the heat flux cospectra, () the location of the zero crossing in the multiresolution decomposition of the heat flux, (t ^*) the ratio of the mixed-layer depth over the convective velocity, and () the convergence time of the vertical velocity and temperature variances. The four time scales are evaluated using high quality, three-dimensional sonic anemometry data acquired at the Surface Layer Turbulence and Environmental Science Test (SLTEST) facility located on the salt flats of Utah’s western desert. Results indicate that and , with t _c achieving values about 2–3 times greater than t ^*. The sensitivity of the eddy covariances to the mean-removal time scale (given a fixed 4-h averaging period during midday) is also demonstrated.     

Kinetics of ammonia and ammonium ion inhibition of the atmospheric oxidation of aqueous sulfur dioxide by oxygen

This is the first study, which shows both NH₃ and NH₄⁺ to inhibit the autoxidation of aqueous SO₂ in the pH range 7.0–8.5. The rate of the autoxidation, R _aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law:

Aircraft Observations of Air-mass Modification Over the Sea of Okhotsk during Sea-ice Growth

In order to quantitatively investigate the role of leads and sea-ice in air-mass modification, aircraft observations were conducted over the partially ice-covered Sea of Okhotsk. We investigated two cold-air outbreak events with different sea-ice concentrations. In both cases, the difference between the temperatures of surface air and the sea surface (ΔT) dropped rapidly with the accumulated fetch-width of leads up to about 35-40 km, and then decreased very slowly. The surface sensible heat flux originating from open water was about 300 W m⁻² within a few kilometres from the coast and decreased with increasing accumulated fetch-width. The sensible heat flux was about 100 W m⁻² on average. These results indicate that the downwind air-mass modification depends mainly on the total (accumulated) extent of open water. The total buoyancy flux calculated by the joint frequency distribution method correlated very well with ice concentration. Such a relationship was not clear in the case of the moisture flux . The ratio between rising thermals and cold downdrafts differed significantly between upwind and downwind regions; that is, the buoyancy flux was dominated by in the developing stage of the boundary layer, while also became important after the development of the boundary layer.     

Two-Dimensional Scalar Spectra in the Deeper Layers of a Dense and Uniform Model Canopy

The turbulent flow inside dense canopies is characterized by wake production and short-circuiting of the energy cascade. How these processes affect passive scalar concentration variability in general and their spectral properties in particular remains a vexing problem. Progress on this problem is frustrated by the shortage of high resolution spatial concentration measurements, and by the lack of simplified analytical models that connect spectral modulations in the turbulent kinetic energy (TKE) cascade to scalar spectra. Here, we report the first planar two-dimensional scalar concentration spectra (ϕ _cc ) inside tall canopies derived from flow visualization experiments. These experiments were conducted within the deeper layers of a model canopy composed of densely arrayed cylinders welded to the bottom of a large recirculating water channel. We found that in the spectral region experiencing wake production, the ϕ _cc exhibits directional scaling power laws. In the longitudinal direction (x), or the direction experiencing the largest drag force, the ϕ _cc (k _x ) was steeper than and followed an approximate at wavenumbers larger than the injection scale of wake energy, where k _x is the longitudinal wavenumber. In the lateral direction (y), the spectra scaled as up to the injection scale, and then decayed at an approximate power law. This departure from the classical inertial subrange scaling (i.e., k ^−5/3) was reproduced using a newly proposed analytical solution to a simplified scalar spectral budget equation. Near the velocity viscous dissipation range, the scalar spectra appear to approach an approximate k ⁻³, a tantalizing result consistent with dimensional analysis used in the inertial-diffusive range. Implications to subgrid modelling for large-eddy simulations (LES) inside canopies are briefly discussed.     

A Parameterization of Third-order Moments for the Dry Convective Boundary Layer

We describe one-dimensional (1D) simulations of the countergradient zone of mean potential temperature observed in the convective boundary layer (CBL). The method takes into account the third-order moments (TOMs) in a turbulent scheme of relatively low order, using the turbulent kinetic energy equation but without prognostic equations for other second-order moments. The countergradient term is formally linked to the third-order moments and , and a simple parameterization of these TOMs is proposed. It is validated for several cases of a dry CBL, using large-eddy simulations that have been realized from the MESO-NH model. The analysis of the simulations shows that TOMs are responsible for the inversion of the sign of in the higher part of the CBL, and budget analysis shows that the main terms responsible for turbulent fluxes and variances are now well reproduced.     

Mass closure of total suspended particles over the coal burning power production area of western Macedonia, Greece

Ambient suspended particles (TSP) were collected from January to June 2001 at seven sampling sites in western Macedonia, Greece, where four thermal power stations are located. TSP samples were chemically characterized for minerals (Fe, Al, Mg, Ca, K, Ti and Si), trace elements (P, Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions , carbonaceous compounds (OC/EC) and polycyclic aromatic hydrocarbons (PAHs). These classes of compounds were consequently compared with PM mass concentrations of TSP in order to perform mass closure. PM chemical compositions exhibited differences at the seven sites. Minerals were found to be more abundant at four sites, electrolytes dominated the composition at two of the sites while carbonaceous material was most abundant only at one site. The fraction unaccounted for ranged between 22 and 34%. Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the site that was closest to the power plants. At the same site ions exhibited high correlations with minerals and the majority of trace elements.     

Spatial Variability of Flow Statistics within Regular Building Arrays

Turbulence statistics obtained by direct numerical simulations are analysed to investigate spatial heterogeneity within regular arrays of building-like cubical obstacles. Two different array layouts are studied, staggered and square, both at a packing density of . The flow statistics analysed are mean streamwise velocity (), shear stress (), turbulent kinetic energy (k) and dispersive stress fraction (). The spatial flow patterns and spatial distribution of these statistics in the two arrays are found to be very different. Local regions of high spatial variability are identified. The overall spatial variances of the statistics are shown to be generally very significant in comparison with their spatial averages within the arrays. Above the arrays the spatial variances as well as dispersive stresses decay rapidly to zero. The heterogeneity is explored further by separately considering six different flow regimes identified within the arrays, described here as: channelling region, constricted region, intersection region, building wake region, canyon region and front-recirculation region. It is found that the flow in the first three regions is relatively homogeneous, but that spatial variances in the latter three regions are large, especially in the building wake and canyon regions. The implication is that, in general, the flow immediately behind (and, to a lesser extent, in front of) a building is much more heterogeneous than elsewhere, even in the relatively dense arrays considered here. Most of the dispersive stress is concentrated in these regions. Considering the experimental difficulties of obtaining enough point measurements to form a representative spatial average, the error incurred by degrading the sampling resolution is investigated. It is found that a good estimate for both area and line averages can be obtained using a relatively small number of strategically located sampling points.     

Characterization of nutrients in the atmospheric wet and dry deposition observed at the two monitoring sites over Yellow Sea and East China Sea

To investigate the atmospheric deposition of nutrients into the coastal and shelf regions of the northwest Pacific Ocean, observation sites were established upon Qianliyan Island (within the Yellow Sea) and the Shengsi Archipelago (within the East China Sea), respectively. Nutrient concentrations, including , were determined in both aerosols and rainwater samples. The analytical results contain clear seasonal signatures, with high values during the dry season and low values during the rainy season. Similar trends are observed for deposition fluxes. The amount of wet deposition is greater than that of dry deposition for the studied nutrient species. The influence of meteorological factors such as rainfall means that samples from Qianliyan Island record higher nutrient values than those from Shengsi. Along with riverine inputs, atmospheric deposition plays an important role in determining the biogeochemistry of nutrient species in coastal and shelf oceans. An erratum to this article can be found at