Composition and major sources of organic compounds in urban aerosols

Total suspended particles (TSP), collected during June 2002 to July 2003 in Guangzhou, a typical economically developed city in South China, were analyzed for the organic compound compositions using gas chromatography–mass spectrometry (GC/MS). Over 140 organic compounds were detected in the aerosols and grouped into different classes including n-alkanes, hopanoids, polycyclic aromatic hydrocarbons, alkanols, fatty acids, dicarboxylic acids excluding oxalic acid, polyols/polyacids, lignin products, phytosterols, phthalates and water-soluble sugars. The total amounts of the identified organic compounds including unresolved complex mixture (UCM) ranged from 3112 ng/m³ in spring to 5116 ng/m³ in winter, comprising on seasonal average 2.8% of TSP. Primary organic compounds peaked in winter although there are no heating systems burning fuels in Guangzhou. The highest saccharide levels occurred in fall due to agricultural activities. This study demonstrated that utilization of fossil fuels, biomass burning, soil resuspension and plastic/refuse burning are the major contributors to the identified organic compounds in the urban atmosphere of South China.     

Enhancements of CO and O3 from burnings in sugar cane fields

The manual harvest of sugar cane requires the burning of its foliage. This burning has strongly increased in Brazil after the National Alcohol Program was started which substituted automobile gasoline engines for alcohol engines. Presently, the source strength per unit area of this rural pollution is comparable to the well-known biomass burning source in Amazonia. The observed concentrations of CO and O₃ in the rural area of the state of São Paulo during the 1988 burning season were twice as large as those reported from an aircraft experiment of 1985 for biomass burnings of the tropical rain forest. Results are reported from airplane measurements and from three fixed ground stations. Mixing ratios of ozone and carbon monoxide in the height range below 6 km are normally less than 40 and 100 ppbv, (parts per billion by volume), respectively, in the absence of burnings. A strong O₃ and CO layer was observed during the burning period with peak concentrations of 80 ppbv of ozone and 580 ppbv of CO at about 2 km. The concentrations of CH₄ and CO₂ were also large, 1756 ppbv and 409 ppmv, respectively, at 1500 m. During the dry season period of the experiment, the ground based O₃ average diurnal variations obtained at the rural sites were practically identical to the typical urban variation observed at São José dos Campos, with daytime ozone values between 45 and 60 ppbv. A second three-day airplane excursion to the surgar cane fields in the wet season of 1989 has produces results to be contrasted with the dry (burning) season of 1988 and 1989. Carbon monoxide concentrations were below 100 ppbv at all heights and ozone concentrations were around 30–40 ppbv. The maximum daytime concentrations at the ground station Bauru was 25 ppbv of O₃, and at Jaboticabal it was 35 ppbv of O₃, only one half of what was observed in the dry season.Universidade Estadual de São Paulo.     

Concentrations and sources of PAHs at three stations in Istanbul,Turkey

The chemical mass balance model was applied to atmospheric Polycyclic Aromatic Hydrocarbons (PAHs) in Istanbul, Turkey. A total of 326 airborne samples were collected and analyzed for 16 PAHs and Total Suspended Particles (TSP) in the September 2006–December 2007 period at three monitoring stations: Yildiz, DMO (urban sites) and Kilyos (rural site). The total average PAH concentrations were 100.66 ± 61.26, 84.63 ± 46.66 and 25.12 ± 13.34 ng m^?3 and the TSP concentrations were 101.16 ± 53.22, 152.31 ± 99.12, 49.84 ± 18.58 μg m^?3 for Yildiz, DMO and Kilyos stations respectively. At all the sites, the lighter compounds were the most abundant, notably Nap, AcPy and PA. The average correlation values between TSP and total heavier PAH were greater than 0.5 for Yildiz and DMO stations. The patterns of PAH and TSP concentrations showed spatial and temporal variations. PAH concentrations were evaluated for the PAH contribution from four sources (diesel engines, gasoline engines, natural gas combustion, and coal + wood burning). Vehicle emissions appear to be the major source with contributions of 61.2%, 63.3% and 54.1% for Yildiz, DMO and Kilyos stations respectively. Seasonal and yearly variations had different trends for all sites.     

Emissions of Polycyclic aromatic hydrocarbons by savanna fires

Although Polycyclic aromatic hydrocarbons (PAH) are known as anthropogenic compounds arising from the combustion or the pyrolysis of fossil fuels, they may be also emitted by the combustion of vegetation. A field study was carried out in January 1991 at Lamto (Ivory Coast) as part of the FOS DECAFE experiment (Fire Of Savanna). Some ground samplings were devoted to the qualitative and quantitative characterization of atmospheric emissions by savanna fires during prescribed burns and under background conditions. Specific collections for gaseous and particulate PAHs have shown that the African practice of burning the savanna biomass during the winter months is an important source of PAHs. These compounds are emitted mainly in gaseous form but a significant fraction, essentially heavy PAHs, is associated with fine carbonaceous particles and can therefore represent a hazard for human health, since some of these compounds are mutagenic and carcinogenic. Twelve compounds were identified during the fire episodes and in the atmospheric background. The total concentration in the fires is of the order of 10 ng m^–3 for the gas phase and from 0.1 to 1 ng m^–3 in the aerosols. In the atmospheric background the mean concentrations are regular, 0.15 ng m^–3 and 2 pg m^–3, respectively. These concentrations are comparable with what is observed in European rural zones. The particulate emissions of PAHs by the savanna fires are distinguished by the abundance of some compounds which can be considered as tracers, although they are also slightly emitted by fossil fuel sources. These compounds are essentially pyrene, chrysene and coronene. In the gas phase, although no individual PAH may be considered as specific of the biomass combustion emissions, the relative abundances of the main PAHs are characteristic of the biomass burning. The concentrations of pyrene and fluorene are always predominant; these compounds could be considered as characteristic emission products of smoldering and flaming episodes, respectively. In the background the PAH composition shows that in a tropical region the air consists of a mixture coming from the various sources, but the biomass combustion is by far the most important source.The fluxes of total PAH emitted by savanna biomass burning in Africa were estimated to be of the order of 17 and 600 ton yr^–1, respectively, for the particulate PAHs and the gaseous PAHs, respectively.     

An experimental technique for studying heterogeneous reactions of polyaromatic hydrocarbons on particle surfaces

An experimental technique for studying atmospheric heterogeneous reactions of polyaromatic hydrocarbons (PAH) on particle surfaces is reported. Particle bound organics were reacted in a 200 liter Teflon continuous stirred tank reactor (CSTR), with vapor phase oxidants. To provide a source of chemically stable particles for the CSTR, soot particles from a residential wood stove were first introduced during under darkness into a 25 m³ outdoor Teflon chamber. Air containing the particles was then added at a constant flow to the CSTR. The rates of heterogeneous reactions were obtained by comparing reacted particle samples with unreacted ones. The derivation of rate expressions for heterogeneous reactions in the CSTR is described. The use of the technique for a study of the nitration of selected soot particle bound PAH species by NO₂ and HNO₃ is demonstrated.     

The differences of the size distribution of polycyclic aromatic hydrocarbons (PAHs) between urban and rural sites of Guangzhou, China

Size distribution aerosol samples collected at two urban locations (Liwan and Wushan) and a suburban location (Xinken) in Guangzhou (South China) in autumn using a MOUDI (Micro-orifice Uniform Deposit Impactor) have been analyzed for 13 polycyclic aromatic hydrocarbons (PAHs) by gas chromatography with mass selective detection (GC-MS). Different PAH size distribution models were found for urban locations and a suburban location. The particle size distributions of PAHs tend to shift toward a larger size in a suburban location than in an urban location caused by aerosol aging processes. The ratios of total-PAH/TSP changed greatly during different sampling periods, even though the samplings were conducted consecutively. This can be the result of reactions between PAHs and atmospheric photooxidants, and the formation of SOAs (secondary organic aerosols) during the aging process. Adsorption behavior on available aerosol surface area, absorption behavior in available aerosol organic mass and multilayer adsorptive accumulation in coarse mode aerosols were the three mechanisms which control the size distribution of PAHs.     

Vertical coherence and phase delay between wind components in strong winds below 20 m

Vertical coherence and phase delay between wind components in strong winds in the lowest 20 m over uniform terrain in New Zealand have been analysed. The vertical decay constants and slopes for the horizontal wind components could be described as linear functions of the ratio of vertical spacing to mean height (δz/z), with relatively little scatter. The decay constants for the lateral were smaller than for the longitudinal components, the slopes larger for the lateral components, as found previously. The coherence of vertical velocity is best described by exponential decay functions multiplied by a parameter which decreases linearly from 1 (for δz/z=0) to 0.5 (for δz/z=1). The decay constants increased linearly with δz/z, as in the case of the horizontal components. There were no significant phase differences for the vertical components. Lateral and vertical decay constants for the longitudinal wind component could be fitted to identical functions of δy/z and δz/z, respectively.     

Seasonal variation of particulate organic compounds in atmospheric PM10 in the biggest municipal waste landfill of Algeria

The average composition and seasonal variations of atmospheric organic particulates with respect to n-alkanes, n-alkanoic acid, polycyclic aromatic hydrocarbon (PAHs), and nitrated polycyclic aromatic hydrocarbons (N-PAHs) were determined at the biggest municipal waste landfill in Algeria located in Oued Smar, 13 km east of downtown Algiers. Samplings were carried out from August 2002 to February 2003, and organic compounds adsorbed in air particles having an aerodynamic diameter lower than 10 μm (PM₁₀) were characterized using gas chromatography coupled with mass spectrometric detection (GC/MSD). Total concentrations ranged from 828 to 11,068 ng per cubic meter of air for n-alkanes, from 1714 to 21,710 ng per cubic meter of air for n-alkanoic acids, from 13 to 212 ng per cubic meter of air for PAHs and from 93 to 205 pg per cubic meter of air for N-PAHs. n-Alkanoic acids accounted for 85 and 56% of the total organic composition of the aerosol measured in summer and winter, respectively, were the biggest fraction. The distribution profiles and the diagnostic ratios of some marker compounds allowed to identify the combustion and microbial activity as the major sources of particulate organic pollutants associated with direct emission. The year-time dependence of organic fraction content of aerosol in Oued Smar appeared to be related to average meteorological conditions as well as variability of rate and nature of materials wasted into the landfill.     

A note on vertical coherence of wind measured in an urban boundary layer

The coherence, γ, between levels of the horizontal components of wind velocity are examined for data obtained on a 118-m tower at Victoria Dock, an urban site in Melbourne, Australia. The coherence is analysed to determine the influence of various parameters on its variation; it is found to be strongly dependent on f=n δz/U (n frequency, δz interlevel spacing and U the mean wind speed), and to a lesser degree on thermal stability and wind component. The empirical relation γ=exp(?af) is found to be reasonable and estimates of a are given. The data conform to observations reported at other sites.     

The Parameterisation of Scalar Transfer over Rough Ice

We test a surface renewal model that is widely used over snow and ice surfaces to calculate the scalar roughness length (z _s ), one of the key parameters in the bulk aerodynamic method. For the first time, the model is tested against observations that cover a wide range of aerodynamic roughness lengths (z ₀). During the experiments, performed in the ablation areas of the Greenland ice sheet and the Vatnajökull ice cap in Iceland, the surface varied from smooth snow to very rough hummocky ice. Over relatively smooth snow and ice with z ₀ below a threshold value of approximately 10^?3 m, the model performs well and in accord with earlier studies. However, with growing hummock size, z ₀ increases well above the threshold and the bulk aerodynamic flux becomes significantly smaller than the eddy-correlation flux (e.g. for z ₀ = 0.01 m, the bulk aerodynamic flux is about 50% smaller). Apparently, the model severely underpredicts z _s over hummocky ice. We argue that the surface renewal model does not account for the deep inhomogeneous roughness sublayer (RSL) that is generated by the hummocks. As a consequence, the homogeneous substrate ice grain cover becomes more efficiently ‘ventilated’. Calculations with an alternative model that includes the RSL and was adapted for use over hummocky ice, qualitatively confirms our observations. We suggest that, whenever exceedance of the threshold occurs (z ₀  >  10^?3 m, i.e., an ice surface covered with at least 0.3-m high hummocks), the following relation should be used to calculate scalar roughness lengths, ln (z _s /z ₀)  =  1.5  ? 0.2 ln (Re _*)  ? 0.11(ln (Re _*))².     

Two years observations on the diurnal evolution of coastal atmospheric boundary layer features over Thiruvananthapuram (8.5<Superscript>∘</Superscript> N, 76.9<Superscript>∘</Superscript> E), India

The atmospheric boundary layer (ABL) over a given coastal station is influenced by the presence of mesoscale sea breeze circulation, together with the local and synoptic weather, which directly or indirectly modulate the vertical thickness of ABL (z _ABL). Despite its importance in the characterization of lower tropospheric processes and atmospheric modeling studies, a reliable climatology on the temporal evolution of z _ABL is not available over the tropics. Here, we investigate the challenges involved in determination of the ABL heights, and discuss an objective method to define the vertical structure of coastal ABL. The study presents a two year morphology on the diurnal evolution of the vertical thickness of sea breeze flow (z _SBF) and z _ABL in association with the altitudes of lifting condensation level (z _LCL) over Thiruvananthapuram (8.5^° N, 76.9^° E), a representative coastal station on the western coastline of the Indian sub-continent. We make use of about 516 balloon-borne GPS sonde measurements in the present study, which were carried out as part of the tropical tropopause dynamics field experiment under the climate and weather of the sun-earth system (CAWSES)–India program. Results obtained from the present study reveal major differences in the temporal evolution of the ABL features in relation to the strength of sea breeze circulation and monsoonal wind flow during the winter and summer monsoon respectively. The diurnal evolution in z _ABL is very prominent in the winter monsoon as against the summer monsoon, which is attributed to the impact of large-scale monsoonal flow over the surface layer meteorology. For a majority of the database, the z _LCL altitudes are found to be higher than that of the z _ABL, indicating a possible decoupling of the ABL with the low-level clouds.     

The distribution of light nonmethane hydrocarbons over the mid-Atlantic: Results of the Polarstern cruise ANT VII/1

During the cruise ANT VII/1 (September/October 1988) of the German research vessel Polarstern the latitudinal distributions of several nonmethane hydrocarbons were measured over the Atlantic between 45°N and 30°S by in-situ gas chromatography.On the average, the highest mixing ratios of ethane, propane, i- and n-butane, ethene and acetylene were observed in the Northern Hemisphere around 40° N and just north of the intertropical convergence zone, respectively. South of the equator, a bulge in the mixing ratios of ethane and acetylene was observed indicating aged biomass burning emissions. This observation coincided with enhanced tropospheric ozone found in this region at this season. On the average ethane and acetylene mixing ratios were around 500 and 100 ppt, respectively, whereas the levels of the other NMHC were in the range of some ppt up to 100 ppt.compared with the results of the cruise ANT V/5 (March/April, 1987), the ethane mixing ratios in September/October proved to be a factor of 3 lower in the Northern Hemisphere and a factor of 2 higher in the Southern Hemisphere, probably due to seasonal effects. Possible causes are the higher OH radical concentrations in summer, which result in a faster removal of ethane or stronger emission from biomass burning which also peaks in the dry season.The relative pattern of the hydrocarbons just north of the ITCZ was very similar for both measurement series. In this region, the NMHC were advected by long-range transport from the continent, whereas generally the ocean itself acts as a major NMHC source. This is supported by the results of a balance calculation between oceanic emissions and atmospheric removal rates.     

Aerodynamic Roughness Length of Fresh Snow

This study presents the results from a series of wind-tunnel experiments designed to investigate the aerodynamic roughness length z ₀ of fresh snow under no-drift conditions. A two-component hot-film anemometer was employed to obtain vertical profiles of velocity statistics in a zero pressure gradient turbulent boundary layer for flow over naturally deposited snow surfaces. The roughness of these snow surfaces was measured by means of digital photography to capture characteristic length scales that can be related to z ₀. Our results show that, under aerodynamically rough conditions, the mean value of the roughness length for fresh snow is \({\langle{z}_{0}\rangle= 0.24}\) mm with a standard deviation σ(z ₀) = 0.05 mm. In this study, we show that variations in z ₀ are associated with variations in the roughness geometry. The roughness measurements suggest that the estimated values of z ₀ are consistent with the presence of irregular roughness structures that develop during snowfalls that mimic ballistic deposition processes.     

A suggested refinement for O'Brien's convective boundary layer Eddy exchange coefficient formulation

With observational data collected and interpreted by Crane et al. (1977), the adequacy of the O'Brien polynomial to represent the exchange profile of heat and pollution in a convective boundary layer is examined and a refinement suggested. Also, it is shown that the height of the surface layer, h=0.04 z _i , developed by Blackadar and Tennekes (1968) for a neutrally stratified boundary layer (with z _z =0.25u _*/f) appears to be equally valid for the convective boundary layer where z _i , defined as the top of the mixed layer, is used.     

Climatological aspects of Hadley, Walker and monsoon circulations in two phases of the Pacific Decadal Oscillation

Summary Reanalyzed 200 hPa velocity potential (χ) fields for the 1958–2005 period are used to examine the influences of the Pacific Decadal Oscillation (PDO) in the average Hadley, Walker and monsoon circulations. These circulations are quantified and separated from each other by computing their components contained in the 200 hPa χ fields for the 1958–1976 and 1977–1995 periods. The main results found here are that the Hadley and monsoon circulations show small differences between the two periods, while the Walker circulation shows weaker action centers during the second period, with its center in the western Pacific being located further west. The differences in intensity and locations of the main action centers of the Walker circulation between the first and second periods are analyzed here in terms of the PDO influences. Authors’ address: Mary T. Kayano, Samia R. Garcia, Instituto Nacional de Pesquisas Espaciais/CPTEC, Avenida dos Astronautas 1758, 12227-010 S?o José dos Campos, SP, Brazil.     

Impact of terrain complexity on the turbulence drag coefficient: A case study from the Indian Himalayan region

The aerodynamic drag coefficient (C_D) is conjectured to change (or remains almost uniform) with the horizontal wind speed (U) over a flexible (or fixed) surface element, which is represented with the surface roughness (z₀). This conjecture is tested for the near neutral atmospheric turbulence (i.e. when surface stability z/L is almost equal to 0, where z is the measurement height and L is Obukhov length) of monsoon and winter season at an on-slope and a ridge-top site in the Indian Himalaya, wherein the ridge-top site is associated with a higher degree of sensitivity to the roughness element and terrain attributes. This hypothesis is successfully verified for two conditions, (i) the monsoon period observations of ridge-top site are found to have higher z₀ due to vegetative growth than the winter period for flows having similar terrain signature, and (ii) the monsoon and winter period observations of on-slope site are noted to have similar z₀ for flows having signature of steep terrain. Subsequently, constants (i.e. a and b) of the power-law relationships between C_D and U (i.e. C_D = aU^b), as a function of z₀, are optimized. It is noted that the relationship between C_D and U has higher sensitivity towards the terrain slope than the vegetative growth.     

The Influences of Thermodynamic Characteristics on Aerodynamic Roughness Length over Land Surface

It has previously been shown that aerodynamic roughness length changes significantly along with nearsurface atmospheric thermodynamic state; however, at present, this phenomenon remains poorly understood, and very little research concerning this topic has been conducted. In this paper, by using the data of different underlying surfaces provided by the Experimental Co-observation and Integral Research in Semi-arid and Arid Regions over North China, aerodynamic roughness length (z₀) values in stable, neutral, and unstable atmospheric stratifications are compared with one another, and the relationship between z₀ and atmospheric thermodynamic stability (ζ) is analyzed. It is found that z₀ shows great differences among the stable, neutral, and unstable atmospheric thermodynamic states, with the difference in z₀ values between the fully thermodynamic stable condition and the neutral condition reaching 60% of the mean z₀. Furthermore, for the wind speed range in which the wind data are less sensitive to z₀, the surface z₀ changes more significantly with ζ, and is highly correlated with both the Monin-Obukhov stability (ζ₀) and the overall Richardson number (R_ib), with both of their correlation coefficients greater than 0.71 and 0.47 in the stable and unstable atmospheric stratification, respectively. The empirical relation fitted with the experimental observations is quite consistent with the Zilitinkevich theoretical relation in the stable atmosphere, but the two are quite distinct and even show opposite variation tendencies in the unstable atmosphere. In application, however, verification of the empirical fitted relations by using the experimental data finds that the fitted relation is slightly more applicable than the Zilitinkevich theoretical relation in stable atmospheric stratification, but it is much more suitable than the Zilitinkevich relation in unstable atmospheric stratification.     

Impact of surface variations on the momentum flux above the urban canopy

Based on the momentum flux–wind profile relationship of the Monin–Obukhov Similarity (MOS) theory, the observational data from the urban boundary layer field campaign in Nanjing are used to calculate the friction velocity ( $ {u_*} $ ) at the top of the urban canopy and the calculated results are evaluated. The urban surface roughness parameters (the roughness length z ₀ and zero-plane displacement height z _d) are estimated with the Ba method (Bottema’s morphological method). Two different regimes are employed for the calculations. In the homogeneous approach, z ₀ and z _d are averagely derived from the surface elements in the whole study area; while in the heterogeneous approach, z ₀ and z _d are locally derived from the surface elements in the corresponding upwind fetches (or source areas). The calculated friction velocities are compared to the measurement data. The results show that the calculated friction velocities from the heterogeneous approach are in better agreement with the observed values than those from the homogeneous approach are. This study implies that the local roughness parameters can properly represent the dynamical heterogeneity of urban surface, and its application can significantly improve the performance of parameterizations based on the MOS theory in the urban roughness sublayer.     

Characteristics of Turbulent Transfer during Episodes of Heavy Haze Pollution in Beijing in Winter 2016/17

We analyzed the structure and evolution of turbulent transfer and the wind profile in the atmospheric boundary layer in relation to aerosol concentrations during an episode of heavy haze pollution from 6 December 2016 to 9 January 2017. The turbulence data were recorded at Peking University’s atmospheric science and environment observation station. The results showed a negative correlation between the wind speed and the PM_2.5 concentration. The turbulence kinetic energy was large and showed obvious diurnal variations during unpolluted (clean) weather, but was small during episodes of heavy haze pollution. Under both clean and heavy haze conditions, the relation between the non-dimensional wind components and the stability parameter z/L followed a 1/3 power law, but the normalized standard deviations of the wind speed were smaller during heavy pollution events than during clean periods under near-neutral conditions. Under unstable conditions, the normalized standard deviation of the potential temperature σ _θ /|θ_*| was related to z/L, roughly following a –1/3 power law, and the ratio during pollution days was greater than that during clean days. The three-dimensional turbulence energy spectra satisfied a –2/3 power exponent rate in the high-frequency band. In the low-frequency band, the wind velocity spectrum curve was related to the stability parameters under clear conditions, but was not related to atmospheric stratification under polluted conditions. In the dissipation stage of the heavy pollution episode, the horizontal wind speed first started to increase at high altitudes and then gradually decreased at lower altitudes. The strong upward motion during this stage was an important dynamic factor in the dissipation of the heavy haze.     

Trace elements in the atmospheric aerosols at Delhi,North India

The total suspended particulate (TSP) levels at Delhi (north India) were measured on 116 days between February and October 1980. The observations were stratified according to season and the values of cross-correlation of the TSP and its components were evaluated. High TSP (209 g m^-3) levels were found during the summer period associated with hot and dry weather in the region and low TSP (109 g m^-3) were found during the monsoon period. Most of the TSP mass was associated with natural soil elements, such as Fe, Al, Mn, Ca, and K. Only a fraction of the mass of the TSP was comprised of elements from anthropogenic sources, e.g., Pb, Ni, Cd, Sb, Cu, and Zn. The aerosols at Delhi were potentially basic in nature, unlike those in European countries which are acidic in nature and cause acid rainfall.