An experimental study on absorption properties of NO,NO2, NH3, CO2 and H2O by using line-tunable co laser

Measurements of absorption properties of some gases in the atmosphere were made by using CO line-tunable laser. Experimental equipment and method are briefly described. Absorption coefficients of NO, NO2, NH3, CO2 and H2O at some definite laser wavelengths are given, and variations of absorption properties with both partial and total pressures are discussed.     

Measurements of stratospheric NO2 profiles using a gas correlation radiometer in the solar occultation mode

Compact two-channel IR radiometers for solar occultation experiments have been constructed in order to measure concentration profiles of stratospheric trace gases. The instruments can be used as filter-or gas correlation-type radiometers depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the gas correlation-type measurements, profiles of the trace gas NO₂ are inferred for the altitude region between about 20 km and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the NO₂ profiles. The derived profiles are compared among themselves and are assessed against the observations of other authors by accounting for the diurnal, latitudinal and seasonal changes of NO₂. As a by-product of our measurements, the mean absorption of the O₂ collision-induced band at 6.4 m was determined within the range of the interference filter used and compared with calculations based on known absorption coefficients.     

Physicochemical Transformation and Photochemical Reactions in High-Disperse Substance State: Chemical Decomposition in Aerosols and Thin Films Made from Pesticide Fipronil (Adonis)

A chemical substance being in a high-disperse state (fine aerosol particles and very thin films) in the environment reveals specific chemical and physicochemical features which differ from the processes in a relatively coarse disperse object and, even more, in ordinary liquid and solid “test-tube” assays. The kinetics and the mechanism of the direct and sensitized photochemical destruction of pesticide compound fipronil C₁₂H₄Cl₂F₆N₄OS have been experimented as applied to the aerosol particles ≈0.12–1.3 μm in diameter and thin films ≈0.02–0.6 μm thick on the glass plates. A non-photochemical (“dark”) reaction of fipronil molecules with the OH radicals which spontaneously proceeds in the ambient air was also observed. Quantitative estimations based on experimental results show that the fipronil pollutant, observed in the atmosphere in the form of levitated aerosols, can convert chemically in the above reaction with the OH radicals for a very short time (from several minutes for a particle 2 μm in diameter to 12–24 h for a particle of 20–30 μm). The fipronil residues presented on foliage either in the form of 1–20 μm films or as a group of deposited 2–30 μm aerosols react under sunlight by two photochemical pathways (photooxidation and photodecay). The lifetime of these residues in the ambient conditions is expected to be 11–25 days. Besides, adding a small amount of the Shirvanol 2 sensitizer to the fipronil formulation, one can increase the overall decomposition rate to 8–12 days.     

Microscopic morphology and size distribution of particles in PM<Subscript>2.5</Subscript> of Guangzhou City

Samples of airborne PM_2.5 particles in Guangzhou urban area were collected during the autumn of 2006 and the spring of 2007. The morphologies and elemental compositions of individual particles were determined by Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectrometer (SEM-EDX). The obtained images were further analyzed for size distribution by an image analysis system. Based on the morphology, particles in PM_2.5 were classified into four groups: soot aggregates, minerals, fly ash and others. The amount of soot aggregates and minerals were higher than that of fly ashes. The distributions of particles by number and size in two seasons were bimodal with 90% less than 1.0 μm in diameter. The primary peak from the autumn samples was in the size range of 0.4 ~ 0.5 μm, and 0.3 ~ 0.4 μm for the spring samples. More soot aggregates (36.1%) and minerals (61.5%) were found than fly ash (2.4%) in autumn, but soot aggregates (89.9%) was the dominant particle type in spring. The size distribution of particles according to the volume was generally opposite to that according to the number. Particles less than 1.0 μm were as high as 89.5% in number but contributed only 18.9% in volume, indicating that fine particles contributed relatively little in volume although existing in large numbers.     

Laser desorption/ionization mass spectrometric study of secondary organic aerosol formed from the photooxidation of aromatics

Five aromatic hydrocarbons – benzene, toluene, ethylbenzene, p-xylene and 1,2,4-trimethylbenzene – were selected to investigate the laser desorption/ionization mass spectra of secondary organic aerosols (SOA) resulting from OH-initiated photooxidation of aromatic compounds. The experiments were conducted by irradiating aromatic hydrocarbon/CH₃ONO/NO _X mixtures in a home-made smog chamber. The aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the aerodynamic size and chemical composition of individual secondary organic aerosol particles in real-time. Experimental results showed that aerosol created by aromatics photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and different aromatic hydrocarbons SOA mass spectra have eight same positive laser desorption/ionization mass spectra peaks: m/z = 18, 29, 43, 44, 46, 57, 67, 77. These mass spectra peaks may come from the fragment ions of the SOA products: oxo-carboxylic acids, aldehydes and ketones, nitrogenated organic compounds, furanoid and aromatic compounds. The possible reaction mechanisms leading to these products were also discussed.     

A Case Study of CO<Subscript>2</Subscript>, CO and Particles Content Evolution in the Suburban Atmospheric Boundary Layer Using a 2-μm Doppler DIAL,a 1-μm Backscatter Lidar and an Array of In-situ Sensors

A network of remote and in-situ sensors was deployed in a Paris suburb in order to evaluate the mesoscale evolution of the daily cycle of CO₂ and related tracers in the atmospheric boundary layer (ABL) and its relation to ABL dynamics and nearby natural and anthropogenic sources and sinks. A 2-μm heterodyne Doppler differential absorption lidar, which combines measurements of, (1) structure of the atmosphere, (2) radial velocity, and (3) CO₂ differential absorption was a particularly unique element of the observational array. We analyse the differences in the diurnal cycle of CO, CO₂, lidar reflectivity (a proxy for aerosol content) and H₂O using the lidar, airborne measurements in the free troposphere and ground-based measurements made at two sites located few kilometres apart. We demonstrate that vertical mixing dominates the early morning drawdown of CO and aerosol content trapped in the former nocturnal layer but not the H₂O and CO₂ mixing ratio variations. Surface fluxes, vertical mixing and advection all contribute to the ABL CO₂ mixing ratio decrease during the morning transition, with the relative importance depending on the rate and timing of ABL rise. We also show evidence that when the ABL is stable, small-scale (0.1-km vertical and 1-km horizontal) gradients of CO₂ and CO are large. The results illustrate the complexity of inferring surface fluxes of CO₂ from atmospheric budgets in the stable boundary layer.     

A parameterization of cooling rate calculation under the non-LTE condition: Multi-level model

Calculations of cooling rate by CO2 15 μm band in the earth’s upper mesosphere and lower thermosphere be-come very difficult because of the non-LTE. This is primarily due to the nonlinear vibration-vibrational (VV) transi-tion processes between CO2 molecules in different states. This paper suggests that the non-LTE source function be parameterized as a linear combination of two limiting source functions. One limiting source function neglects the VV transitions while the other limiting source function assumes VV transitions being dominant. These two limiting source functions can be derived by linear models. The parameterization schemes proposed here can be applied 10 the general circulation models including those non-LTE regions.     

Effect of atmospheric overlapping bands and their treatment on the calculation of thermal radiation

The effect of the overlapping band of atmospheric gases and its treatment on the calculation of flux and cooling rate due to the long wave radiation is investigated in detail by a new transmission model for overlapping bands, taking the 15 μm band of CO2 as an example. It is found that the presence of band overlapping has a quite significant influence on radiative fluxes and cooling rates in the upper stratosphere and the troposphere, in particular, at the earth's surface. However, in the middle-lower stratosphere, the overlapping effect appears to be insignificant. It is also shown that the usual wide-band transmission model treating the overlapping effect overestimates the net longwave fluxes in the lower stratosphere and, in particular, in the troposphere including the surface. But, in the middle-upper stratosphere, the contrary is the case.     

Quantum yields for the photodissociation of acetone in air and an estimate for the life time of acetone in the lower troposphere

The room-temperature photodecomposition of acetone diluted with synthetic air was studied at nine wavelengths in the spectral region 250–330 nm. The quantum yields for the products CO₂ and CO indicated that it was not possible to suppress secondary reactions sufficiently, even with acetone/air mixing ratios as low as 150 ppmv, to derive from these data primary acetone photodissociation quantum yields. The behavior of CO₂ and CO formation nevertheless provides some insight into the mechanism of acetone photodecomposition. When small amounts of NO₂ are added to acetone/air mixtures, peroxyacetyl nitrate (PAN) is formed. Quantum yields for PAN are reported. They are better suited to represent primary quantum yields for acetone photodissociation, because PAN is a direct indicator for the formation of acetyl radicals. The data were combined with absorption cross-sections for acetone measured at wavelengths up to 360 nm to calculate photodissociation coefficients applicable to the ground-level atmosphere at 40° northern latitude. Comparison with the rates for the reaction of acetone with OH radicals shows that both processes contribute almost equally to the total acetone losses in the lower atmosphere. The resulting atmospheric life time at 40° northern latitude is 32 days, on average. This value must be considered an upper limit, since it does not take into account acetone losses due to the reaction of excited triplet acetone with oxygen.     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

In situ Measurement of H2O and CH4 with Telecommunication Laser Diodes in the Lower Stratosphere: Dehydration and Indication of a Tropical Air Intrusion at Mid-Latitudes

Telecommunication laser diodes emitting near 1.39 m and 1.65 m in combination with direct-differential absorption spectroscopy are efficient tools to monitor in situ stratospheric H₂O andCH₄ with a good precision error (a few percents), a high temporal resolution (ranging from 10 ms to 1 s), a large dynamic range in the concentration measurements (four orders of magnitude) and a high selectivity in the analyte species. To illustrate the capability of laser probing technique, we report balloonborne H₂Oand CH₄ simultaneous measurements obtained on October 2001 atmidlatitudes (43° N). The H₂O vertical profile achieved with the lasersensor in the lower stratosphere is compared with the H₂O data yielded by a balloonborne frost-point hygrometer. The total hydrogen mixing ratio in the lower stratosphere, 2[CH₄] + [H₂O], appears to beconstant at 7.5 ± 0.1 ppmv. Nevertheless, an unexpected largedehydration of 0.5 ppmv was detected by both the laser sensor and thehygrometer between 16 km and 23 km. We suspect the occurrence of a tropicalair intrusion into mid-latitudes. We support this interpretation using a high-resolution advection model for potential vorticity.     

Atmospheric aerosol characterization in 2010 anomalous summer season in the Moscow region

Daily measurements of atmospheric aerosol characteristics were carried out in Dolgoprudny (Moscow region) in June–August 2010. The particle concentrations at 11 size gradations within the range of 0.01–10 μm and the concentrations of cloud condensation nuclei active at water vapor supersaturation of 0.2–1% were determined. It is shown that the long anticyclonic conditions and the burning of forests and peat bogs resulted in the increase in total aerosol concentration in surface air by more than 1.5 times and in concentrations of particles with the diameter of 0.1–1 μm and > 1 μm by 5 and 10 times, respectively. The fire smoke mainly consisted of the particles with the size of 0.1–3 μm. The particles with the size of more than 5 μm were not observed. The recurrent visibility decrease up to hundreds of meters was caused by the increase in the concentration of particles with the diameter of more than 0.32μm in the air. During the smoke blanketing, the concentration of active condensation nuclei in aerosol increased almost by 20 times that created an opportunity for watering of aerosol particles and formation of the acid smog.     

Extreme Particulate Levels at a Western Pacific Coastal City: The Influence of Meteorological Factors and the Contribution of Long-Range Transport

The 4-year data sets (1998–2001) of PM₁₀ and other gaseous pollutants at four rural and urban monitoring sites provided by Environmental Protection Department of Hong Kong have been analyzed for days of extremely high and low PM₁₀ levels. The annual means of PM₁₀ concentrations are between 37 and 57 μg/m³. The level of high PM₁₀ concentration is defined from the comparison of local and international standards. Episode days are mainly controlled by different meteorological conditions: the continental outflow, the land-sea breeze/weak synoptic forcings and the approaching tropical cyclones. Integrated approaches have been used to distinguish between the predominantly “territory wide” and “long-range transport” (LRT) episode days. Case studies of these types of episodes are presented and the number of episode days per year for each type has been estimated. It is found that the LRT contributions are significant and account for ∼66% of the PM₁₀ episode days. Very high correlations between CO and PM₁₀ concentrations, and between SO₂ and PM₁₀ concentrations, can be found during the “territory wide” episode days which implies the important contributions of fossil fuel combustion to the PM₁₀ episodes. The number of “low level” PM₁₀ days per year has decreased by a factor near 3 from 1998 to 2001. Precipitation scavenging is the major process causing low levels of PM₁₀, irrespective of the associated weather systems. The regional annual background level is ∼9 μg/m³. With the exception of seasalt components, the average elemental concentrations of major inorganic species are similar for all of the sites during LRT events and constitute representative compositions of PM₁₀ during such events.     

Particle composition and size distributions in and around a deep-pit swine operation,Ames, IA

The contribution of emissions from agricultural facilities is rapidly becoming a major concern for local and regional air quality. Characterization of particle properties such as physical size distribution and chemical composition can be valuable in understanding the processes contributing to emissions and ultimate fate of particulate matter from agricultural facilities. A measurement campaign was conducted at an Iowa, deep-pit, three-barn swine finishing facility to characterize near-source ambient particulate matter. Size-specific mass concentrations were determined using minivol samplers, with additional size distribution information obtain using optical particle counters. Particulate composition was determined via ion chromatographic analysis of the collected filters. A thermal-CO₂ elemental/organic carbon analyzer measured particulate carbon. The chemical composition and size distribution of sub-micron particles were determined via real-time aerosol mass spectrometry. Primary particulate was not found to be a major emission from the examined facility, with filter-based impactor samples showing average near-source increases (~15–50 m) in ambient PM₁₀ of 5.8 ± 2.9 μg m⁻³ above background levels. PM_2.5 also showed contribution attributable to the facility (1.7 ± 1.1 μg m⁻³). Optical particle counter analysis of the numerical size distributions showed bimodal distributions for both the upwind and downwind conditions, with maximums around 2.5 μm and below the minimum quantified diameter of 0.3 μm. The distributions showed increased numbers of coarse particles (PM₁₀) during periods when wind transport came from the barns, but the differences were not statistically significant at the 95% confidence level. The PM₁₀ aerosols showed statistically increased concentrations of sulfate, nitrate, ammonium, calcium, organic carbon, and elemental carbon when the samplers were downwind from the pig barns. Organic carbon was the major constituent of the barn-impacted particulate matter in both sub-micron (54%) and coarse size (20%) ranges. The AMS PM₁ chemical speciation showed similar species increases, with the exception of and Ca⁺², the latter not quantified by the AMS.     

Analysis of Carbon Dioxide Variations in the Atmosphere of Srednja Bijambarska Cave,Bosnia and Herzegovina

The results of one year’s monitoring in Srednja Bijambarska Cave (Bosnia and Herzegovina) are presented and discussed. Temporal variations of the carbon dioxide (CO₂) concentration are controlled by the switching between two ventilation regimes driven by outside temperature changes. A regression model with a simple perfectly mixed volume applied to a cave sector (“Music hall”) resulted in an estimate of ventilation rates between 0.02 h⁻¹ and 0.54 h⁻¹. Carbon dioxide input per plan surface unit is estimated by the model at around 50 × 10⁻⁶ mh⁻¹ during the winter season and up to more than 1000 × 10⁻⁶ mh⁻¹ during the first temperature falls at the end of summer (0.62 μmoles m⁻² s⁻¹ and 12.40 μmoles m⁻² s⁻¹ for normal conditions respectively). These values have been found to be related to the cave ventilation rate and dependent on the availability of CO₂ in the surrounding environment. For airflow close to zero the values of CO₂ input per plan surface have a range in the order of magnitude of a few units × 10⁻⁶ mh⁻¹. Based on two experiments, the anthropogenic contribution from cave visitors has been calculated, at between 0.35 l_CO2 min⁻¹ person⁻¹ and 0.45 l_CO2min⁻¹person⁻¹.     

Applying size segregation to relate the surrounding aerosol pollution to its source

Size segregated sampling of aerosol particles at the coal-fired power station Šoštanj, Slovenia was performed by a newly developed system. In addition, simultaneous sampling of particles was performed at two locations, Velenje and Veliki vrh, chosen on the basis of long term monitoring of SO₂ in the influential area of power plant. The signature of the power plant (e.g. characteristic size distributions of some typical trace elements) was identified. For elements, like As, Mo, Cd and Ga, which are typical for coal combustion, the highest concentrations were observed in the size range between 1 and 4 μm. For Se and sometimes for Ga two modes were identified, first between 0.1 and 0.5 μm and second between 1 and 4 μm. Ratios between the average concentrations of selected elements in fine and coarse particles collected at Veliki vrh (the most influenced location) and Velenje (usually not influenced by the thermo power station) were significantly higher than 1 in the case of Mo and Se for coarse and fine size range, while for As the ratio was higher than 1 for the coarse fraction. Consequently, Mo, Se and As were found as the most important tracers for the emissions from the investigated source. On the basis of the ratios between the concentrations of elements measured in particles at low and high SO₂ concentrations at Veliki vrh, Cd was shown to be a typical tracer as well. Our results definitely showed that size segregated measurements of particles at the source and in the influenced area give more precise information on the influence of source to the surrounding region. It was found that patterns of size distributions for typical trace elements observed at the source are found also in the influenced area, i.e. Veliki vrh.     

Airborne Lidar Observations of the Transition Zone Between the Convective Boundary Layer and Free Atmosphere During the International H<Subscript>2</Subscript>O Project (IHOP) in 2002

Airborne, light detection and ranging (lidar) backscatter observations of the convective boundary layer from the International H₂O Project (IHOP) in 2002 are analysed to study the structure of the transition zone; the backscatter gradient between the convective boundary layer and free atmosphere. A new mathematical algorithm is developed and used to extract high-resolution (15 m) transition-zone boundaries from 6,500 km (flight legs) of airborne observations. The cospectra of transition-zone boundaries and its thickness indicate that thickness changes occur from boundaries moving in opposite directions (vertically) at small wavelengths (<1 km), while at longer wavelengths (>1 km) both boundaries move coherently, with the lower boundary changing altitude more rapidly. Daily probability distributions of the transition-zone thickness are positively skewed with a mode of 60 m. The structure of the transition zone shows no dependence on the “overall” Richardson number, unlike the entrainment zone. This study provides the first quantitative characterization of the structure of the instantaneous transition zone, a contribution towards an improved understanding of convective boundary-layer entrainment.     

A study to discriminate local,urban and regional source contributions to the particulate matter concentrations in the city of Dresden,Germany

The fractions of local traffic (LT), urban background (UBG) and regional background (RBG) of the particle pollution at a traffic-influenced kerbside in Dresden, Germany, were determined by measurements of size-segregated mass concentration, chemical composition and particle size distributions in a network of five measurement stations partly existing and partly set up for this study. Besides the kerbside station, one urban background site and three rural sites were included in the study. Using data from these different sites, the LT, UBG, and RBG contributions were calculated, following the approach of Lenschow et al. (2001). At the kerbside site, 19% of the total number concentration (Dp_St = 10–600 nm) could be attributed to the RBG, 15% to the UBG, and 66% to the LT immediately nearby. Particle mass concentrations up to Dp_aer = 420 nm RBG amounts to 68%, UBG to 21%, and LT only to 11%. Highest mass concentrations were observed at all stations in autumn and winter during easterly inflow directions. The local traffic fraction of PM₁₀ mass at the kerbside station was found to be 30% for westerly inflow, but only 7% for southeasterly inflow due to the dominating transport fraction from up to 80% of the particle mass at this inflow direction. Size-resolved investigation showed the main fractions in both the particle size ranges of Dp_aer = 0.42 to 1.2 and 0.14 to 0.42 μm at all stations. The main components sulphate, ammonium and total carbon showed higher concentrations at south-eastern/eastern inflow in autumn at all stations, while nitrate at the kerbside and urban background site was higher during westerly inflow in winter. The chemical composition at the regional background site at westerly inflow (12% nitrate, 8% sulphate, 11% total carbon) was significantly different from that at easterly inflow (3% nitrate, 15% sulphate, 22% total carbon). The prevailing part of the ionic mass was always found in the fine particle range of Dp_aer = 0.14 to 1.2 μm at all stations. For all inflow directions highest total carbon concentrations were observed at the kerbside station, especially in the ultra-fine size range of Dp_aer = 0.05 to 0.14 μm with up to 30% of the whole carbon. PAH concentrations were always higher at south-eastern/eastern inflow especially during wintertime. Trace metal components and silicon were found mainly in the coarse mode fraction at the kerbside resulting from abrasion or resuspension.     

Modelling dust distributions in the atmospheric boundary layer on Mars

A time and height dependent eddy diffusion model is used to investigate possible scenarios for the size distribution of dust in the lower atmosphere of Mars. The dust is assumed to either have been advected from a distant source or to have originated locally. In the former case, the atmosphere is assumed to initially contain dust particles with sizes following a modified gamma distribution. Larger particles are deposited relatively rapidly while small particles are well mixed up to the maximum height of the afternoon boundary layer and are deposited more slowly. In other cases, a parameterization of the dust source at the surface is proposed. Model results show that smaller particles are rapidly mixed within the Martian boundary layer, while larger particles (r > 10 μm) are concentrated near the ground with a stronger diurnal cycle. In all simulations we assume that the initial concentration or surface source depend on a modified gamma function distribution. For small particles (cross- sectional area weighted mean radius, r_eff = 1.6 μm) distributions retain essentially the same form, though with variations in the mean and variance of the area-weighted radius, and the gamma function can be used to represent the particle size distribution reasonably well at most heights within the boundary layer. In the case of a surface source of larger particles (mean radius 50 μm) the modified gamma function does not fit the resulting particle size distribution. All results are normalised by a scaling factor that can be adjusted to correspond to an optical depth for assumed particle optical scattering properties.     

Peculiarities of seasonal variations of atmospheric aerosol concentration in the surface air of Moscow environs

The seasonal variations of the concentration of particles of different sizes in the atmospheric surface layer are studied on the basis of the data of daily measurements of atmospheric aerosol characteristics in the town of Dolgoprudny (20 km from the center of Moscow) carried out in 2006–2009. It is revealed that the steady variations of monthly mean aerosol concentration are observed within the particle diameter interval of 0.02–1 μm. The annual course of concentration of these particles has two maxima, in February-March and in September–October, and one minimum in June. The concentrations of particles with the size of 0.01–0.02 μm defined by the general atmospheric background and the concentrations of particles of >1 μm associated with the local sources do not have clearly pronounced seasonal variations. It is shown that the regularities of the annual concentration variations of particles with the size of 0.02–1 μm are mainly explained by the sign and value of the lapse rate in the layer up to 925 hPa that indicates the prevalence of the vertical mixing in the processes of aerosol scattering in the surface layer as compared with the horizontal transfer.