NO<Subscript>2</Subscript> content variations near St. Petersburg as inferred from ground-based and satellite measurements of scattered solar radiation

An automatic spectral complex developed at the Institute of Physics, St. Petersburg State University, is described. This complex is used for regular ground-based spectroscopic measurements of the total NO₂ content in the vertical column of the atmosphere during the twilight and daylight hours of the day near St. Petersburg (Petrodvorets). In 2004–2006, a number of ground-based twilight measurements of the total NO₂ content were obtained near St. Petersburg, and variations in the NO₂ content in the troposphere were estimated from the results of daytime ground-based measurements. An example of the spatial annual mean distribution of the NO₂ content (central and northern Europe, northwestern Russia) based on the data of satellite measurements over the period 2003–2005 is presented. This example demonstrates the main sources of anthropogenic pollution. An increase in the mean annual contents of tropospheric NO₂ near Moscow and St. Petersburg is preliminarily estimated for the entire period of satellite observations with the GOME instrument at about 30–40% over ten years.     

Nitrogen dioxide in the air basin of St. Petersburg: Remote measurements and numerical simulation

The results of ground-based and satellite spectroscopic measurements of the tropospheric NO₂ content near St. Petersburg in January–March 2006 are presented. It is shown that the increased concentrations of NO₂ observed in St. Petersburg and its vicinities in this period were caused by NO₂ accumulation due to unfavorable weather conditions, which is confirmed by an analysis of meteorological data and the results of a numerical simulation of the dispersion of urban air pollutants. Data from satellite and ground-based measurements agree with each other satisfactorily (a correlation coefficient of 0.5) and with model calculations of tropospheric NO₂ conducted for the coordinates of a station of ground-based measurements (a correlation coefficient of 0.6). The HYSPLIT dispersion model also made it possible to estimate the scale of the NO₂ spatial-temporal variability in the near-surface layer in the vicinities of St. Petersburg.     

Integral emission of nitrogen oxides from the territory of St. Petersburg based on the data of mobile measurements and numerical simulation results

The results of spectroscopic measurements of tropospheric NO₂ content performed on a closed route along the circular road around the city of St. Petersburg in 2012, 2014, and 2015 are presented. A procedure for determining the integral emission of NO _x based on the data of measurements on the route enveloping the sources under study is described. An analysis of the experimental data together with the results of a numerical simulation of air pollutant dispersion (the HYSPLIT model) provided an estimate of the total volume of NO _x emitted by all sources located inside the circular road. The average emission rate of NO _x according to the sources of the megacity of St. Petersburg is 57000 t/yr, which correlates satisfactorily with the official data of a municipal inventory of the sources of air pollution (62000–63 000 t/yr).     

Comparing data obtained from ground-based measurements of the total contents of O<Subscript>3</Subscript>, HNO<Subscript>3</Subscript>,HCl,and NO<Subscript>2</Subscript> and from their numerical simulation

Chemistry climate models of the gas composition of the atmosphere make it possible to simulate both space and time variations in atmospheric trace-gas components (TGCs) and predict their changes. Both verification and improvement of such models on the basis of a comparison with experimental data are of great importance. Data obtained from the 2009–2012 ground-based spectrometric measurements of the total contents (TCs) of a number of TGCs (ozone, HNO₃, HCl, and NO₂) in the atmosphere over the St. Petersburg region (Petergof station, St. Petersburg State University) have been compared to analogous EMAC model data. Both daily and monthly means of their TCs for this period have been analyzed in detail. The seasonal dependences of the TCs of the gases under study are shown to be adequately reproduced by the EMAC model. At the same time, a number of disagreements (including systematic ones) have been revealed between model and measurement data. Thus, for example, the EMAC model underestimates the TCs of NO₂, HCl, and HNO₃, when compared to measurement data, on average, by 14, 22, and 35%, respectively. However, the TC of ozone is overestimated by the EMAC model (on average, by 12%) when compared to measurement data. In order to reveal the reasons for such disagreements between simulated and measured data on the TCs of TGCs, it is necessary to continue studies on comparisons of the contents of TGCs in different atmospheric layers.     

Regional space monitoring of nitrogen dioxide in the troposphere

Satellite instruments for the routine global monitoring of NO₂ in the atmosphere—the Global Ozone Monitoring Experiment (GOME) on the ERS-2 satellite, the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) on the ENVISAT satellite, the Ozone Monitoring Instrument (OMI) on the AURA satellite, and the GOME-2 on the MetOp satellite—are briefly described. It is shown that the error of measuring the NO₂ total column amount (∼10% for the background conditions in the troposphere) substantially increases in regions subject to anthropogenic pollution. Examples of practically using multiyear satellite measurements for the regional monitoring of NO₂ in the troposphere are presented, including mapping the tropospheric NO₂ in Russia, identifying the weekly and annual cycles in tropospheric NO₂ variations for megalopolises (St. Petersburg, Moscow, Paris), and estimating the long-term linear trend in 1995–2007.     

Stratospheric NO2 content according to data from ground-based measurements of solar IR radiation

Atmospheric NO₂ content data obtained from regular ground-based measurements of solar IR radiation in the St. Petersburg region using a spectrometer with a high spectral resolution are analyzed. The absorption spectra of the NO₂ multiplet in the vicinity of ～2915 cm^?1 allow one to obtain data on variations in the stratospheric total content of NO₂ in 2009–2011. The accuracy of these data is estimated from their comparison with data obtained from independent ground-based and satellite measurements. The parameters of the seasonal cycle of the stratospheric content of NO₂ are estimated. The body of data accumulated during these measurements in the IR region made it possible to isolate the component of a daytime photochemical increase in the stratospheric content of NO₂ and estimate its rate.     

Validating NO<Subscript>2</Subscript> measurements in the vertical atmospheric column with the OMI instrument aboard the EOS Aura satellite against ground-based measurements at the Zvenigorod Scientific Station

Data on the NO₂ content in the vertical column of the atmosphere obtained with the Ozone Monitoring Instrument (OMI) aboard the EOS Aura satellite (United States) in the period from October 2004 to October 2007 are compared with the results of ground-based measurements at the Zvenigorod Scientific Station (55.7° N, 36.8° E). The “unpolluted”; part of the total NO₂ content in the atmospheric column, which mostly represents the stratosphere, and the NO₂ contents in the vertical column of the troposphere, including the lower layer, which is subject to pollution, are included in the comparison. The correlation coefficient between the results of ground-based and satellite measurements of the “unpolluted” total NO₂ content is ∼0.9. The content values measured with the OMI instrument are smaller than the results of ground-based measurements (on average, by (0.30 ± 0.03) × 10¹⁵ cm⁻² or by (11 ± 1)%). Therms discrepancy between the satellite and ground-based data is 0.6 × 10¹⁵ cm⁻². The NO₂ content in the vertical column of the troposphere from the results of satellite measurements is, on average, (1.4 ± 0.5) × 10¹⁵ cm⁻², (or about 35%) smaller than from the results of ground-based measurements, and the rms discrepancy between them is about 200%. The correlation coefficient between these data is ∼0.4. This considerable discrepancy is evidently caused by the strong spatial (horizontal) inhomogeneity and the temporal variability of the NO₂ field during episodes of pollution, which leads to different (and often uncorrelated) estimates of the NO₂ content in the lower troposphere due to different spatial resolutions of ground-based and satellite measurements.     

Assessment of the influence of air invasions from the upper troposphere on the CO total column amount in the St. Petersburg region

The influence of air invasions from the upper troposphere on the CO total column amount is studied on the basis of spectroscopic measurements of the CO total column amount, backward trajectories of air-mass motions (the HYSPLIT model), and meteorological data. It is shown that the observed invasions of substratospheric and upper-troposphere air masses determine the minimum CO total column amount in late January-late March. The invasion of air masses from the upper troposphere can result in a decrease in the CO total column amount to 30% (of its mean values). Using January 31, 2000, as an example, we show the influence of the invasion of Arctic air masses from the upper troposphere on the CO total column amount in the St. Petersburg region: the results of measurements of the CO total column amount in the St. Petersburg region and at the Kiruna polar station (NDACC) are in agreement to within 1% if the vertical transport of air masses is taken into account. Thus, for a correct combined analysis of measurement data on the CO total column amount for different observation stations, it is necessary to use data on air-mass trajectories.     

Gaseous admixtures in the atmosphere over Moscow during the 2010 summer

In the summer of 2010, the Moscow megacity during two months was within the zone of action of a blocking anticyclone. The accumulation of pollutants in a closed air mass sharply changed the surface air quality. At the end of July-the first half of August, the extreme situation became even more complicated, because the air from regions of turf and grass fires came into Moscow. According to measurement data of the Moscow IAP RAS station, the maximal hourly mean concentrations of chemically active gases NO, NO₂, CO, O₃, and SO₂ were 175.9, 217.4, 15.8, 134.2, and 15.2 ppb, respectively. For NO₂ and CO, these values are largest over the entire decadal period of observations at the station and many times exceed the MPC level (see table). The concentrations of greenhouse gases CO₂, CH₄, and nonmethane hydrocarbons also sharply increased. Analysis of the variability of gas contents in the surface air and in the atmospheric boundary layer showed a close relation between extreme changes in the atmospheric composition and its vertical stratification.     

Variability of trace gases in the atmospheric surface layer from observations in the city of Moscow

The results of continuous minute measurements of the surface concentrations of ozone, nitric oxide, nitrogen dioxide, carbon monoxide, and sulfur dioxide during the 2002–2004 period at the environmental station of the Oboukhov Institute of Atmospheric Physics, Russian Academy of Sciences (IAP), and the Faculty of Geography, Moscow State University (MSU), are discussed. It is shown that the conditions of Moscow’s southwestern region remote from large local pollution sources reflect the general regularities of the variability of trace gases in an urban atmosphere. This is manifested in the mean annual value of the ratio NO/NO₂ (a little less than 1), decreased daylight values of O₃, increased values of the rest of the trace gases as compared to the background region, and the presence of a secondary nocturnal maximum in the diurnal cycle of O₃. The features of the annual and diurnal cycles of the concentrations of the substances under analysis are discussed. In the diurnal cycle of the primary products of combustion (NO and CO), an excess of the morning maximum (over the evening one) is observed during both warm and transition periods and higher values of the night maximum (as compared to the daylight one) are noted for summer. The temperature stratification properties determined from the MSU long-term acoustic sounding data serve as a possible cause for both of the effects revealed. The annual cycle of the concentration of surface ozone is characterized by the highest values for spring and summer. The annual cycles of NO, NO₂, CO, and SO₂ do not demonstrate any obvious seasonal regularities. A significant seasonal variation of the ratio NO/NO₂, which is associated with the oxidizing properties of the urban atmosphere, is revealed. The record high concentrations of trace gases in the atmosphere over Moscow are given, and the meteorological conditions for their accumulation are discussed.     

Winter–spring anomalies in stratospheric O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> contents over the Moscow region in 2010 and 2011

Using results of ground-based spectrometric measurements, we analyze the anomalies in the stratospheric contents of O₃ and NO₂ in the Moscow region related to the sudden stratospheric warming and associated distortion of the stratospheric circumpolar vortex in early February 2010 and to the latitudinal displacement of the vortex towards the European sector in late March 2011 before the final spring warming. In the former case, the O₃ concentration increased up to 85% and the stratospheric column NO₂ content increased twice; in the latter case, the O₃ concentration decreased by a quarter and the NO₂ content decreased twice in comparison with average values for the time periods preceding the onsets of the anomalies. Estimates of the statistical correlationship of the stratospheric O₃ and NO₂ contents with potential vorticity and geopotential have been obtained.     

The effects of sodium sulfate on the emissions characteristics of an emulsified marine diesel oil-fired furnace

Degraded diesel oils are commonly used in marine power plants to conform to the demands of shipowners for fuel economy. The burning of these marine fuel oils, which frequently contain various extents of oxides of iron, silicon, calcium, vanadium and potassium, such as Na₂SO₄, Fe₂O₃, SiO₂, CaO, V₂O₅, etc., are susceptible to form much more complex compounds of either gaseous or solid phases. The release of these emissions to the environment may cause atmospheric pollution and a health hazard to human beings. Emulsification of a fuel oil with water to produce a micro-water-particles-dispersed-in-oil (W/O) emulsion has been considered as one of the promising techniques to improve combustion characteristics of low-grade marine oils and in turn effectively help to reduce the release of air pollutants. Marine fuel oil A, which approximates ASTM No. 2D oil was used as the test oil and the surfactant Span 80 was used to promote the affinity and integrating force between the components of the emulsion. An emulsifying/homogenizing machine was employed to stir the emulsion mixture of the marine oil, distilled water, surfactant Span 80 and sodium sulfate (Na₂SO₄) powder of 300 ppm. The mechanically blended emulsion mixture was injected, atomized and burned in an oil-fired furnace using an automatic burner. Burning gas composition, burning efficiency and gas temperature were measured and analyzed. Compared to neat marine diesel oil, W/O emulsions had higher combustion efficiencies, higher concentrations of O₂ and SO₂, while gas temperatures were lowered and CO and NO_x production was reduced. The addition of sodium sulfate decreased combustion efficiency and NO_x concentration and increased O₂, CO, and SO₂ concentrations.     

Ground-based spectroscopic measurements of the total nitric acid content in the atmosphere

The results of the first ground-based spectroscopic measurements in Russia of the total content (TC) of nitric acid in the atmosphere near St. Petersburg over the period April 2009–October 2011 are presented. These measurements show a substantial seasonal trend of the HNO₃ TC with maximal values in the winter period and early in the spring and minimal values in the summer time. The seasonal trends and variations in the daily mean values of HNO₃ TC near St. Petersburg in the winter and spring periods agree well with observations at the Kiruna station of the international NDACC network.     

Analysis of the weekly cycle in the atmosphere near Moscow

Using the spectral method and the method of grouping by days of week, we analyzed the weekly cycles by standard air sounding data obtained at the Dolgoprudny station near Moscow and by the results of measurements of NO₂ content in the stratosphere and the atmospheric boundary layer at the Zvenigorod Research Station of the Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, in 1990–2010. We revealed weekly cycles of the NO₂ content in the vertical column of the stratosphere, temperature, geopotential, meridional wind velocity in the troposphere and lower stratosphere, and the tropopause height in the warm half of the year (mid-April to mid-October). The weekly variations in temperature in the troposphere are positive in the first half of the week and negative in the second half, and the variations in temperature in the tropopause layer and in the lower stratosphere are opposite in sign to the tropospheric variations. The weekly cycle of the tropopause height is approximately in phase with the cycle of tropospheric temperature, and the weekly cycle of the NO₂ content in the stratospheric column is opposite in phase to the cycle of the tropopause height. Weekly variations were also observed in the total ozone content over Moscow. This finding was confirmed by calculations based on regression relationships between the vertical distribution of ozone and tropopause height. Conceptual mechanisms of weekly cycles were proposed.     

Variations in the column-average dry-air mole fractions of CO2 in the vicinity of St. Petersburg

The results obtained from ground-based spectroscopic measurements of column-average dry-air mole fractions of CO₂ in the atmosphere over the St. Petersburg region are given for the period April 2009–October 2011 (～900 measurement runs, 151 measurement days). These results show significant variations in the CO₂ mixing ratio in the atmosphere over the St. Petersburg region. The minimum value of this mixing ratio (373.1 ppm) was observed on April 27, 2011, and its maximum value (420.8 ppm) was observed on February 10, 2010. The typical seasonal behavior of the CO₂ mixing ratio with its summer minimum was observed in 2009. In July 2010 and 2011, the values of the CO₂ mixing ratio increased apparently due to high air temperatures. In 2010 an additional contribution to this increase in the CO₂ mixing ratio could have been made by strong natural fires.     

Peculiarities of the disturbance in the mesosphere composition and optical emissions caused by high-altitude discharges

The suggested equation system, including 267 chemical reactions and corresponding parametrizations of disturbances of the electric field and electron temperature, describes the dynamics of the mesosphere composition under the influence of high-altitude discharges (sprites and halos). Based on this system, the ionic disturbance, neutral components, and optical emissions of the night mesosphere caused by the sprites were modeled for a height of 77–85 km. Most attention was paid to the dynamics of disturbances of concentrations of electrons and O ₂ ⁺ , NO⁺, H₃O⁺, H₅O ₂ ⁺ , and N ₂ ⁺ typical of the studied heights. The major chemical reactions leading to the disturbance of ionic contents are determined and the relaxation dynamics of the chemical components is reviewed. The account of the excited atoms and molecules of nitrogen and oxygen allowed us to model the radiation of the sprite flash, calculate the volumetric velocity of the photon emission, and study the influence of the sprite on the neutral components of the mesosphere.     

Emission characteristics of marine furnaces burned at varying inlet air temperatures and humidity

Marine power plants are frequently operated under varying atmospheric air temperature and humidity conditions. The effects of inlet air temperatures and humidity of marine furnaces such as incinerators and boilers thus attract much research interest. An industrial furnace incorporated with an automatic burner was employed to experimentally investigate the influences of the inlet air temperature and humidity on the emission characteristics. The inlet air humidity and temperature were adjusted using an air-conditioning machine to preset values before being admitted into the burner. ASTM No. 2D diesel oil was atomized, mixed with the inlet air and burned inside the industrial furnace. Eight small rectangular slots were cut on the upper side of the furnace to allow gas analyzer and thermocouple probes to be inserted into the furnace center to measure the axial variations in the gas temperature, burning efficiency and burning gas compositions such as NO_x, SO₂, CO. The experimental results show that the O₂ and NOx emission concentrations decreased while the CO₂ emission concentration and burning efficiency increased with either increasing inlet air humidity or temperature.     

A model of the impact of solar proton events on the ionic and gaseous composition of the mesosphere

A one-dimensional ionic-photochemical model of the gaseous composition of the atmosphere that describes the formation of the D layer of the ionosphere is presented. Based on this model, the vertical profiles of the concentration of electrons and ions in the D layer of the ionosphere were calculated, as were the vertical distributions of minor gaseous constituents in the atmosphere up to a height of 86 km for undisturbed conditions and after a powerful solar proton events (SPE) at the end of October 2003. The calculations showed that SPEs significantly increase NO_x in the mesosphere of polar latitudes. In the lower mesosphere of polar caps, the NO_x mixing ratio increases by 20–50 ppb; in the upper mesosphere it increases by 100 ppb and more. High NO_x levels in zones of their formation can be retained for several weeks, producing a long-term but comparatively small ozone decrease in the lower mesosphere. The main ozone decrease is caused by a short-term HO_x increase after SPEs and is also of a short-term character in the conditions of the illuminated mesosphere. After the SPE in October 2003, model calculations yield an ozone concentration decrease by 40% in the middle and upper mesosphere at 75 ° S and by 70% at the same heights at 70 ° N. The results of modeling NO_x and O₃ changes after the SPE in October 2003 agree well with the data of satellite measurements. The changes in minor gases of the mesosphere after the SPE obtained in the model with parameterized sources of HO_x and NO_x are compared with their changes obtained in the complete ionic-photochemical model. The changes in HO_x, NO_x, and O₃ coincide rather well, whereas the changes in ClO noticeably differ, especially in the lower mesosphere. Thus, at a height of about 60 km, the parameterized photochemical model underestimated twofold the ClO formation after the SPE.     

Air pollution over European Russia and Ukraine under the hot summer conditions of 2010

Variations in the concentrations of both primary (PM₁₀, CO, and NO_x) and secondary (ozone) pollutants in the atmosphere over the Moscow and Kirov regions, Kiev, and Crimea under the conditions of the anomalously hot summer of 2011 are given and analyzed. The concentrations of ozone, PM₁₀, CO, and NO_x in the atmosphere over the Moscow region exceeded their maximum permissible levels almost continuously from late July to late August 2010. The highest level of atmospheric pollution was observed on August 4–9, when the Moscow region was within a severe plume of forest and peatbog fires. The maximum single concentrations of ozone, which exceeded its maximum permissible level two-three times, were accompanied by high concentrations of combustion products: the concentrations of PM₁₀ and CO were also three-seven times higher than their maximum permissible concentrations. The maximum levels of air pollution were observed under the meteorological conditions that were unfavorable for pollution scattering, first of all, at a small vertical temperature gradient in the lower atmospheric boundary layer. The number of additional cases of mortality due to the exceeded maximum permissible concentrations of PM₁₀ and ozone in the atmosphere over Moscow was estimated. Under the weather conditions that were close to those for the Moscow region, the air quality remained mainly satisfactory in the Kirov region, Kiev, and Crimea, which were almost not affected by fires.     

Microscale gradients of planktonic microbial communities above the sediment surface in a mangrove estuary

The microscale (1 and 4 cm sampling resolution) distributions of chemical (O₂, NH₃, NO₃⁻, NO₂⁻, PO₄³⁻) and biological (Chl a, phytoplankton, bacterioplankton, viruses) parameters were measured in the 16 cm of water immediately overlaying the sediment-water interface (SWI) within a temperate mangrove estuary in South Australia during December 2003 and March 2004. Shear velocities (u_*) during the time of sampling were very low (<0.1 cm s⁻¹), and we consequently predict that resuspension of organisms and materials was negligible. In December 2003, profiles were often characterised by strong gradients in nutrients and organisms, with the highest concentrations often observed within 0.5 cm of the SWI. Microscale patterns in O₂, NH₃, NO₃⁻ and NO₂⁻ indicated that a variety of anaerobic and aerobic transformation processes probably occurred at the SWI and within profiles. Strong gradients in PO₄³⁻ were indicative of nutrient flux across the SWI as a consequence of degradation processes in the sediments. Pico- and nanophytoplankton concentrations were strongly correlated (p < 0.01) to PO₄³⁻, and exhibited 12- and 68-fold changes in abundance, respectively, with highest concentrations observed nearest to the SWI. Several bacterial subpopulations were discriminated using flow cytometry and significant shifts in the ‘cytometric structure’ of the bacterial community were observed within microscale profiles. Two populations of viruses were correlated to the phytoplankton and low DNA (LDNA) bacteria, and each exhibited elevated concentrations within 0.5 cm of the SWI. In March 2004, microscale distributions of O₂ and nutrients were more homogenous than in December 2003, and dissimilar microbial community structure and patterns were observed above the SWI. The patterns observed here support the prediction that benthic processes can strongly influence the ecology of planktonic communities in the overlaying water, and provide further evidence for the existence of microscale variability amongst communities of aquatic microorganisms.