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.     

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.     

Dynamics of surface-air pollution during the passage of a cold front

The dynamics of meteorological parameters, of sodar data on the temperature stratification of the atmospheric boundary layer, and of surface contents of pollutants (nitrogen oxides, carbon monoxide, and ozone) during the passage over Moscow of a structurally complex prominent cold front are discussed. It is shown that the cold front passage is accompanied by stepwise increases in the NO, NO₂, and CO surface contents. A probable cause of this phenomenon is a quick entrainment of smoke plumes from high-altitude sources of pollution into the surface turbulent air near the frontal boundary. Intense advection of cold air at the rear of the cyclone can lead to the development of an unstable stratification in the atmospheric boundary layer even in the nighttime. Under these conditions, the minute-scale variability of contents of trace gases increases abruptly as compared to that occurring in the frontal zone of the cyclone prior to the passage of the front. This effect is statistically significant. The dynamics of surface ozone reflects an increase in its background concentrations in arctic air masses.     

Methane, carbon monoxide, and carbon dioxide concentrations measured in the atmospheric surface layer over continental Russia in the TROICA experiments

The principal statistical regularities typical of the behaviors of the CH₄, CO, and CO₂ concentrations in the atmospheric surface layer over the continental Russian territory are revealed from the measurements performed in 1997–2004 along the Trans-Siberian Railroad from Moscow to Khabarovsk with a mobile laboratory. The data obtained under the conditions of the atmosphere free of anthropogenic pollutants are analyzed. For near-background conditions, the typical continental methane, carbon monoxide, and carbon dioxide concentrations and characteristic features of their large-scale spatial distributions and daily variations, including those caused by surface inversions, are determined. Variations in the concentrations of these trace gases over industrial regions are analyzed. Our results are compared to the data obtained at background stations of the world network of atmospheric monitoring and to the data of a numerical simulation.     

Temporal variations in carbon dioxide and methane concentrations under urban conditions

Temporal variations in the surface concentrations of two greenhouse gases (carbon dioxide and methane) in the atmosphere over a large city are studied on the basis of the data obtained during the 2003–2005 observations at a Moscow station for environmental monitoring. This station is based on the TROICA mobile observatory and located at the meteorological station of the Faculty of Geography, Moscow State University, on Vorob’evy gory. The methods of isolating the background concentrations of greenhouse gases under urban conditions are proposed, and the excess concentrations of CO₂ and CH₄ over their background values are estimated for different seasons and times of day. The CO₂ and CH₄ concentrations are shown to have more pronounced diurnal cycles in summer than in winter. The main causes of temporal variations in the surface concentrations of CO₂ and CH₄ under urban conditions and the differences between the mean concentrations of these greenhouse gases in Moscow and other areas of Russia are analyzed. It is shown that variations in the surface concentrations of carbon dioxide and methane on different time scales are caused by different atmospheric processes (global circulation, mesoscale gravity waves, surface temperature inversions, etc.)     

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.     

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.     

Carbon dioxide in surface seawaters of the Seto Inland Sea,Japan

Observations were made of time variations of carbon dioxide in seawater, pCO₂, and in the atmosphere, PCO₂, in the Seto Inland Sea of Japan. The pCO₂ data showed well defined diurnal variation; high values at nighttime and low values during daylight hours. The pCO₂ correlated negatively with dissolved oxygen. These results denote that the diurnal variation of pCO₂ is associated with effects of photoplankton's activity in seawater. The pCO₂ measured in the Seto Inland Sea showed higher values than the PCO₂ during June to November, denoting transport of carbon dioxide from the sea surface to the atmosphere, and lower values during December to May, denoting transport of carbon dioxide from the atmosphere to the sea surface. The exchange rates of carbon dioxide were calculated using working formula given by Andriéet al. (1986). The results showed that the Seto Inland Sea gained carbon dioxide of 1.0 m-mol m^–2 d^–1 from the atmosphere in March and lost 1.7 m-mol m^–2 d^–1 to the atmosphere in August.     

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.     

A role for nitrite in the production of nitrous oxide in the lower euphotic zone of the oligotrophic North Pacific Ocean

Understanding the role of the oceans in the Earth's changing climate requires comprehension of the relevant metabolic pathways which produce climatically important trace gases. The global ocean represents one of the largest natural sources of nitrous oxide (N₂O) that is produced by selected archaea and/or bacteria during nitrogen (N) metabolism. In this study, the role of nitrite (NO₂⁻) in the production of N₂O in the upper water column of the oligotrophic North Pacific Subtropical Gyre was investigated, focusing primarily on the lower euphotic zone where NO₂⁻ concentrations at the primary NO₂⁻ maximum reached 195 nmol L⁻¹. Free-drifting sediment trap arrays were deployed to measure N cycle processes in sinking particulate material and the addition of selected N substrates to unpreserved sediment traps provided an experimental framework to test hypotheses regarding N₂O production pathways and controls. Sinking particles collected using NO₂⁻-amended, unpreserved sediment traps exhibited significant production of N₂O at depths between 100 and 200 m. Subsequent stable isotope tracer measurements conducted on sediment trap material amended with ¹⁵NO₂⁻ yielded elevated δ¹⁵N values of N₂O, supporting N₂O production via a NO₂⁻ metabolism pathway. Experiments on seawater collected from 150 m showed N₂O production via NO₂⁻ metabolism also occurs in the water-column and indicated that the concentration of NO₂⁻ relative to NH₄⁺ availability may be an important control. These findings provide evidence for the production of N₂O via nitrifer-denitrification in the lower euphotic zone of the open ocean, whereby NO₂⁻ is reduced to N₂O by ammonia-oxidizing microorganisms.     

Latitudinal dependence of variations in stratospheric NO<Subscript>2</Subscript> content

Diurnal and annual variations in the NO₂ total content (TC), the effect of its decrease owing to the products of the eruption of Mt. Pinatubo, its variations during an 11-year cycle of solar activity, and its linear trends are analyzed on the basis of data obtained from the ground-based spectrometric measurements of the NO₂ TC in stratospheric vertical columns over the stations of the Network for the Detection of Atmospheric Composition Change. Latitudinal dependence of the indicated variations and trends is revealed. The annual estimates of the linear trends of the NO₂ TC are found to be mostly positive for the middle and low latitudes of the Southern Hemisphere and negative for the middle and low latitudes of the Northern Hemisphere. The maximum values of the positive and negative trends amount to ～10% per ten years. In the high and polar latitudes of both hemispheres, the annual trend estimates are statistically insignificant. Seasonal estimates of the trends may differ from their annual estimates. The trends and solar-activity effect in the NO₂ TC, which were estimated by using the two-dimensional model SOCRATES, as well as the analytical estimates of a zonal mean trend of the NO₂ TC, on the whole, significantly differ from the estimates obtained from the measurements.     

Time variability of the total methane content in the atmosphere over the vicinity of St. Petersburg

The results of measuring the methane content in the entire atmospheric thickness over the St. Petersburg region are given for 1991–2007. It is shown that, within this period, the mean annual cycle of the total methane content is characterized by its maximum values in December–January and its minimum values in June–August when the annual-cycle amplitude amounts to ∼3.6%. In this case, the annual variations in the total methane content may differ significantly from the mean annual cycle obtained in some years. A statistically significant linear trend of the total CH₄ content has not been revealed for 1991–2007. The obtained values of the linear-trend index have opposite signs in the winter and summer months (positive for January 0.6 ± 0.2%/year and February 0.4 ± 0.2%/year and negative for July 0.3 ± 0.2%/year and August 0.2 ± 0.1%/year). This fact suggests the tendency for an increase in the amplitude of the annual cycle of the total CH₄ content. The results of a spectral analysis of a series of data on the total CH₄ content show that, for 1991–2007, the following harmonics are pronounced with a confidence of 95%: 12 months (annual harmonic), 32 months (quasi-biennial oscillations), and 55 months (4.5 years), which are also pronounced in the series of meteorological parameters and total ozone content.     

Long-term changes in the aerosol optical thickness in moscow and correction under strong atmospheric turbidity

We have estimated and compensated the error in long-term series of the aerosol optical thickness (AOT) calculated from the data on direct integral solar radiation measured by a standard actinometer at the Meteorological Observatory of the Moscow State University (MO MSU) for strong atmospheric turbidity conditions. The necessary corrections have been obtained by the Monte-Carlo simulation of the actinometry measurements for different atmospheric conditions, taking into account the angular size of the field of view of the instrument; and a special correctional formula has been obtained. This correction formula has been applied for all timed AOT values of above 0.5 observed at the MO MSU for the entire time period from 1955 to 2013. Changes in the long-term average AOT values in Moscow occurred only when the smoky haze from the forest and peat fires affected the aerosol turbidity of the atmosphere. Here, the significant decreasing trend of aerosol optical depth of the atmosphere from 1955 to 2013 has been retained with the same confidence level.     

Atmospheric trace gas measurements during SEEDS-II over the northwestern pacific

Atmospheric trace gas measurements were conducted during SEEDS-II. Atmospheric dimethylsulfide (DMS) was continuously measured by GC-MS during the R/V Hakuho cruise. Further, ambient air was sampled into canisters (42 samples) and analyzed by GC-MS and GC-FID for various biogenic and anthropogenic volatile organic compounds (VOCs) after the cruise. CO, O₃, SO₂, and NOx were monitored continuously aboard the ship.A fertilization experiment was conducted in a high-nitrate, low-chlorophyll (HNLC) region (48°N, 165°E). The atmospheric concentrations inside a patch (fertilized area) were compared with those outside it (natural area); however, clear differences were not observed for biogenic trace gasses (DMS, CH₃Cl, CH₃I, isoprene, and alkenes) in the atmosphere. However, a high DMS concentration was observed over the northwestern Pacific Ocean. The fertilized area was also observed by R/V Kilo Moana, and DMS was measured by GC-FPD. A good agreement was observed between the results of the measurements made aboard the two independent ships by different measurement methods.The atmospheric SO₂ concentration was compared with the atmospheric DMS concentration. The SO₂ concentration was found to vary with the atmospheric DMS concentration. A diurnal variation of the atmospheric DMS concentration was observed around the fertilized region. The DMS content tends to increase during the night and decrease during the day. A box model calculation was conducted to explain the diurnal variation of the atmospheric DMS. Since there was no diurnal variation of the wind speed, a constant DMS flux from the ocean surface was assumed. Further, the atmospheric OH radical concentration was assumed to be dependent on sunlight. The box model can roughly reproduce the atmospheric DMS diurnal variation mainly caused by its removal reaction with OH radicals.     

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.     

Hydrocarbons in an urban atmosphere

Statistical characteristics of variations in surface-layer concentrations of methane, non-methane and aromatic hydrocarbons, carbon dioxide, and formaldehyde are compared with the characteristics of variations in the concentration of carbon monoxide in the air basin of Moscow. Differences in the annual cycle of concentrations of methane, carbon dioxide, non-methane hydrocarbons, and carbon monoxide are determined. It is found that the maximum concentration of carbon monoxide at most sites with an elevated surface-air pollution level and over the city as a whole tends to occur in the summer season. The seasonal variability of the diurnal mean cycle of methane, carbon dioxide, and non-methane and aromatic hydrocarbons is analyzed.     

海洋中生源活性气体的来源与迁移转化

海洋生源活性气体主要包括二甲基硫（DMS）、甲烷（CH₄）、氧化亚氮（N₂O）、一氧化碳（CO）、挥发性卤代烃（VHCs）和非甲烷烃（NMHCs）等。它们通过海-气交换进入大气,不仅在全球碳、氮和硫循环中发挥关键作用,而且会直接或间接地对环境和气候变化产生重要影响。海洋释放的活性气体一类属于温室效应气体（CH₄、N₂O、VHCs和CO等）,另一类会在大气中发生化学反应,控制着大气氧化平衡和臭氧浓度（VHCs和NMHCs）。而DMS属于负温室效应气体,其在大气中被快速氧化形成硫酸盐气溶胶,进而对云的形成和辐射强迫产生重要影响。本文综述了国内外海洋生源活性气体的研究现状,着重介绍了DMS、CH₄和N₂O的来源、迁移转化、海-气通量及其影响机制,并指明了该领域存在的科学问题及今后的研究方向。     

Seasonal features of quasi-biennial variations of NO<Subscript>2</Subscript> stratospheric content derived from ground-based measurements

Seasonal and latitudinal distributions of amplitudes of quasi-biennial variations in total NO₂ content (NO₂ TC), total ozone content (TOC), and stratospheric temperature are obtained. NO₂ TC data from ground-based spectrometric measurements within the Network for the Detection of Atmospheric Composition Change (NDACC), TOC data from satellite measurements, and stratospheric temperature data from ERA-Interim reanalysis are used for the analysis. The differences in the NO₂ TC diurnal cycles are identified between the westerly and easterly phases of the quasi-biennial oscillations (QBO) of equatorial stratospheric wind. The QBO effects in the NO₂ TC, TOC, and stratospheric temperature in the Northern (NH) and Southern (SH) hemispheres are most significant in the winter–spring periods, with essential differences between the NH and SH. The NO₂ TC in the Antarctic is less for the westerly phase of the QBO than that for the easterly phase, and the NO₂ TC quasi-biennial variations in the SH mid-latitudes are opposite of the variations in the Antarctic. In the NH, the winter values of the NO₂ TC are generally less during the westerly QBO phase than during the easterly phase, whereas in spring, on the contrary, the values for the westerly QBO phase exceed those for the easterly phase. Along with NO₂, the features of the quasi-biennial variations of TOC and stratospheric temperature are discussed. Possible mechanisms of the quasi-biennial variations of the analyzed parameters are considered for the different latitudinal zones.     

Seasonal Study of Methane and Nitrous Oxide in the Coastal Waters of the Southern Baltic Sea

Atmospheric and dissolved methane (CH₄) and nitrous oxide (N₂O) were measured in the unique coastal ecosystem of theBoddenwaters, including the western Oder estuary, (southern Baltic Sea) during five campaigns between 1994 and 1997. The CH₄saturations, ranging from 105–15 500%, showed great spatial and temporal variability with maximum values in September and minimum values in December. The N₂O saturations were in the range of 91–312% with a maximum in March. Enhanced concentrations of both gases were observed only in the western Oder estuary near the mouth of the Peene River. Thus, we conclude that the distributions of CH₄and N₂O in the investigatedBoddenwaters are, directly or indirectly, linked to the Peene River runoff and not to the Oder River. Our estimate of the annual CH₄emissions from theBoddenwaters to the atmosphere indicates a significant contribution (c. 17%) to the overall CH₄emissions from the Baltic Sea. In contrast, theBoddenwaters represent only a small source for atmospheric N₂O.CH₄production rates estimated from sediment slurry experiments revealed a significant spatial variability and indicated that methanogenic activity was related to acetate consumption in the surface sediment layer. Sedimentary CH₄production might depend on different amounts of accumulation of organic material.     

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.