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.     

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.     

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.     

Analysis of satellite observations of the tropospheric NO<Subscript>2</Subscript> content over the Moscow region

The tropospheric NO₂ content over the Moscow region is analyzed on the basis of data of the satellite Ozone Monitoring Instrument (OMI) in the period 2004–2009. The spatial distributions of NO₂ are presented, and some of their features are interpreted. The characteristics of the seasonal and weekly cycles of NO₂ are described, as are its interannual and long-term variations. The relationship between the variabilities of the NO₂ content and the aerological parameters is investigated on different time scales. The mutual influence of regional pollution and meteorological regimes is discussed. The seasonal and weekly NO₂ cycles over Moscow are compared with those over the largest worldwide agglomerations.     

Changes in Vertical Distribution and Column Content of NO<Subscript>2</Subscript> under the Influence of Sudden Stratospheric Warmings

Characteristic features of changes in the vertical distribution and column content of NO₂, total ozone, and stratospheric temperature have been revealed as a result of major sudden stratospheric warmings (SSWs). Strong negative anomalies of column NO₂, total ozone and stratospheric temperature are caused by the displacement of the stratospheric circumpolar vortex aside from the pole. Strong positive anomalies of column NO₂ and total ozone are observed more frequently under SSWs accompanied by splitting of the stratospheric circumpolar vortex and are caused by the transport of stratospheric air from the low latitudes. Major SSWs can lead to significant changes in the vertical profile of NO₂. The changes in different stratospheric layers can be opposite to each other when the edge of the polar vortex is over a site of ground-based observations.     

The influence of the spatial heterogeneity of vegetation cover and surface topography on vertical CO<Subscript>2</Subscript> fluxes within the atmospheric surface layer

The influence of the spatial heterogeneity of vegetation cover and topography on CO₂ fluxes in the atmospheric surface layer is estimated using a two-dimensional (2D) hydrodynamic model of turbulent exchange. A ~4.5-km-long profile that crossed a hilly area with a mosaic vegetation cover in Tula region was selected for model experiments. During the first experiment, a wind field and vertical fluxes were calculated by the 2D model for the entire selected profile with respect to the horizontal heterogeneity of the vegetation cover and surface topography. In the second experiment, the profile was considered an assemblage of elementary independent homogeneous segments; for each of them, vertical fluxes were calculated by the 2D model with the assumption of ‘zero’ horizontal advection, i.e., the required functions are independent of the horizontal coordinates. The influences of any boundary effects that appear at the interface between the different vegetation communities and at topographical irregularities on the turbulent regime are ignored in this case. For the profile selected, ignoring the horizontal advection, disturbances in the wind field that appeared at surface topography irregularities, and boundaries between different vegetation communities can lead to a 26% underestimation of the total CО₂ absorption by the ground surface on a clear sunny day under summer weather conditions.     

Retrieval of total ozone in the mesosphere with a new model of electronic-vibrational kinetics of O<Subscript>3</Subscript> and O<Subscript>2</Subscript> photolysis products

The paper presents a new model of electronic-vibrational kinetics of the products of ozone and molecular oxygen photodissociation in the terrestrial middle atmosphere. The model includes 45 excited states of the oxygen molecules O₂(b ¹, Σ _g ⁺ ,v= 0−2), O₂ (a ¹Δ _g , v= 0−5), and O₂(X ³Σ _g ⁻ , v= 1−35) and of the metastable atom O (¹ D) and over 100 aeronomic reactions. The model takes into account the dependence of quantum yields of the production of O₂(a ¹Δ _g , v= 0−5) in a singlet channel of ozone photolysis in the Hartley band on the wavelength of photolytic emission. Taking account of the electronic-vibrational kinetics is important in retrieval of the vertical profiles of ozone concentration from measured intensities of the Atm and IR Atm emissions of the oxygen bands above 65 km and leads to an increase in the ozone concentration retrieved from the 1.27-μm emission, in contrast to the previous model of pure electronic kinetics. Sensitivity analysis of the new model is made for variations in the concentrations of atmospheric constituents ([O₂], [N₂], [O(³P)], [O₃], [CO₂]), the gas temperature, rate constants of the reactions, and quantum yields of the reaction products. A group of reactions that most strongly affect the uncertainty of ozone retrieval from measured intensities of atmospheric emissions of molecular oxygen O₂(b ¹Σ _g ⁺ , v) and O₂(a ¹Δ _g , v) has been determined. Original Russian Text ? V.A. Yankovsky, V.A. Kuleshov, R.O. Manuilova, A.O. Semenov, 2007, published in Izvestiya AN. Fizika Atmosfery i Okeana, 2007, Vol. 43, No. 4, pp. 557–569.     

Ventilation time and anthropogenic CO<Subscript>2</Subscript> in the Bering Sea and the Arctic Ocean based on carbon tetrachloride measurements

The Arctic Ocean is connected to the Pacific by the Bering Sea and the Bering Strait. During the 4th Chinese National Arctic Research Expedition, measurements of carbon tetrachloride (CCl₄) were used to estimate ventilation time-scales and anthropogenic CO₂ (C_ant) concentrations in the Arctic Ocean and Bering Sea based on the transit time distribution method. The profile distribution showed that there was a high-CCl₄ tongue entering through the Canada Basin in the intermediate layer (27.6?<?σ_θ?<?28), at latitudes between 78 and 85°N, which may be related to the inflow of Atlantic water. Between stations B09 and B10, upwelling appeared to occur near the continental slope in the Bering Sea. The ventilation time scales (mean ages) for deep and bottom water in the Arctic Ocean (~?230–380 years) were shorter than in the Bering Sea (~?430–970 years). Higher mean ages show that ventilation processes are weaker in the intermediate water of the Bering Sea than in the Arctic Ocean. The mean C_ant column inventory in the upper 4000 m was higher (60–82 mol m^?2) in the Arctic Ocean compared to the Bering Sea (35–48 mol m^?2).     

Rare earth elements and Opal/CaCO<Subscript>3</Subscript> ratio of sinking particles observed with a time-series sediment trap at the mouth of Tokyo Bay

A time-series sediment trap was deployed from December 1994 to February 2002 at the mouth of Tokyo Bay (35°03′ N, 139°40′ E; water depth, 850 m). Sinking particles were obtained with a time interval of one week at a depth of approximately 100 m above the sea floor. Observed total mass fluxes varied from 3.3 to 226.7 g/m²/day with an average of 28.0 g/m²/day. Concentrations of rare earth elements, Al, Ca and Si in particulate materials were measured. The combustible fraction at 450°C is assumed to be equivalent to the organic matter content. Contents of biogenic materials, namely organic matter, opal and calcium carbonate, were about 30% and the content of lithogenic material was about 70%. Using La/Yb ratios of particles from the sediment trap and Tama-gawa River and surface sediment of Tokyo Bay, it was estimated that about 50% of the lithogenic particles collected in the sediment trap at the mouth of Tokyo Bay originated from resuspended surface sediment in Tokyo Bay. An increasing trend of Opal/CaCO₃ ratio in the sinking particles was found in the spring season. It is suggested that the relative increase of diatoms is due to the decreasing dissolved inorganic nitrogen input into Tokyo Bay.     

Alkalinity of sea ice in the high-latitudinal arctic according to the surveys performed at north pole drifting station 34 and characterization of the role of the arctic ice in the CO<Subscript>2</Subscript> exchange

The variability of the total alkalinity in the sea ice of the high-latitudinal Arctic from November 2005 to May 2006 is considered. For the bulk of the one- and two-year sea ice, the alkalinity dependence on the salinity is described as TA = k × Sal, where k is the salinity: alkalinity ratio in the under-ice water. The given relationship is valid within a wide salinity range from 0.1 psu in the desalinated fraction of two-year ice to 36 psu in the snow on the young ice surface. Geochemically significant deviations from the relationship noted were observed exclusively in the snow and the upper layer of one-year ice. In the upper layer of one-year ice, an alkalinity deficiency is observed (ΔTA ～ ?0.07 mequiv/kg, or ?15%). In the snow on the surface of the one-year ice, an alkalinity excess is formed under the desalination (ΔTA is as high as 1.3 mequiv/kg, 380%). The deviations registered are caused by the possibility of carbonate precipitation in the form of CaCO₃ · 6H₂O under the seawater freezing. It is shown that the ice formation and the following melting might cause a loss of the atmospheric CO₂ of up to 3 × 10¹² g C/year.