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.     

Sudden stratospheric warmings: statistical characteristics and influence on NO<Subscript>2</Subscript> and O<Subscript>3</Subscript> total contents

Statistical characteristics of major and minor sudden stratospheric warmings (SSWs) in the Northern Hemisphere (NH) for 1958–2015 are analyzed using data of NCEP-NCAR, ERA 40, and ERA-Interim reanalyses. Dependencies of the number of major SSWs with the displacement of the circumpolar stratospheric vortex and the number of minor SSWs on the phase of the quasi-biennial oscillation (QBO) of the equatorial stratospheric wind and on the level of solar activity (SA) in the 11-year solar cycle have been revealed. Major SSWs accompanied by a displacement of the polar vortex occur more often at a high level of SA and at the easterly phase of the QBO in the 50–40 hPa layer, while minor SSWs occur more often at a low SA level and at the westerly phase of the QBO. An analysis of spatiotemporal dynamics of the stratospheric polar vortex at major SSWs is performed. The most probable directions of vortex displacement caused by SSWs have been revealed. Influences of the major SSWs on the total contents of NO₂ and ozone, as well as on stratosphere temperature, are analyzed.     

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 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.     

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.     

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.     

Effects of CO<Subscript>2</Subscript> Enrichment on Marine Phytoplankton

Rising atmospheric CO₂ and deliberate CO₂ sequestration in the ocean change seawater carbonate chemistry in a similar way, lowering seawater pH, carbonate ion concentration and carbonate saturation state and increasing dissolved CO₂ concentration. These changes affect marine plankton in various ways. On the organismal level, a moderate increase in CO₂ facilitates photosynthetic carbon fixation of some phytoplankton groups. It also enhances the release of dissolved carbohydrates, most notably during the decline of nutrient-limited phytoplankton blooms. A decrease in the carbonate saturation state represses biogenic calcification of the predominant marine calcifying organisms, foraminifera and coccolithophorids. On the ecosystem level these responses influence phytoplankton species composition and succession, favouring algal species which predominantly rely on CO₂ utilization. Increased phytoplankton exudation promotes particle aggregation and marine snow formation, enhancing the vertical flux of biogenic material. A decrease in calcification may affect the competitive advantage of calcifying organisms, with possible impacts on their distribution and abundance. On the biogeochemical level, biological responses to CO₂ enrichment and the related changes in carbonate chemistry can strongly alter the cycling of carbon and other bio-active elements in the ocean. Both decreasing calcification and enhanced carbon overproduction due to release of extracellular carbohydrates have the potential to increase the CO₂ storage capacity of the ocean. Although the significance of such biological responses to CO₂ enrichment becomes increasingly evident, our ability to make reliable predictions of their future developments and to quantify their potential ecological and biogeochemical impacts is still in its infancy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of Introduced CO<Subscript>2</Subscript> on Deep-Sea Metazoan Meiofauna

An experiment was performed to determine the effect of injected CO₂ on the deep-sea (3200 m) meiofaunal community in the Monterey Canyon. Approximately 20 L of liquid CO₂ was added to each of three cylindrical corrals (PVC rings pushed into the seabed) that were arranged in a triangular array 10 m on a side. After a 30-day period, sediment cores were collected within an area exposed to the dissolution plume emanating from the CO₂ pools and from a reference site approximately 40 m away; cores were also collected from within two of the CO₂ corrals. Sediment cores were sectioned into 0–5, 5–10, and 10–20 mm layers. Abundances of major groups (harpacticoid copepods, nematodes, nauplii, kinorhynchs, polychaetes, and total meiofauna) were determined for each layer. CO₂ exposure did not significantly influence the abundances or vertical distributions of any of the major taxa. However, other evidence suggests that abundance alone did not accurately reflect the effect of CO₂ on meiofauna. We argue that slow decomposition rates of meiofaunal carcasses can mask adverse effects of CO₂ and that longer experiments and/or careful examination of meiofaunal condition are needed to accurately evaluate CO₂ effects on deep-sea meiofaunal communities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Perspectives on Biological Research for CO<Subscript>2</Subscript> Ocean Sequestration

Feasibility studies recently suggest that sequestration of anthropogenic CO₂ in the deep ocean could help reduce the atmospheric CO₂ concentration. However, implementation of this strategy could have a significant environmental impact on marine organisms. This has highlighted the urgent need of further studies concerning the biological impact of CO₂ ocean sequestration. In this paper we summarize the recent literature reporting on the biological impact of CO₂ and discuss the research work required for the future. Although fundamental research of the effect of CO₂ on marine organisms before the practical consideration of CO₂ ocean sequestration was limited, laboratory and field studies concerning biological impacts have been increasing after the first international workshop in 1991 discussing CO₂ ocean sequestration. Acute impacts of CO₂ ocean sequestration could be determined by laboratory and field experiments and assessed by simulation models as described by the following papers in this section. On the other hand, chronic effects of CO₂ ocean sequestration, those directly related to the marine ecosystem, would be difficult to verify by means of experiments and to assess using ecosystem models. One of the practical solutions for this issue implies field experiments starting with controlled small scale and eventually to a large scale of CO₂ injection intended to determine ecosystem alteration. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Effects of Direct Ocean CO<Subscript>2</Subscript> Injection on Deep-Sea Meiofauna

Purposeful deep-sea carbon dioxide sequestration by direct injection of liquid CO₂ into the deep waters of the ocean has the potential to mitigate the rapid rise in atmospheric levels of greenhouse gases. One issue of concern for this carbon sequestration option is the impact of changes in seawater chemistry caused by CO₂ injection on deep-sea ecosystems. The effects of deep-sea carbon dioxide injection on infaunal deep-sea organisms were evaluated during a field experiment in 3600 m depth off California, in which liquid CO₂ was released on the seafloor. Exposure to the dissolution plume emanating from the liquid CO₂ resulted in high rates of mortality for flagellates, amoebae, and nematodes inhabiting sediments in close proximity to sites of CO₂ release. Results from this study indicate that large changes in seawater chemistry (i.e. pH reductions of ∼0.5–1.0 pH units) near CO₂ release sites will cause high mortality rates for nearby infaunal deep-sea communities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Small Scale Field Study of an Ocean CO<Subscript>2</Subscript> Plume

We have carried out a small-scale (∼20 l) CO₂ sequestration experiment off northern California (684 m depth, ∼5°C, background ocean pH ∼7.7) designed as an initial investigation of the effects of physical forcing of the fluid, and the problem of sensing the formation of a low pH plume. The buoyant CO₂ was contained in a square frame 1.2 m high, exposing 0.21 m² to ocean flow. Two pH electrodes attached to the frame recorded the signal; a second frame placed 1.9 m south of the CO₂ pool was also equipped with two recording pH electrodes. An additional pH electrode was held in the ROV robotic arm to probe the fluid interface. Local water velocities of up to 40 cm sec⁻¹ were encountered, creating significant eddies within the CO₂ box, and forcing wavelets at the fluid interface. This resulted in rapid CO₂ dissolution, with all CO₂ being depleted in a little more than 2 days. The pH record from the sensor closest (∼10 cm) to the CO₂ showed many spikes of low pH water, the extreme value being ∼5.9. The sensor 1 m immediately below this showed no detectable response. The electrodes placed 1.9 m distant from the source also recorded very small perturbations. The results provide important clues for the design of future experiments for CO₂ disposal and biogeochemical impact studies. These include the need for dealing with the slow CO₂ hydration kinetics, better understanding of the fluid dynamics of the CO₂-water interface, and non-point source release designs to provide more constant, controlled local CO₂ enrichments within the experimental area. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Vertical structure of the M<Subscript>2</Subscript> tidal current in the Yellow Sea

The vertical structure of the M₂ tidal current in the Yellow Sea is analyzed from data acquired using an acoustic Doppler current profiler. The observed vertical profiles of the M₂ tidal current are decomposed into two rotating components of counter-clockwise and clockwise, and restructured using a simple one-point model with a constant vertical eddy viscosity. The analyzed results show that the internal fictional effect dominates the vertical structure of the tidal current in the bottom boundary layer. In the Yellow Sea, the effect of the bottom friction reduces the current speed by about 20–40% and induces the bottom phase advance by about 15–50 minutes. In the shallower coastal regions, the effects of bottom topography are more prominent on the vertical structure of tidal currents. The vertical profile of the tidal current in summer, when the water column is strongly stratified, is disturbed near the pycnocline layer. The stratification significantly influences the vertical shear and distinct seasonal variation of the tidal current.     

Recent increase in surface fCO<Subscript>2</Subscript> in the western subtropical North Pacific

We observed unusually high levels (> 440 μatm) of carbon dioxide fugacity (fCO₂) in surface seawater in the western subtropical North Pacific, the area where Subtropical Mode Water is formed, during summer 2015. The NOAA Kuroshio Extension Observatory moored buoy located in this region also measured high CO₂ values, up to 500 μatm during this period. These high sea surface fCO₂ (fCO_2SW) values are explained by much higher normalized total dissolved inorganic carbon and slightly higher normalized total alkalinity concentrations in this region compared to the equatorial Pacific. Moreover, these values are much higher than the climatological CO₂ values, even considering increasing atmospheric CO₂, indicating a recent large increase in sea surface CO₂ concentrations. A large seasonal change in sea surface temperature contributed to higher surface fCO_2SW in the summer of 2015.     

Spatial structure of the <Emphasis Type="Italic">M</Emphasis><Subscript>2</Subscript> tidal wave in the canadian arctic archipelago

The surface M ₂ tide in the Canadian Arctic Archipelago (CAA) is reproduced on the basis of the QUODDY-4 three-dimensional finite-element hydrodynamic model. Particular emphasis has been placed on comparing model estimates for the amplitudes and phases of tidal elevations and the parameters of ellipses (major semiaxis and eccentricity) of the barotropic tidal current velocity with observational data. We present their spatial distributions and the distributions of averaged (over a tidal cycle) values of the density, horizontal transfer, and dissipation rate of barotropic tidal energy. It is found that the CAA is a much less effective dissipator of barotropic tidal energy than the World Ocean.     

Effects of CO<Subscript>2</Subscript> on Marine Fish: Larvae and Adults

CO₂-enriched seawater was far more toxic to eggs and larvae of a marine fish, silver seabream, Pagrus major, than HCl-acidified seawater when tested at the same seawater pH. Data on the effects of acidified seawater can therefore not be used to estimate the toxicity of CO₂, as has been done in earlier studies. Ontogenetic changes in CO₂ tolerance of two marine bony fishes (Pag. major and Japanese sillago, Sillago japonica) showed a similar, characteristic pattern: the cleavage and juvenile stages were most susceptible, whereas the preflexion and flexion stages were much more tolerant to CO₂. Adult Japanese amberjack, Seriola quinqueradiata, and bastard halibut, Paralichthys olivaceus, died within 8 and 48 h, respectively, during exposure to seawater equilibrated with 5% CO₂. Only 20% of a cartilaginous fish, starspotted smooth-hound, Mustelus manazo, died at 7% CO₂ within 72 h. Arterial pH initially decreased but completely recovered within 1-24 h for Ser. quinqueradiata and Par. olivaceus at 1 and 3% CO₂, but the recovery was slower and complete only at 1% for M. manazo. During exposure to 5% CO₂, Par. olivaceus died after arterial pH had been completely restored. Exposure to 5% CO₂ rapidly depressed the cardiac output of Ser. quinqueradiata, while 1% CO₂ had no effect. Both levels of ambient CO₂ had no effect on blood O₂ levels. We tentatively conclude that cardiac failure is important in the mechanisms by which CO₂ kills fish. High CO₂ levels near injection points during CO₂ ocean sequestration are likely to have acute deleterious effects on both larvae and adults of marine fishes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Seasonal variability of surface and internal M<Subscript>2</Subscript> tides in the Arctic Ocean

The modeling results of surface and internal M₂ tides for summer and winter periods in the Arctic Ocean (AO) are presented. We employed a modified version of the three-dimensional finite-element hydrothermodynamic model QUODDY-4 differing from the original model by using a rotated (instead of spherical) coordinate system and by considering the equilibrium-tide effects. It has been shown that the modeling results for the surface tide differs little from the results obtained earlier by other authors. According to these results, the amplitudes of internal tidal waves (ITWs) in the AO are significantly lower than in other oceans and the ITWs proper have the character of trapped waves. Their source of generation is located at the continental slope northwest of the New Siberian Islands. Our results are consistent with the fields of average (over a tidal cycle) and integral (by depth) densities of baroclinic tidal energy, the maximum baroclinic tidal velocity, and the coefficient of diapycnic mixing. The local rate of baroclinic tidal energy dissipation at the AO ridges increases as it approaches the bottom, as was observed on Mid-Atlantic and Hawaii ridges (but merely within the bottom boundary layer) and is two to three orders of magnitude lower than in other oceans. The ITW degeneration scale in the AO is several hundreds of kilometers in summer and winter, remaining within the range of its values between 100 and 1000 km in mid- and low-latitude oceans. In both seasons, the integral (over the AO area) rate of baroclinic tidal energy dissipation is two orders of magnitude lower than the global estimate (2.5 × 10¹² W).     

Features of coastal upwelling regions that determine net air-sea CO<Subscript>2</Subscript> flux

The influence of the coastal ocean on global net annual air-sea CO₂ fluxes remains uncertain. However, it is well known that air-sea pCO₂ disequilibria can be large (ocean pCO₂ ranging from ∼400 μatm above atmospheric saturation to ∼250 μatm below) in eastern boundary currents, and it has been hypothesized that these regions may be an appreciable net carbon sink. In addition it has been shown that the high productivity in these regions (responsible for the exceptionally low surface pCO₂) can cause nutrients and inorganic carbon to become more concentrated in the lower layer of the water column over the shelf relative to adjacent open ocean waters of the same density. This paper explores the potential role of the winter season in determining the net annual CO₂ flux in temperate zone eastern boundary currents, using the results from a box model. The model is parameterized and forced to represent the northernmost part of the upwelling region on the North American Pacific coast. Model results are compared to the few summer data that exist in that region. The model is also used to determine the effect that upwelling and downwelling strength have on the net annual CO₂ flux. Results show that downwelling may play an important role in limiting the amount of CO₂ outgassing that occurs during winter. Finally data from three distinct regions on the Pacific coast are compared to highlight the importance of upwelling and downwelling strength in determining carbon fluxes in eastern boundary currents and to suggest that other features, such as shelf width, are likely to be important.     

Air-sea CO<Subscript>2</Subscript> flux by eddy covariance technique in the equatorial Indian Ocean

Direct measurements of the air-sea CO₂ flux by the eddy covariance technique were carried out in the equatorial Indian Ocean. The turbulent flux observation system was installed at the top of the foremast of the R/V MIRAI, thus minimizing dynamical and thermal effects of the ship body. During the turbulent flux runs around the two stations, the vessel was steered into the wind at constant speed. The power spectra of the temperature or water vapor density fluctuations followed the Kolmogorov −5/3 power law, although that of the CO₂ density fluctuation showed white noise in the high frequency range. However, the cospectrum of the vertical wind velocity and CO₂ density was well matched with those of the vertical velocity and temperature or water vapor density in this frequency range, and the CO₂ white noise did not influence the CO₂ flux. The raw CO₂ fluxes due to the turbulent transport showed a sink from the air to the ocean, and had almost the same value as the source CO₂ fluxes due to the mean vertical flow, corrected by the sensible and latent heat fluxes (called the Webb correction). The total CO₂ fluxes including the Webb correction terms showed a source from the ocean to the air, and were larger than the bulk CO₂ fluxes estimated using the gas transfer velocity by mass balance techniques.