Variations in gaseous pollutants in the air basin of Moscow

Variations in the concentrations of gaseous pollutants in the air basin of Moscow are statistically analyzed. The basic statistical characteristics of variations in the concentrations of carbon monoxide, nitric oxide, nitrogen dioxide, ozone, formaldehyde, and a number of aromatic compounds are calculated. The main properties of intradiurnal, synoptic, seasonal, and interannual variations in the concentrations of gaseous pollutants are described. The power spectral densities of variations in the concentrations of carbon monoxide and nitrogen oxides are analyzed. The contributions made by variations in the concentration of carbon monoxide on different time scales to the total variance are calculated. The effect of the atmospheric air polluted with carbon monoxide and nitrogen oxides on the ecological situation in the city is estimated. The probabilities of an excess over the single maximum allowable concentrations are determined for carbon monoxide and nitrogen oxides. The absorption of shortwave solar radiation by nitrogen dioxide in the atmospheric boundary layer is estimated.     

Variations in the total column amounts of carbon monoxide and methane in the Antarctic atmosphere

The results of measuring the total contents of carbon monoxide and methane via the method of solar-absorption spectroscopy are presented. The measurements were performed at the Molodezhnaya Station in 1977–1978, at the Mirny Observatory from 1982 to 1992, and at the Novolazarevskaya Station from 2003 to 2006. The character of seasonal variations in the contents of these gases in the Antarctic atmosphere is described and compared to the intra-annual variation of their surface concentrations measured at the Syowa Station (Japan). Synchronous intra-annual variations in the contents of carbon monoxide in the atmospheric column and in its surface concentrations are observed, while the spring maximum content of methane is observed three months after the maximum of its surface concentration. Synchronous seasonal variations in the total content of methane and ozone are observed, which makes it possible to suggest that the Antarctic circumpolar vortex has a significant influence on the characteristics of the vertical distribution of methane during Antarctic spring. Quantitative estimates of the parameters of multiyear variations in the contents of CO and CH₄ are given. The content of methane was increasing (although with different rates) during the entire observation period 1977–2006. The content of CO was observed to increase until 1992 and to decrease during 2003–2006.     

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.     

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。     

Chemistry of free and dissolved gases of Matupit Bay,Rabaul caldera,Papua New Guinea

Free gases from fumaroles of the Tavurvur and Rabalanakaia volcanoes are liberated as bubbles from the seafloor of Matupit Bay. The free gases contain methane (as high as 0.02%), heavy hydrocarbons (0.00001–0.0004%), carbon dioxide (more than 90%), and hydrogen sulfide (up to 27.9%). Background levels of dissolved methane are 30–50 nl/liter; they become seven times higher in the area of sea-floor uplift in the bay, and 10–20 times higher in the hot-water lateral zone. The hydrogen concentration is as high as 100–300 nl/liter. Average content of carbon dioxide is 0.16–0.36 ml/liter and increases up to 5.5 ml/liter in the gasbubbling area.     

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.)     

Climate and carbon cycle variations in the 20th and 21st centuries in a model of intermediate complexity

The climate model of intermediate complexity developed at the Oboukhov Institute of Atmospheric Physics, Russian Academy of Sciences (IAP RAS CM), has been supplemented by a zero-dimensional carbon cycle model. With the carbon dioxide emissions prescribed for the second half of the 19th century and for the 20th century, the model satisfactorily reproduces characteristics of the carbon cycle over this period. However, with continued anthropogenic CO₂ emissions (SRES scenarios A1B, A2, B1, and B2), the climate-carbon cycle feedback in the model leads to an additional atmospheric CO₂ increase (in comparison with the case where the influence of climate changes on the carbon exchange between the atmosphere and the underlying surface is disregarded). This additional increase is varied in the range 67–90 ppmv depending on the scenario and is mainly due to the dynamics of soil carbon storage. The climate-carbon cycle feedback parameter varies nonmonotonically with time. Positions of its extremes separate characteristic periods of the change in the intensity of anthropogenic emissions and of climate variations. By the end of the 21st century, depending on the emission scenario, the carbon dioxide concentration is expected to increase to 615–875 ppmv and the global temperature will rise by 2.4–3.4 K relative to the preindustrial value. In the 20th–21st centuries, a general growth of the buildup of carbon dioxide in the atmosphere and ocean and its reduction in terrestrial ecosystems can be expected. In general, by the end of the 21st century, the more aggressive emission scenarios are characterized by a smaller climate-carbon cycle feedback parameter, a lower sensitivity of climate to a single increase in the atmospheric concentration of carbon dioxide, a larger fraction of anthropogenic emissions stored in the atmosphere and the ocean, and a smaller fraction of emissions in terrestrial ecosystems.     

Compositional changes in natural gas bubble plumes: observations from the Coal Oil Point marine hydrocarbon seep field

Detailed measurements of bubble composition, dissolved gas concentrations, and plume dynamics were conducted during a 9-month period at a very intense, shallow (22-m water depth) marine hydrocarbon seep in the Santa Barbara Channel, California. Methane, carbon dioxide, and heavier hydrocarbons were lost from rising seep bubbles, while nitrogen and oxygen were gained. Within the rising seawater bubble plume, dissolved methane concentrations were more than 4 orders of magnitude greater than atmospheric equilibrium concentrations. Strong upwelling flows were observed and bubble-rise times were ~40 s, demonstrating the rapid exchange of gases within the bubble plume.     

Structure of time variations in carbon dioxide in the atmospheric thickness over central Eurasia (Issyk Kul Monitoring Station)

The results are presented of statistical analysis of the data obtained from the 1980–2006 systematic measurements of the volume concentration of carbon dioxide in the atmospheric thickness over central Eurasia. The trends of both monthly and yearly means of CO₂ concentration are determined. During these 26 years, the yearly mean concentration increased by ～42 ppm at a mean rate of (1.56 ± 0.18) ppm per year and reached ～382.7 ppm. General statistical characteristics are found. The distribution function of the monthly mean concentrations of CO₂ is characterized by the presence of a second maximum and a bias of the principal mode toward large values, and the mean (over the measurement time) monthly concentration and the median almost coincide. The distribution function of the yearly mean concentrations of CO₂ is close to a normal distribution, and the mean (over the measurement time) yearly concentration, the median, and the mode also coincide. The trends of short-and long-period variations in the carbon dioxide concentration and their possible relation to a number of geophysical phenomena are revealed. Spectral analysis of the measuring data on CO₂ revealed oscillations with periods of 4, 6, 12, 15, 21, 29, 40, 53, 84, and 183 months. A statistical model with the parameters of these oscillations describes the experimental monthly mean concentrations of carbon dioxide with an rms deviation of 2.3 ppm (±0.6% of the mean over the entire period 361.9 ppm) and the yearly mean concentrations with an rms deviation of 0.9 ppm (～±0.3%).     

Interaction of the methane cycle and processes in wetland ecosystems in a climate model of intermediate complexity

The climate model of the Institute of Atmospheric Physics of the Russian Academy of Sciences (IAP RAS CM) has been supplemented with a module of soil thermal physics and the methane cycle, which takes into account the response of methane emissions from wetland ecosystems to climate changes. Methane emissions are allowed only from unfrozen top layers of the soil, with an additional constraint in the depth of the simulated layer. All wetland ecosystems are assumed to be water-saturated. The molar amount of the methane oxidized in the atmosphere is added to the simulated atmospheric concentration of CO₂. A control preindustrial experiment and a series of numerical experiments for the 17th–21st centuries were conducted with the model forced by greenhouse gases and tropospheric sulfate aerosols. It is shown that the IAP RAS CM generally reproduces preindustrial and current characteristics of both seasonal thawing/freezing of the soil and the methane cycle. During global warming in the 21st century, the permafrost area is reduced by four million square kilometers. By the end of the 21st century, methane emissions from wetland ecosystems amount to 130–140 Mt CH₄/year for the preindustrial and current period increase to 170–200 MtCH₄/year. In the aggressive anthropogenic forcing scenario A2, the atmospheric methane concentration grows steadily to ≈3900 ppb. In more moderate scenarios A1B and B1, the methane concentration increases until the mid-21st century, reaching ≈2100–2400 ppb, and then decreases. Methane oxidation in air results in a slight additional growth of the atmospheric concentration of carbon dioxide. Allowance for the interaction between processes in wetland ecosystems and the methane cycle in the IAP RAS CM leads to an additional atmospheric methane increase of 10–20% depending on the anthropogenic forcing scenario and the time. The causes of this additional increase are the temperature dependence of integral methane production and the longer duration of a warm period in the soil. However, the resulting enhancement of the instantaneous greenhouse radiative forcing of atmospheric methane and an increase in the mean surface air temperature are small (globally < 0.1 W/m² and 0.05 K, respectively).     

An oxygenating additive for improving the performance and emission characteristics of marine diesel engines

Diesel engines provide the major power sources for marine transportation and contribute to the prosperity of the worldwide economy. However, the emissions from diesel engines also seriously threaten the environment and are considered one of the major sources of air pollution. The pollutants emitted from marine vessels are confirmed to cause the ecological environmental problems such as the ozone layer destruction, enhancement of the greenhouse effect, and acid rain, etc. Marine diesel engine emissions such as particulate matter and black smoke carry carcinogen components that significantly impact the health of human beings. Investigations on reducing pollutants, in particular particulate matter and nitrogen oxides are critical to human health, welfare and continued prosperity. The addition of an oxygenating agent into fuel oil is one of the possible approaches for reducing this problem because of the obvious fuel oil constituent influences on engine emission characteristics. Ethylene glycol monoacetate was found to be a promising candidate primarily due to its low poison and oxygen-rich composition properties. In this experimental study ethylene glycol monoacetate was mixed with diesel fuel in various proportions to prepare oxygenated diesel fuel. A four-cylinder diesel engine was used to test the engine performance and emission characteristics. The influences of ethylene glycol monoacetate ration to diesel oil, inlet air temperature and humidity parameters on the engine’s speed and torque were considered. The experimental results show that an increase in the inlet air temperature caused an increase in brake specific fuel consumption (BSFC), carbon monoxide, carbon dioxide emission, and exhaust gas temperature, while decreasing the excess air, oxygen and nitrogen oxide emission concentrations. Increasing the inlet air humidity increased the carbon monoxide concentration while the decreased excess air, oxygen and nitrogen oxide emission concentrations. In addition, increasing ethylene glycol monoacetate ratio in the diesel fuel caused an increase in the BSFC while the excess air and oxygen emission concentrations decreased.     

海洋中CO的研究进展

研究海洋中的CO具有重要的生物地球化学意义,因为它在控制大气中羟基自由基的浓度、参与全球碳循环进而影响全球气候变化等方面起着重要作用。对过去几十年来海洋中CO的研究进展进行评述。详细介绍了海洋环境中CO浓度的分布特征、通量、来源及去除途径。指出在这一研究领域我国和国际的差距以及一些有待于进一步研究的问题。     

Estimation of the uncertainty of future changes in atmospheric carbon dioxide concentration and its radiative forcing

An ensemble experiment with the IAP RAS CM was performed to estimate future changes in the atmospheric concentration of carbon dioxide, its radiative forcing, and characteristics of the climate-carbon cycle feedback. Different ensemble members were obtained by varying the governing parameters of the terrestrial carbon cycle of the model. For 1860–2100, anthropogenic CO₂ emissions due to fossil-fuel burning and land use were prescribed from observational estimates for the 19th and 20th centuries. For the 21st century, emissions were taken from the SRES A2 scenario. The ensemble of numerical experiments was analyzed via Bayesian statistics, which made the uncertainty range of estimates much narrower. To distinguish between realistic and unrealistic ensemble members, the observational characteristics of the carbon cycle for the 20th century were used as a criterion. For the given emission scenario, the carbon dioxide concentration expected by the end of the 21st century falls into the range 818 ± 46 ppm (an average plus or minus standard deviation). The corresponding global instantaneous radiative forcing at the top of the atmosphere (relative to the preindustrial state) lies in the uncertainty range 6.8 ± 0.4 W m^?2. The uncertainty range of the strength of the climate-carbon cycle feedback by the end of the 21st century reaches 59 ± 98 ppm in terms of the atmospheric carbon dioxide concentration and 0.4 ± 0.7 W m^?2 in terms of the radiative forcing.     

Carbon monoxide concentrations in surface waters of the east tropical pacific in 1974: comparison with earlier values

Concentrations of carbon monoxide were measured in the surface waters of the east tropical Pacific during a cruise aboard USNS “Hayes” from Ecuador to Panama via Hawaii and Tahiti in the late winter and early spring of 1974. Data comparisons were made for time spans of 1.3–3.7 years at several locations where the cruise track intersected or closely paralleled portions of our two earlier Pacific cruise tracks. The comparisons showed remarkable consistency, considering the range of variability of carbon monoxide concentration. Latitudinal variations of concentrations found during the earlier cruises were reconfirmed.     

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.     

Investigation of the mechanism of the long-term evolution of the carbon cycle in the ecosystem of the Sevastopol bay

We analyze the components of the carbon system of the Sevastopol bay waters and the balance of main sediment-forming substances using the data of field investigations in 1998–2008. The interannual variations of total inorganic carbon and the equilibrium partial pressure of carbon dioxide in the bay water are noted. An increase in the flux of carbon dioxide into the bay and in the content of organic carbon in bottom sediments is revealed, and an explanation of this phenomenon is given. The priority accumulation of organic carbon in the sediments of the bay is established. We assess the interannual variation in the relative abundances of organic and inorganic carbon as an index of the carbon cycle stability.     

缅甸安达曼海域中部天然气成因与气源

位于主动大陆边缘的缅甸安达曼海域中部天然气资源丰富,成因多样。天然气成因类型直接影响勘探领域与方向的确定。通过气体组分、CH4和CO2碳同位素资料,对缅甸安达曼海域中部天然气成因类型及气源岩进行了判识。结果表明:上新统部分天然气具有较轻CH4碳同位素,为生物成因气,部分碳同位素较重的天然气属于热成因气;中新统及渐新统天然气CH4碳同位素均较重,属于热成因气;CO2碳同位素显示其存在无机、有机2种成因;此外,还存在少量生物气与热成因气或无机气的混源气。认为该区无机成因CO2与CH4共存体系通过基底断裂来源于地壳深部或上地幔;上新统生物气来自上新统未熟源岩;产于上新统、中新统热成因气,来源于上新统下部、中新统或渐新统上部等深层高-过成熟烃源岩。     

Numerical studies of methane production from Class 1 gas hydrate accumulations enhanced with carbon dioxide injection

Class 1 gas hydrate accumulations are characterized by a permeable hydrate-bearing interval overlying a permeable interval with mobile gas, sandwiched between two impermeable intervals. Depressurization-induced dissociation is currently the favored technology for producing gas from Class 1 gas hydrate accumulations. The depressurization production technology requires heat transfer from the surrounding environment to sustain dissociation as the temperature drops toward the hydrate equilibrium point and leaves the reservoir void of gas hydrate. Production of gas hydrate accumulations by exchanging carbon dioxide with methane in the clathrate structure has been demonstrated in laboratory experiments and proposed as a field-scale technology. The carbon dioxide exchange technology has the potential for yielding higher production rates and mechanically stabilizing the reservoir by maintaining hydrate saturations. We used numerical simulation to investigate the advantages and disadvantages of using carbon dioxide injection to enhance the production of methane from Class 1 gas hydrate accumulations. Numerical simulations in this study were primarily concerned with the mechanisms and approaches of carbon dioxide injection to investigate whether methane production could be enhanced through this approach. To avoid excessive simulation execution times, a five-spot well pattern with a 500-m well spacing was approximated using a two-dimensional domain having well boundaries on the vertical sides and impermeable boundaries on the horizontal sides. Impermeable over- and under burden were included to account for heat transfer into the production interval. Simulation results indicate that low injection pressures can be used to reduce secondary hydrate formation and that direct contact of injected carbon dioxide with the methane hydrate present in the formation is limited due to bypass through the higher permeability gas zone.     

Hydrocarbons in the Surface Layer of Bottom Sediments in the Northwestern Caspian Sea

The paper presents research results on the concentrations and compositions of aliphatic and polycyclic aromatic hydrocarbons in the surface layer of bottom sediments in the Northwestern Caspian Sea (2014) and compares them to data for sediments of the Middle and Southern Caspian (2012–2013). The seepage of hydrocarbons out of the sediment mass, resulting in abnormally high concentrations of aliphatic hydrocarbons per dry weight (up to 468 μg/g), as well as within the C_org composition (up to 35.2%), is considered the main source of hydrocarbons in sediments in the surveyed area of the Northern Caspian. This is also confirmed by the absence of any correlation between the hydrocarbon and C_org distributions, as well as by the transformed oil composition of high-molecular alkanes. The distribution of markers within polycyclic aromatic hydrocarbons points to a mixed genesis—petrogenic and pyrogenic—with prevalence of the latter. Unlike the shallow-water northern part of the Caspian Sea, the content and composition of hydrocarbons in deep-seated sediments are affected by facial conditions of sedimentation and by matter exchange at the water–bottom interface. Therefore, despite high C_org concentrations (up to 9.9%), sediments in deep-water depressions are characterized by a quite low concentration of aliphatic hydrocarbons (52 μg/g on average; 0.2% of C_org) with prevailing natural allochthonous alkanes.     

Dissolved gases of the near-bottom water layer in the area of Epi island,Vanuatu

The distribution of dissolved gases in the near-bottom water layer over the submarine volcanoes of the Epi caldera in the New Hebrides off northeastern Australia is widespread. Maximum contents of methane and carbon dioxide in the near-bottom layer were as high as 440 nl/liter and 1.1 ml/liter, respectively. Composition and anomalous concentrations of hydrocarbon gases (C₁–C₅) suggest a thermogenic source and an inflow from surrounding sediment. Accumulation of carbon dioxide is connected with fumarolic activity of the Epi-b Volcano.