Journal of Atmospheric Chemistry最新文献

Comprehensive atmospheric studies have demonstrated that carbonaceous particles are one of the main components of atmospheric aerosols over Europe. The aim of our study was to establish an automated elemental analyser interfaced to a stable isotope mass spectrometer (EA-IRMS) method at the Hertelendi Laboratory of Environmental Studies (HEKAL), as a suitable method of quantification of total carbon mass in individual PM_2.5 aerosol samples. Total carbon (TC) mass and simultaneous stable isotopic?ratios were determined for both test standard and genuine aerosol samples. Finally, the results were compared to the ones obtained independently by an alternative sealed tube combustion method developed previously at HEKAL. The TC recovery tests of standard material prepared by the sealed tube method confirmed at least a carbon recovery?yield of 92% for a broad range of carbon mass (100–2000?μg). The stable isotopic results confirmed that sealed?tube method is reproducible and suitable to be used as a reference to verify?our new EA-IRMS method. The EA-IRMS TC measurements of genuine aerosols gave on average 3% higher carbon recovery yield, relative to the uncorrected results of the sealed?tube method. The comparison of the stable isotopic results by the two methods for aerosols also showed minimal differences. Consequently, the possibility of simultaneous TC and stable isotopic analyses makes the EA-IRMS method a very attractive alternative for continuous measurement of aerosols, with an accuracy and reliability similar to other commercial devices.

Measurements of hydroperoxides (H₂O₂ and MHP) at ground level were made from 2012 to 2015 in Imizu City, Toyama Prefecture in central Japan. H₂O₂ and MHP concentrations ranged from 0.01 to 3.5 ppb and from below the level of detection (< 0.01 ppb) to 1.4 ppb, respectively. The concentrations of H₂O₂ and MHP were high in the summer and low in the winter. The H₂O₂ concentration was at its maximum in July and August, whereas the concentration of O₃ in the daytime was highest in May and June. The ratio of [H₂O₂]/[SO₂] presented clear seasonal variations. Many cases showed the condition of [H₂O₂] < [SO₂], called oxidant limitation especially in the cold months. Hydroperoxide concentrations in the rainwater were also high in the summer. The concentrations of MHP were much lower than those of H₂O₂ in the rain water. High concentrations of H₂O₂ (> 2.5 ppb) were detected in the summer during the inflow of air pollution. The concentrations of H₂O₂ were significantly high in July and August of 2013. The H₂O₂ was well correlated with the O₃ in July and August whereas there was no correlation between O₃ and H₂O₂ in May and June. There was a negative correlation between NO_X and H₂O₂.

Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500?m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.

The hydroxyl radical (OH) is important in both tropospheric and stratospheric chemical processes that occur in Earth’s atmosphere. The OH radical can also strongly hydrogen-bond to form complexes with other atmospheric constituents, like water molecules. Consequently, there is potential for altered reaction dynamics/kinetics as a result of this complexation. Without direct measurements of the abundances of such complexes in Earth’s atmosphere, we have adopted a theoretical approach to determine such abundances. Electronic structures, enthalpies and free Gibbs energies of formation of OH, H₂O and H₂O-HO were calculated at CCSD(T) and QCISD(T) levels of theory with either 6–311++G(2d,2p) or aug-cc-pVTZ basis. Statistical thermodynamic concepts were then used to assess the abundance of the complex as function of altitude.

Halogenated Very Short-lived Substances (VSLS), such as bromoform, dibromomethane and methyl iodide, are naturally produced in the oceans and are involved in ozone depletion in the troposphere and the stratosphere. The effect of climate change on the oceanic emissions of these compounds is not well quantified. Based on present-day observed global oceanic and atmospheric concentrations, and historic and future data from three CMIP5 models, past and future sea-to-air fluxes of these VSLS are calculated. The simulations are used to infer possible effects of projected changes of physical forcing on emissions in different oceanic regimes. CMIP5 model output for 1979–2100 from the historical scenario and the RCP scenarios 2.6 and 8.5 are used as input data for the emission calculations. Of the parameters that have the main influence on the sea-to-air fluxes, the global sea surface temperatures show a steady increase during the twenty-first century, while the projected changes of sea surface wind speed is very small. The calculated emissions based on the historical CMIP5 model runs (1979–2005) increased over the 26?year period and agree well with the emissions based on ERA-Interim data. The future sea-to-air fluxes of VSLS generally increase during the twenty-first century under the assumption of constant concentration fields in the ocean and atmosphere. The multi-model mean global emissions of bromoform increase by 29.4% (9.0%) between 1986 and 2005 and 2081–2100 under RCP 8.5 (2.6) and dibromomethane and methyl iodide emissions increase by 23.3% (6.4%) and 5.5% (1.5%), respectively. Uncertainties of the future emission estimates, driven by ongoing environmental changes such as changing oceanic productivity (not considered in this study) are discussed.

We investigated and evaluated the occurrence of fault zone tracer gases (CO₂, He, Rn), volatile organohalogens (CH₃Cl, CHCl₃, CHBr₃), alkanes and limonene in soil and nest gases of red wood ants (RWA) in comparison to ambient air, in a seismically active area. In this new approach, we compared RWA-free areas to RWA-areas by combining different investigation and analytical methods. In soil gas, the fault zone tracer gas Rn was surprisingly highly correlated to limonene, suggesting a combination of biotic production of limonene and abiotic degassing of Rn in a seismically active area; moderate correlations were found with trihalomethanes and other halocarbons. In RWA nests a variety of elevated concentrations of haloforms were found, while remaining below the atmospheric background values in RWA-free areas. The evidence of CHCl₃ in RWA nests is the first record. Its average concentrations in nests of F. rufa and F. polyctena were up to 3 fold higher than atmospheric background and up to 28–70 fold higher compared to e.g. volcanic emissions being considered as one of its main geogenic sources. Thus, RWA nests could possibly be an additional source for CHCl₃ liberation. Consequently, apart from RWA being bioindicators for seismically active degassing faults, they might also be used as bioindicators for CHCl₃ formation in forest soils. Although we cannot yet differentiate between a geogenic/abiotic and a biotic formation. RWA nests will have to be reconsidered for halocarbon formation in future quantifications of geochemical cycles at global scale, since they impact organic soil chemistry through biotic and/or abiotic pathways. Therefore, further larger-scale research in different tectonic settings but also in well-known CHCl₃ “hot spot” study areas such as the Klosterhede area (Denmark) should focus directly on gas sampling from confirmed active fault systems. Nests of other ant species should be addressed to compare seasonal, diurnal and nocturnal variations of degassing procedures in relation to earth tides, different geologic settings, and tectonic events such as earthquakes and on quantifying the fluxes to the atmosphere.

The size distribution of atmospheric aerosols together with their composition, sources and sinks, is a key element in understanding aerosol effects on the Earth’s climate. Aerosol particle size distribution and chemical composition were measured over the Southern Ocean and at Antarctic region during December 2009–March 2010. Aerosol samples were collected using multi-stage low volume Air Sampler, and an aerosol size spectrometer was employed to monitor PM mass concentration continuously. The mean mass concentrations for PM₁₀, PM_2.5 and PM₁ were 1.5, 1.0 and 0.6?μg/m³, respectively at the Bharati station and were almost 2.5 times higher at the Maitri station. The mass size distribution of the aerosols measured by using a low volume air sampler exhibited a bimodal feature with a peak each in the size range of 0.4 to 0.7?μm and 3 to 5?μm. The difference in concentrations between the two locations for fine particles was comparatively lower than that for simultaneously measured coarse particles. Aerosol samples were analyzed for various water-soluble ionic constituents e.g. Na⁺, K⁺, Ca²⁺, Mg²⁺, NH₄ ⁺, Cl^?, SO₄ ^2? and NO₃ ^?. Sea-salt aerosols contributed to 86% of the measured mass over the Southern Ocean, 80% over Bharati and 76% at Maitri. The Southern Ocean being the most significant source of the particles during summer time, controls the aerosols at Bharati and Maitri sites. The present study will be helpful in simulating atmospheric processes responsible for aerosol characterization over coastal Antarctica and understanding its environmental implications related to radiation budget and climate over this region.

The seasonal intensive sampling of gases and particulate matter in ambient air was conducted at the site established in urban area of Japan to study the seasonal difference of the temporal variation of gases and particulate matter concentrations in urban atmosphere as well as to illustrate the different transport regimes that impacts air pollutants. The sample was collected by the four-stage filter-pack method with 6-h interval for one week in four seasons (spring, summer, autumn and winter). The trans-boundary transport of air pollutants with high concentration was characteristically observed in the spring sampling. On the other hand, we could successfully detect the in-country transports of air pollutants in the summer sampling. Four-season’s intensive survey considered, we could show the characteristic transport of air pollutants to provide the episodic high concentration for ambient air in the urban area of Japan, and successfully illustrate the seasonal-dependent transport regimes to impact on air pollutants.

Methyl Chloride (CH₃Cl) is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion (Carpenter et al. 2014). In the global CH₃Cl budget, the atmospheric CH₃Cl emissions is predominantly maintained by natural sources, of which magnitudes have been relatively well-constrained. However, significant uncertainties still remain in the CH₃Cl emission strengths from anthropogenic sources. High-frequency and high-precision in situ measurements of atmospheric CH₃Cl concentrations obtained since 2008 at Gosan station (a remote background site in the East Asia) reveal significant pollution events superimposed on the seasonally varying regional background levels. Back trajectory statistics showed that air masses corresponding to the observed CH₃Cl enhancement largely originated from regions of intensive industrial activities in China. Based on an inter-species correlation method, estimates of CH₃Cl emissions from manufacturing industries including coal combustion, use of feedstocks, or process agents in chemical production for China (2008–2012) are 297?±?71 Gg yr.^?1 in 2008 to 480?±?99 Gg yr.^?1 in 2009, followed by a gradual decrease of about 25% between 2009 and 2012 (398?±?92 Gg yr.^?1 for 2010; 286?±?68 Gg yr.^?1 for 2011; 358?±?92 Gg yr.^?1 for 2012). The annual average of industrial CH₃Cl emissions for 2008–2012 (363?±?85 Gg yr.^?1) in China is comparable to the known total global anthropogenic CH₃Cl emissions accounting only for coal combustion and indoor biofuel use. This may suggest that unless emissions from the chemical industry are accounted for, global anthropogenic emissions of CH₃Cl have been substantially underestimated. In particular, since industrial production and use of CH₃Cl have not been regulated under the Montreal Protocol (MP) or its successor amendments, continuous monitoring of Chinese CH₃Cl outflow is important to properly evaluate its anthropogenic emissions.

Volatile organic iodine compounds (VOIs) emitted from the ocean surface to the air play an important role in atmospheric chemistry. Shipboard observations were conducted in Funka Bay, Hokkaido, Japan, bimonthly or monthly from March 2012 to December 2014, to elucidate the seasonal variations of VOI concentrations in seawater and their sea-to-air iodine fluxes. The bay water exchanges with the open ocean water of the North Pacific twice a year (early spring and autumn). Vertical profiles of CH₂I₂, CH₂ClI, CH₃I, and C₂H₅I concentrations in the bay water were measured bimonthly or monthly within an identified water mass. The VOI concentrations began to increase after early April at the end of the diatom spring bloom, and represented substantial peaks in June or July. The temporal variation of the C₂H₅I profile, which showed a distinct peak in the bottom layer from April to July, was similar to the PO₄ ^3? variation profile. Correlation between C₂H₅I and PO₄ ^3? concentrations (r?=?0.93) suggests that C₂H₅I production was associated with degradation of organic matter deposited on the bottom after the spring bloom. CH₂I₂ and CH₂ClI concentrations increased substantially in the surface and subsurface layers (0–60?m) in June or July resulted in a clear seasonal variation of the sea-to-air iodine flux of the VOIs (high in summer or autumn and low in spring).