Journal of Atmospheric Chemistry最新文献

Measurements of the concentrations of H₂O₂ and methyl hydroperoxide (MHP), O₃, and SO₂ over Imizu City, Toyama Prefecture, Japan were performed in March using a helicopter. H₂O₂ concentrations were higher at an altitude of approximately 2,400 m (8,000 ft). The H₂O₂ concentrations (< 0.8 ppb) in the spring were much lower than those observed during the summer observations. MHP was also higher in the high-altitude atmosphere. Lower concentrations of H₂O₂ were observed when high air pollutants were actively transported from Asian continent. The concentrations of H₂O₂ were mostly lower than those of SO₂; this condition is called oxidant limitation. If H₂O₂ concentration rises in cold months, the acidification of cloud water may be accelerated at high elevations in central Japan where air pollution is actively transported.

To determine the effects of long-range transport of aerosols from an upwind area in East Asia to a downwind area in Japan, we chemically analyzed aerosols collected simultaneously on Tuoji Island (Shandong Province, China), Fukue Island (Nagasaki Prefecture, Japan), and Cape Hedo (Okinawa Prefecture, Japan). We focused on changes in the metallic composition of PM_2.5 aerosols during long-range transport. The average mass concentrations of PM_2.5 at the three sites decreased in the order Tuoji Island > Fukue Island ≈ Cape Hedo (48.3 ± 4.5, 13.9 ± 1.5, and 13.2 ± 0.9 μg/m³, respectively). The fraction of coarse particles in total suspended particles estimated by (1–PM_2.5/TSP) was highest on Cape Hedo, indicating that the contribution of sea salts was increased by long-range transport of the aerosols over the ocean. Enrichment factor analysis revealed that at all three sites, Al, K, Ca, Mn, Fe, Co, Sr, and Ba originated from soil; whereas Cr, Ni, Cu, Zn, As, Mo, Ag, Cd, Sn, Sb, Tl, and P appeared to be of anthropogenic origin. Na was the most abundant element on Cape Hedo, indicating the addition of sea salts during aerosol transport. The V concentration was highest at Fukue Island, which was ascribed to V emission from ships. Sixty-one percent of the V on Fukue Island and 62% of the V on Cape Hedo were determined to have originated from ships, implicating of data obtained on dates during which backward trajectory analysis indicated that the same air mass passed over Tuoji Island, Fukue Island, and Cape Hedo in that order.

This study provides an analysis of a five-year time series chemical composition of the bulk deposition (2009–2013), collected within a farm surrounded by industrial and urban settlements in a semi-rural area of the Po Valley, with the aim of characterizing potential emission sources affecting precipitation composition at the site. Most monitoring efforts in this region, recognized as one of the most polluted in the world both due to the intense industrialisation and urbanisation as well as to frequent air stagnation conditions, are presently devoted more to gaseous and particulate pollutants than to precipitation chemistry. The bulk deposition samples were very concentrated in chemical species, both acidic and alkaline, high compared to other polluted sites in the world and to locations in the same district. The mean ions concentrations (in μeq l^?1) are: NO₃ ^? (243)?>?SO₄ ^2? (220)?>?PO₄ ^3? (176)?>?Cl^? (153)?>?NO₂ ^? (29)?>?F^? (2.6); NH₄ ⁺ (504)?>?Ca²⁺ (489)?>?K⁺ (151)?>?Na⁺ (127)?>?Mg²⁺ (127). pH data shows a trend toward slightly alkaline conditions attributed to the large presence of ammonium and crustal elements, in spite of high concentrations of nitrates and sulphates. The relevant concentrations of Ca²⁺ and Mg²⁺ further suggests that these alkaline conditions might be due to the correspondingly significant concentrations of carbonates/bicarbonates in our dataset. While back-trajectories analysis suggests the stronger importance of local resuspension over long-range transport, statistical analyses on ion composition highlight the key role exerted by agricultural activity, especially in the case of NH₄ ⁺, K⁺, Ca²⁺ and PO₄ ^3? (especially linked to fertilisation practices and soil resuspension due to mechanical operations). Apart from Na⁺ and Cl^? ions which correlate well as expected, indicating their likely common origin from marine salt, the identification of the origin of the other ions is very complex due to the contribution of diverse local sources, such as industrial and residential settlements.

An hourly quantification of inorganic water-soluble PM₁₀ ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO₂ gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO₃ ^?, SO₄ ^2? and NH₄ ⁺ measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl^?, NO₃ ^?, SO₄ ^2? and NH₄ ⁺, respectively. A HONO comparison with a batch denuder shows large scatter (R² = 0.41). The MARGA HNO₃ is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH₃ was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl^?, NO₃ ^?, SO₄ ^2?, NH₄ ⁺, K⁺ and gaseous SO₂ to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO₃ ^? and SO₄ ^2? compared to NH₄ ⁺.

Investigations about VOSCs (volatile organic sulfur compounds) have been received increasing attention for their significant contribution to the nonvolcanic background sulfate layer in the stratosphere and the earth’s radiation balance and as a potential tool to understand the carbon budget. In this study, COS and CS₂ were always recorded throughout the entire rice cultivation season of 2014. COS fluxes appeared as emission in non-planted soil and as uptake in planted soil, the corresponding results were obtained as 2.66 and ?2.35 pmol·m^?2·s^?1, respectively. For CS₂, both planted and non-planted paddy fields acted as sources with an emission rate of 1.02 pmol·m^?2·s^?1 and 2.40 pmol·m^?2·s^?1, respectively. COS emission or uptake rates showed a distinct seasonal variation, with the highest fluxes at the jointing-booting stage. COS and CS₂ fluxes increased with increasing N fertilizer use because of improved plant and microbial growth and activity. Plots treated with both N and S reduced COS and CS₂ fluxes slightly compared with plots with only-N treatment. Light, soil moisture or temperature showed no significant correlation with COS and CS₂ fluxes, but revealed the important impacts on the magnitude and direction of gases fluxes. The results also showed that the (available) sulfur contents in soil and roots had a certain effect on VOSCs emission or uptake. Our results highlight the significance of biotic and abiotic production and consumption processes existing in the soil.

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.