Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

Processing of oxidised nitrogen compounds by passage through winter-time orographic cloud

Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO _y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO _y , called NO _z , was neither NO nor NO₂. This NO _z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO _z to NO₃ ^- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO₃ and N₂O₅ by aerosol of surface area proportional to the NO₂ mixing ratio, shows that NO₃ and N₂O₅ may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N₂O₅ forming NO₃ ^- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N₂O₅ was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO₂ and the cloud liquid water content were related to each other. Also, indications of conversion of NO _x to NO _z were found. To explain these observations, scavenging of NO _x and HNO₂ by cloud droplets and/or aqueous-phase oxidation of NO₂ ^- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO _x or SO₂, NO₃ ^- which had entered the cloud as aerosol particles was liberated as HNO₃ vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO₃ to particulate NO₃ ^-, was observed.     

武汉市冬季灰霾期PM2.5中水溶性无机离子的特征

2018年1月,利用颗粒物采样器采集武汉市大气PM_2.5样品并进行水溶性无机离子（F^-、Cl^-、NO₃^-、SO₄^2-、Na⁺、NH₄⁺、K⁺、Mg²⁺、Ca²⁺）的分析.结果表明,NO₃^-、SO₄^2-、NH₄⁺是PM_2.5中最主要的3种水溶性无机离子,除Mg²⁺与Ca²⁺外,PM_2.5与WSⅡs （水溶性无机离子）之间的相关性显著,且移动源贡献占主导地位.阴阳离子平衡表明武汉市冬季灰霾期PM_2.5呈中性或弱酸性.通过混合单粒子拉格朗日综合轨迹模式模拟并采用分层聚类得出了4种主要的后向气流轨迹及相应的PM_2.5和水溶性离子浓度,结果表明区域传输对此次灰霾期影响较大.     

On the wet removal of gaseous and particulate sulfur and nitrogen species from the atmosphere

The role of trace gases and aerosol particles in the control of sulfur and nitrogen levels in atmospheric precipitation is estimated on the basis of the enrichment factor in the precipitation of these elements relative to particulate matter in the air. By using air and precipitation chemistry data obtained at a Hungarian background air pollution station (K-puszta) it is found that the fraction of ammonium, nitrate and sulfate in precipitation, due to the removal of particulate matter is at least 59, 27 and 31%, respectively. The relationship between wet depositions and air concentrations of different species is determined statistically by applying daily data set. The regression equations obtained make the estimation of the sub-cloud scavenging ratios possible and they give some information on the magnitude of in-cloud scavenging processes. The results show that the in-cloud scavenging is a determining factor for precipitation sulfate, while it is relatively unimportant in the case of ammonium. The sub-cloud scavening of NO₂ and SO₂ is not too significant. However, for HNO₃, and NH₃ it is an effective process. The sub-cloud scavenging ratio of sulfur and nitrogen-containing particles varies around 0.25×10⁶.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

Chemical Composition and Association of Size-Differentiated Aerosols at a Suburban Site in a Semi-Arid Tract of India

Size-differentiated concentrations of SPM, F, Cl, NO₃, SO₄, Na, K, Ca, Mg and NH₄ in atmospheric aerosols were measured in a suburban area of Agra city during December 1992 to March 1993. Except for NH₄, Cl and Na, all components were found to have a bimodal distribution. The fine fraction was dominated by NH₄, K, NO₃ and SO₄, while Na, Ca, Mg, F and Cl contributed to the coarse fraction. Fifty-eight percent of SO₄ and 67% of NO₃ were found in the fine mode and the coarse mode comprised 42 and 33% of SO₄ and NO₃, respectively. SO₄ was found to have a peak above the submicron range at 1.1 µm which has been attributed to secondary sulphate formation by heterogeneous oxidation of SO₂ on alkaline particles of Ca and Mg. The total aerosol was basic in nature and dominated by the soil-derived acid neutralising components (Ca, Mg and Na).     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

Chemical composition and source apportionment of rainwater at Guiyang, SW China

This study systematically analyzed the concentrations of cations and anions and determined the pH in the rainwater at Guiyang from Oct. 2008 to Sep. 2009. The pH in the rainwater varied between 3.35 and 9.99 with a volume-weighted mean value of 4.23. The volume-weighted mean concentrations of anions followed the order SO₄ ^2->Cl^->F^->NO₃ ^-, whereas the volume-weighted mean concentrations of cations followed the order Ca²⁺>NH₄ ⁺>Na⁺>Mg²⁺>K⁺. This finding indicates that SO₄ ^2- was the main anion and that Ca²⁺ and NH₄ ⁺ were the main cations. Significant correlations between each pair of ions (SO₄ ^2-, NO₃ ^-, NH₄ ⁺, Ca²⁺, and Mg²⁺) were observed, suggesting that CaSO₄, Ca(NO₃)₂, MgSO₄, Mg(NO₃)₂, NH₄NO₃, (NH₄)₂SO₄, and/or NH₄HSO₄ exist in the atmosphere at Guiyang. The soil-derived species (such as Ca²⁺) played an important role in the neutralization of the acidity in rainwater. The SO₄ ^2- and NO₃ ^- in the rainwater were mainly from anthropogenic sources, and their contributions accounted for 98.1 % and 94.7 %, respectively. NH₄ ⁺ was also most likely derived from anthropogenic sources, such as domestic and commercial sewage, and played an important role in the neutralization of the rainwater at Guiyang.     

Acidity of Aerosols during Winter Heavy Haze Events in Beijing and Gucheng,China

We investigated the acidity and concentrations of water-soluble ions in PM_2.5 aerosol samples collected from an urban site in Beijing and a rural site in Gucheng, Hebei Province from November 2016 to January 2017 to gain an insight into the formation of secondary inorganic species. The average SO₄^2–, NO₃^–, and NH₄⁺ concentrations were 8.3, 12.5, and 14.1 μg m^–3, respectively, at the urban site and 14.0, 14.2, and 24.2 μg m^–3, respectively, at the rural site. The nitrogen and sulfur oxidation ratios in urban Beijing were correlated with relative humidity (with correlation coefficient r = 0.79 and 0.67, respectively) and the aerosol loadings. Based on a parameterization model, we found that the rate constant of the heterogeneous reactions for SO₂ on polluted days was about 10 times higher than that on clear days, suggesting that the heterogeneous reactions in the aerosol water played an essential role in haze events. The ISORROPIA II model was used to predict the aerosol pH, which had a mean (range) of 5.0 (4.9–5.2) and 5.3 (4.6–6.3) at the urban and rural site, respectively. Under the conditions with this predicted pH value, oxidation by dissolved NO₂ and the hydrolysis of N₂O₅ may be the major heterogeneous reactions forming SO₄^2– and NO₃^– in haze. We also analyzed the sensitivity of the aerosol pH to changes in the concentrations of SO₄^2–, NO₃^–, and NH₄⁺ under haze conditions. The aerosol pH was more sensitive to the SO₄^2– and NH₄⁺ concentrations with opposing trends, than to the NO₃^– concentrations. The sensitivity of the pH was relatively weak overall, which was attributed to the buffering effect of NH₃ partitioning.     

Particulate matter and gaseous pollutants during a tropical storm and air pollution episode in Southern Taiwan

Gaseous pollutants and PM_2.5 aerosol particles were investigated during a tropical storm and an air pollution episode in southern Taiwan. Field sampling and chemical analysis of particulate matter and gaseous pollutants were conducted in Daliao and Tzouying in the Kaohsiung area, using a denuder-filter pack system during the period of 22 October to 3 November 2004. Sulfate, nitrate and ammonium were the major ionic species in the PM_2.5, accounting for 46 and 39% of the PM_2.5 for Daliao and Tzouying, respectively. Higher PM_2.5, Cl^?, NO₃^? and NH₄⁺, HNO₂ and NH₃ concentrations were found at night in both stations, whereas higher HNO₃ was found during the day. In general, higher PM_2.5, HCl, NH₃, SO₂, Cl^?, NO₃^?, SO₄^2? and NH₄⁺ concentrations were found in Daliao. The synoptic weather during the experiment was first influenced by Typhoon NOCK-TEN, which resulted in the pollutant concentrations decreasing by about two-thirds. After the tropical thunderstorm system passed, the ambient air quality returned to the previous condition in 12 to 24 h. When there was a strong subsidence accompanied by a high-pressure system, a more stable environment with lower wind speed and mixing height resulted in higher PM_2.5, as well as HNO₂, NH₃, SO₄^2?, Cl^?, NO₃^?, NH₄⁺ and K⁺ concentrations during the episode days. The rainfall is mainly a scavenger of air pollutants in this study, and the stable atmospheric system and the high emission loading are the major reasons for high air pollutant concentrations.     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

Behaviour of H2O2, NH3, and black carbon in mixed-phase clouds during CIME

We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H₂O₂, NH₃ and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H₂O₂ and NH₃ are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H₂O₂ is driven by co-condensation with water vapour onto ice crystals while NH₃ uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH₄⁺ in the ice could explain this result. Finally, it appears that the H₂O₂–SO₂ reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.     

Nitrogen and sulfur species in acrosols at Mawson,Antarctica, and their relationship to natural radionuclides

High volume aerosol samples were collected continuously at Mawson, Antarctica (67°36'S, 62°30'E), from February 1987 through October 1989. All samples were analyzed for Na⁺, Cl^-, SO₄ ⁼, NO₃ ^-, methanesulfonate (MSA), NH₄ ⁺,⁷Be, and²¹⁰Pb. The annual mean concentrations of many of the species are very low, substantially lower than even those over the relatively pristine regions of the tropical and subtropical South Pacific. The concentrations at Mawson are comparable both in magnitude and in seasonality to those which have been measured in long term studies at the South Pole and at the coastal German Antarctic research station, Georg von Neumayer (GvN). This comparability suggests that the aerosol composition may be relatively uniform over a broad sector of the Antarctic. The concentrations of most of the species exhibit very strong and sharply-defined seasonal cycles. MSA, non-sea-salt (nss) SO₄ ⁼ and NH₄ ⁺ all exhibit similar cycles, with maxima during the austral summer (December through February) being more than an order of magnitude higher than the winter minima. The limited⁷Be data appears to exhibit a similar cycle. Although nitrate and²¹⁰Pb also exhibit relatively high concentrations during the austral summer, their cycles are far more complex than those of the previous species with indications of multiple peaks. As expected, the concentration of sea-salt (as indicated by Na⁺ and Cl^-) peaks during the winter. The results from multiple variable regression analyses indicate that the dominant source of nss SO₄ ⁼ is the oxidation of dimethylsulfide (DMS) which produces MSA and nss SO₄ ⁼ in a ratio of about 0.31 (about five times higher than that over the tropical and subtropical oceans). However, a very significant fraction (about 25%) of the nss SO₄ ⁼ is associated with NO₃ ^-, The seasonal cycle of NO₃ ^- is similar to that of²¹⁰Pb and distinctly different from that of⁷Be and MSA. These results indicate that the major source of NO₃ ^- over Antarctica is probably continental as opposed to stratospheric or marine biogenic.     

Measurements of PM<Subscript>10</Subscript> ions and trace gases with the online system MARGA at the research station Melpitz in Germany – A five-year study

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 ⁺.     

The effects of below-cloud aerosol on the acidification process of rain

Using a model of the acidification process of rain, we calculate and analyze the effects and contributions of a below-cloud aerosol in its different concentrations and acidities on the pH and ion components of rain (SO ₄ ^2– , H⁺, NO ₃ ^– , NH ₄ ⁺ , etc.) under the conditions of different concentrations of pollution gases. The results show that the aerosol has an acidification or alkalization effect on the rain which changes the pHs of rain and aerosol. As acidifying pollution gas concentrations (SO₂, HNO₃) are low, the acid aerosol has important effects on the pH and H⁺ of rain, but as the gas concentrations are high, the acid aerosol has very little effect. The alkalizing aerosol makes the pH of rain increase by between 0.3 and 0.5 and neutralizes about 60% of H⁺ in the rain. As alkalizing pollution gas NH₃ exists, the acid aerosol has important effects on the pH and H⁺ of rain. But the alkalizing aerosol has very little effect, especially as the NH₃ concentration is high. The percentage contribution of the aerosol to SO ₄ ^2– in rain is generally 7–15%, the contribution of the aerosol to NO ₃ ^– is nearly the same as that of HNO₃=1 ppb, and the contribution of the aerosol to NH ₄ ⁺ is nearly the same as that of NH₃, from 5 to 7 ppb, and is an important source of NH ₄ ⁺ in rain. Finally, according to the actual conditions of typical regions in the south and north of China (Chongqing and Beijing), we analyze the effects of aerosol and pollution gases on the ion components of rain.     

苏州市大气PM_(2.5)中水溶性无机离子的源解析及其气象因子分析

为了探明PM_(2.5)中水溶性无机离子的来源和气象因子对其浓度变化的影响,利用2012年2、5、8和11月苏州市PM_(2.5)中水溶性无机离子浓度和本站气象观测数据,分析了苏州市水溶性无机离子的时间变化特征,解析了当地PM_(2.5)中水溶性无机离子的主要来源,探讨了气象因素对离子组分的影响。结果表明:(1)苏州市PM_(2.5)中水溶性无机离子年均浓度大小依次为:SO_4~(2-)NO_3~-NH_4~+Na~+Cl~-K~+Ca~(2+)Mg~(2+)F~-;SO_4~(2-)、NH_4~+和NO_3~-为PM_(2.5)中最重要的3种水溶性无机离子物种,其总和占PM_(2.5)总质量浓度的50.9%。各离子的季节浓度特征均为冬季最高、夏季最低。(2)通过运用主成分分析法对苏州市PM_(2.5)中水溶性无机离子进行来源分类解析,发现第一类为二次污染源和生物质燃烧,其贡献率为32.84;第二类为道路扬尘及工业排放,其贡献率为19.99%;第三类为海盐污染,其贡献率为18.43%。(3)通过水溶性无机离子与气象条件的相关性分析发现,风向、风速和温度与水溶性无机离子浓度的相关性较显著,这三者是颗粒物浓度变化的主要影响因子。(4)利用HYSPLIT后向轨迹模式对外来污染物进入苏州市的轨迹进行聚类分析后发现:因受季风气候影响,苏州市外来污染物的输入路径存在明显的季节性变化特征,其中夏半年输送主径源自海上,冬半年主径源自内陆。     

Secondary aerosol formation and identification of regional source locations by PSCF analysis in the Indo-Gangetic region of India

Secondary aerosol formation was studied at Allahabad in the Indo-Gangetic region during a field campaign called Land Campaign-II in December 2004 (northern winter). Regional source locations of the ionic species in PM₁₀ were identified by using Potential Source Contribution Function (PSCF analysis). On an average, the concentration of water soluble inorganic ions (sum of anions and cations) was 63.2 μgm⁻³. Amongst the water soluble ions, average NO₃⁻ concentration was the highest (25.0 μgm⁻³) followed by SO₄²⁻ (15.8 μgm⁻³) and NH₄⁺ (13.8 μgm⁻³) concentrations. These species, contributed 87% of the total mass of water soluble species, indicating that most of the water soluble PM₁₀ was composed of NH₄NO₃ and (NH₄)₂SO₄/NH₄HSO₄ or (NH₄)₃H(SO₄)₂ particles. Further, the concentrations of SO₄²⁻, NO₃⁻, and NH4⁺ aerosols increased at high relative humidity levels up to the deliquescence point (∼63% RH) for salts of these species suggesting that high humidity levels favor the conversion and partitioning of gaseous SO₂, NO_x, and NH₃ to their aerosol phase. Additionally, lowering of ambient temperature as the winter progressed also resulted in an increase of NO₃⁻ and NH₄⁺ concentrations, probably due to the semi volatile nature of ammonium nitrate. PSCF analysis identified regions along the Indo-Gangetic Plain (IGP) including Northern and Central Uttar Pradesh, Punjab, Haryana, Northern Pakistan, and parts of Rajasthan as source regions of airborne nitrate. Similar source regions, along with Northeastern Madhya Pradesh were identified for sulfate.     

Modified HNO3 seasonality in volcanic layers of a polar ice core: Snow-pack effect or photochemical perturbation?

Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO₃ chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO ₄ ^2– and NO ₃ ^– , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO ₃ ^– deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H₂SO₄ particles in the stratosphere may have favored condensation and removal of HNO₃ from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO₃ during summer, caused by direct consumption of OH through oxidation of volcanic SO₂.     

合肥市降水化学组成成分分析

为研究合肥市降水的化学组成成分,于2010年4—9月在合肥市国家基本气象站设立了采样点,进行降水的采集,对降水化学组成成分进行了测定,并系统分析了化学组成成分的特点。结果表明:合肥降水中阴离子主要为SO24-,阳离子主要为NH4+和Ca2+,[SO24-]/[NO3-]当量浓度比值范围为1.23～6.33,大部分样本的比值<3,说明酸雨类型以硝硫混合型为主。降水的酸度与单一离子当量浓度的相关性并不明显,应该是受多种离子综合影响的结果,SO24-与NO3-,Ca2+与Mg2+,NH4+与SO24-,NH4+与NO3-均表现出较好的相关性。