Analysis of chemical characteristics of PM<Subscript>2.5</Subscript> in Beijing over a 1-year period

Beijing is one of the largest and most densely populated cities in China. PM_2.5 (fine particulates with aerodynamic diameters less than 2.5 μm) pollution has been a serious problem in Beijing in recent years. To study the temporal and spatial variations in the chemical components of PM_2.5 and to discuss the formation mechanisms of secondary particles, SO₂, NO₂, PM_2.5, and chemical components of PM_2.5 were measured at four sites in Beijing, Dingling (DL), Chegongzhuang (CG), Fangshan (FS), and Yufa (YF), over four seasons from 2012 to 2013. Fifteen chemical components, including organic carbon (OC), elemental carbon (EC), K⁺, NH₄ ⁺, NO₃ ^?, SO₄ ^2?, Cl^?, Al, Ca, Fe, Mg, Na, Pb, Si, and Zn, were selected for analysis. Overall, OC, SO₄ ^2?, NO₃ ^?, and NH₄ ⁺ were dominant among 15 components, the annual average concentrations of which were 22.62 ± 21.86, 19.39 ± 21.06, 18.89 ± 19.82, and 13.20 ± 12.80 μg·m^?3, respectively. Compared with previous studies, the concentrations of NH₄ ⁺ were significantly higher in this study. In winter, the average concentrations of OC and EC were, respectively, 3 and 2.5 times higher than in summer, a result of coal combustion during winter. The average OC/EC ratios over the four sites were 4.9, 7.0, 8.1, and 8.4 in spring, summer, autumn, and winter, respectively. The annual average [NO₃ ^?]/[SO₄ ^2?] ratios in DL, CG, FS, and YF were 1.01, 1.25, 1.08, and 1.12, respectively, which were significantly higher than previous studies in Beijing, indicating that the contribution ratio of mobile source increased in recent years in Beijing. Analysis of correlations between temperature and relative humidity and between SOR ([SO₄ ^2?]/([SO₄ ^2?] + [SO₂])) and NOR ([NO₃ ^?]/([NO₃ ^?] + [NO₂])) indicated that gas-phase oxidation reactions were the major formation mechanism of SO₄ ^2? in spring and summer in urban Beijing, whereas slow gas-phase oxidation reactions and heterogeneous reactions both occurred in autumn and winter. NO₃ ^? was mainly formed through year-round heterogeneous reactions in urban Beijing.     

Study on water-soluble ionic composition of PM10 and related trace gases over Bay of Bengal during W_ICARB campaign

Aerosol (PM₁₀) samples were collected and its precursor gases, i.e., NH₃, NO, NO₂, and SO₂ measured over Bay of Bengal (BoB) during winter months of December 2008 to January 2009 to understand the relationship between particular matter (PM) and precursor gases. The observations were done under the winter phase of Integrated Campaign on Aerosols, gases and Radiation Budget (W_ICARB). The distribution of water-soluble inorganic ionic composition (WSIC) and its interaction with precursor gases over BoB are reported in present case. Average atmospheric concentration of NH₃, NO, NO_2, and SO₂ were recorded as 4.78?±?1.68, 1.89?±?1.26, 0.31?±?0.14, and 0.80?±?0.30?μg?m^?3, whereas WSIC component of PM₁₀, i.e., NH₄ ⁺, SO₄ ^2?, NO₃ ^?, and Cl^? were recorded as 1.96?±?1.66, 8.68?±?3.75, 1.92?±?1.75, and 2.48?±?0.78?μg?m^?3, respectively. In the present case, abundance of nss-SO₄ ^2? in the particulate matter is recorded as 18?%. It suggests the possibility of long-range transport as well as marine biogenic origin. Higher SO₄ ^2?/(SO₂?+?SO₄ ^2?) equivalent molar ratio during the campaign indicates the gas-to-particle conversion with great efficiency over the study region.     

Size distributions and dry deposition fluxes of water-soluble inorganic nitrogen in atmospheric aerosols in Xiamen Bay,China

Size-segregated aerosol particles were collected using a high volume MOUDI sampler at a coastal urban site in Xiamen Bay, China, from March 2018 to June 2020 to examine the seasonal characteristics of aerosol and water-soluble inorganic ions (WSIIs) and the dry deposition of nitrogen species. During the study period, the annual average concentrations of PM₁, PM_2.5, PM₁₀, and TSP were 14.8?±?5.6, 21.1?±?9.0, 35.4?±?14.2 μg m^?3, and 45.2?±?21.3 μg m^?3, respectively. The seasonal variations of aerosol concentrations were impacted by the monsoon with the lowest value in summer and the higher values in other seasons. For WSIIs, the annual average concentrations were 6.3?±?3.3, 2.1?±?1.2, 3.3?±?1.5, and 1.6?±?0.8 μg m^?3 in PM₁, PM_1-2.5, PM_2.5–10, and PM_>10, respectively. In addition, pronounced seasonal variations of WSIIs in PM₁ and PM_1-2.5 were observed, with the highest concentration in spring-winter and the lowest in summer. The size distribution showed that SO₄^2?, NH₄⁺ and K⁺ were consistently present in the submicron particles while Ca²⁺, Mg²⁺, Na⁺ and Cl^? mainly accumulated in the size range of 2.5–10 μm, reflecting their different dominant sources. In spring, fall and winter, a bimodal distribution of NO₃^? was observed with one peak at 2.5–10 μm and another peak at 0.44–1 μm. In summer, however, the fine mode peak disappeared, likely due to the unfavorable conditions for the formation of NH₄NO₃. For NH₄⁺ and SO₄^2?, their dominant peak at 0.25–0.44 μm in summer and fall shifted to 0.44–1 μm in spring and winter. Although the concentration of NO₃–N was lower than NH₄–N, the dry deposition flux of NO₃–N (35.77?±?24.49 μmol N m^?2 d^?1) was much higher than that of NH₄–N (10.95?±?11.89 μmol N m^?2 d^?1), mainly due to the larger deposition velocities of NO₃–N. The contribution of sea-salt particles to the total particulate inorganic N deposition was estimated to be 23.9—52.8%. Dry deposition of particulate inorganic N accounted for 0.95% of other terrestrial N influxes. The annual total N deposition can create a new productivity of 3.55 mgC m^?2 d^?1, accounting for 1.3–4.7% of the primary productivity in Xiamen Bay. In light of these results, atmospheric N deposition could have a significant influence on biogeochemistry cycle of nutrients with respect to projected increase of anthropogenic emissions from mobile sources in coastal region.

     

Atmospheric ionic species in PM2.5 and PM1 aerosols in the ambient air of eastern central India

This study elucidates the characteristics of ambient PM_2.5 (fine) and PM₁ (submicron) samples collected between July 2009 and June 2010 in Raipur, India, in terms of water soluble ions, i.e. Na⁺, NH ₄ ⁺ , K⁺, Mg²⁺, Ca²⁺, Cl^?, NO ₃ ^? and SO ₄ ^2? . The total number of PM_2.5 and PM₁ samples collected with eight stage cascade impactor was 120. Annual mean concentrations of PM_2.5 and PM₁ were 150.9?±?78.6 μg/m³ and 72.5?±?39.0 μg/m³, respectively. The higher particulate matter (PM) mass concentrations during the winter season are essentially due to the increase of biomass burning and temperature inversion. Out of above 8 ions, the most abundant ions were SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ for both PM_2.5 and PM₁ aerosols; their average concentrations were 7.86?±?5.86 μg/m³, 3.12?±?2.63 μg/m³ and 1.94?±?1.28 μg/m³ for PM_2.5, and 5.61?±?3.79 μg/m³, 1.81?±?1.21 μg/m³ and 1.26?±?0.88 μg/m³ for PM₁, respectively. The major secondary species SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ accounted for 5.81%, 1.88% and 1.40% of the total mass of PM_2.5 and 11.10%, 2.68%, and 2.48% of the total mass of PM₁, respectively. The source identification was conducted for the ionic species in PM_2.5 and PM₁ aerosols. The results are discussed by the way of correlations and principal component analysis. Spearman correlation indicated that Cl^? and K⁺ in PM_2.5 and PM₁ can be originated from similar type of sources. Principal component analysis reveals that there are two major sources (anthropogenic and natural such as soil derived particles) for PM_2.5 and PM₁ fractions.     

Chemical composition of rainwater at Lijiang on the Southeast Tibetan Plateau: influences from various air mass sources

Daily rainwater samples collected at Lijiang in 2009 were analyzed for pH, electrical conductivity, major ion (SO₄ ^2?, Cl^?, NO₃ ^?, Na⁺, Ca²⁺, Mg²⁺, and NH₄ ⁺) concentrations, and δ¹⁸O. The rainwater was alkaline with the volume-weighted mean pH of 6.34 (range: 5.71 to 7.11). Ion concentrations and δ¹⁸O during the pre-monsoon period were higher than in the monsoon. Air mass trajectories indicated that water vapor from South Asia was polluted with biomass burning emissions during the pre-monsoon. Precipitation during the monsoon was mainly transported by flow from the Bay of Bengal, and it showed high sea salt ion concentrations. Some precipitation brought by southwest monsoon originated from Burma; it was characterized by low δ¹⁸O and low sea salt, indicating that the water vapor from the region was mainly recycled monsoon precipitation. Water vapor from South China contained large quantities of SO₄ ^2?, NO₃ ^?, and NH₄ ⁺. Throughout the study, Ca²⁺ was the main neutralizing agent. Positive matrix factorization analysis indicated that crustal dust sources contributed the following percentages of the ions Ca²⁺ 85 %, Mg²⁺ 75 %, K⁺ 61 %, NO₃ ^? 32 % and SO₄ ^2? 21 %. Anthropogenic sources accounted for 79 %, 68 %, and 76 % of the SO₄ ^2?, NO₃ ^? and NH₄ ⁺, respectively; and approximately 93 %, 99 %, and 37 % of the Cl^?, Na⁺, and K⁺ were from a sea salt source.     

Characteristics of gaseous pollutants near a main traffic line in Beijing and its influencing factors

Automobile exhaust emissions are becoming increasingly serious with the drastic increase of the number of vehicles in Beijing. In order to investigate the air pollution level and characteristics in the areas near the main traffic lines in Beijing and to identify the contributions from traffic and other sources, gaseous pollutants including NOx, CO, O₃, SO₂, and meteorological parameters have been monitored at a monitoring site and a contrasting site in winter and summer in 2006. The volumes of vehicles on Beiyuan Road were recorded. The average concentrations of NO, NO₂, NOx, CO, O₃, and SO₂ at the monitoring site were 0.148 mg/m³, 0.107 mg/m³, 0.333 mg/m³, 5.110 mg/m³, 0.006 mg/m³, and 0.157 mg/m³, respectively during the sampling period in winter and 0.021 mg/m³, 0.068 mg/m³, 0.101 mg/m³, 4.170 mg/m³, 0.083 mg/m³, and 0.056 mg/m³, respectively in summer. The high concentrations of CO and O₃ reflect the influence of vehicles emission near the traffic lines evidently. The higher concentrations of CO, NO and O₃ in summer may indicate that the characteristics of traffic pollution were more pronounced in summer. Results of regression analysis showed that in winter the concentrations of SO₂ and CO were significantly positively correlated with the emission of heating boilers at night and negatively correlated with wind speed in daytime. The concentrations of NO and NOx were negatively correlated with wind speed, positively correlated with emission of heating boilers in daytime and positively correlated with traffic density at nighttime. The concentrations of NO₂ were positively correlated with the emission of heating boilers in daytime and traffic density at nighttime. In summer, the air quality at the monitoring site and the contrasting site was mainly influenced by the traffic emissions.     

Chemical and isotopic interpretation of major ion compositions from precipitation: a one-year temporal monitoring study in Wrocław,SW Poland

The chemical compositions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₂ ^?, NO₃ ^?, SO₄ ^2?, HCO₃ ^?) of wet precipitation and nitrogen isotope compositions δ¹⁵N(NH₄ ⁺) were studied from January to December 2010 in Wroc?aw (SW Poland). Results of a principle component analysis show that 82 % of the data variability can be explained by three main factors: 1) F1 (40 %) observed during vegetative season (electrical conductivity, HCO₃ ^?, NO₃ ^?, NO₂ ^?, NH₄ ⁺ and SO₄ ^2?), mainly controlling rainwater mineralization; 2) F2 (26 %) observed during vegetative and heating seasons (K⁺, Ca²⁺ and Mg²⁺), probably representing a combination of two processes: anthropogenic dusts and fertilizers application in agricultural fields, and 3) F3 (16 %) reported mainly during heating season (Na⁺ and Cl^?) probably indicating the influence of marine aerosols. Variations of δ¹⁵N(NH₄ ⁺) from ?11.5 to 18.5?‰ identify three main pathways for the formation of NH₄ ⁺: 1) equilibrium fractionation between NH₃ and NH₄ ⁺; 2) kinetic exchange between NH₃ and NH₄ ⁺; 3) NH₄ ⁺ exchange between atmospheric salts particles and precipitation. The coupled chemical/statistical analysis and δ¹⁵N(NH₄ ⁺) approach shows that while fossil fuels burning is the main source of NH₄ ⁺ in precipitation during the heating season, during the vegetative season NH₄ ⁺ originates from local sewage irrigation fields in Osobowice or agricultural fertilizers.     

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.     

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.     

Methodology of analysis associating survey results by the filter-pack method with those of precipitation- Acid-base balance on acid-related and alkali-related chemical species in urban ambient air and its influence on the acidification of precipitation -

Continuous weekly monitoring on the concentration of gases and aerosols in urban ambient air by a four-stage filter-pack method was carried out for 7 years in order to study not only the acid-base balance of acid-related (HNO₃, NO₃ ⁻, and non-sea-salt-(nss-)SO₄ ²⁻) and alkali-related (NH₃, NH₄ ⁺, and nss-Ca²⁺) chemical species but also its influence on the acidification of precipitation. The concentrations of the total nitrate (= NO₃⁻ + HNO₃) and nss-SO₄²⁻ showed a similar seasonal variation: high in the summer and low in the winter. The total nitrate and nss-SO₄²⁻ accounted for 0.43 and 0.57 of the acid-related species, respectively, on an equivalent basis. The total ammonium (= NH₃ + NH₄⁺) accounted for more than 0.9 of the alkali-related species, except for a springtime nss-Ca²⁺ episodic peak. The alkali-related species were generally overabundant compared with the acid-related species in the HNO₃-NO₃⁻-nss-SO₄²⁻-NH₃-NH₄⁺-nss-Ca²⁺ system. The alkali-rich distribution was especially pronounced in the winter, but the acid-related species was comparable to the alkali-related species in the summer, which was attributed to the larger H⁺ deposition by precipitation in the summer. This study can provide a methodology to associate survey results obtained by a filter-pack method with those of precipitation.     

Continuous observations of water-soluble ions in PM2.5 at Mount Tai (1534 m a.s.l.) in central-eastern China

Near real-time measurements of PM_2.5 ionic compositions were performed at the summit of the highest mountain in the central-eastern plains in the spring and summer of 2007 in order to characterize aerosol composition and its interaction with clouds. The average concentrations of total water soluble ions were 27.5 and 36.7 μg?m^?3, accounting for 44% and 62% of the PM_2.5 mass concentration in the spring and summer, respectively. A diurnal pattern of SO ₄ ^2- , NH ₄ ⁺ and NO ₃ ^- was observed in both campaigns and attributed to the upslope/downslope transport of air mass and the development of the planetary boundary layer (PBL). The average SO₂ oxidation ratio (SOR) in summer was 57% (±27%), more than twice that in spring 24% (±16%); the fine nitrate oxidation ratio (NOR) was comparable in the two seasons (9?±?6% and 11?±?10% in summer and spring, respectively). This result indicates strong summertime production of sulfate aerosol. A principal component analysis shows that short-range and long-range transport of pollution, cloud processing, and crustal source were the main factors affecting the variability of the measured ions (and other trace gases and aerosols) at Mt. Tai. Strong indications of biomass burning were observed in summer. Cloud scavenging rates showed larger variations for different ions and in different cloud events. The elevated concentrations of the water soluble ions at Mt. Tai indicate serious aerosol pollution over the North China plain of eastern China.     

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 ⁺.     

Variation of ambient SO2 over Delhi

The temporal variation of ambient SO₂ and the chemical composition of particulate matters (PM_2.5 and PM₁₀) were studied at National Physical Laboratory (NPL), New Delhi (28°38′N, 77°10′E). Spatial variation of SO₂ at seven air quality monitoring stations over Delhi was also studied simultaneously. Wide range of ambient SO₂ was recorded during winter (2.55 to 17.43 ppb) compare to other seasons. SO₂ mixing ratio was recorded significantly high at industrial sites during winter and summer; however, no significant spatial difference in SO₂ mixing ratio was recorded during monsoon. SO ₄ ^2? /(SO₂+SO ₄ ^2? ) ratio was recorded high (0.74) during winter and low (0.69) during summer. Monthly variation of PSCF was analyzed using HYSPLIT seven days backward trajectories and daily average SO₂ data. PSCF analysis suggests that, during winter (December, January, February) ambient SO₂ at the study site might have contributed from long distance sources, located towards west and southwest directions; during monsoon (July, August, September) marine contribution was noticed; whereas, during summer (April, May and June) it was from regional sources (located within few 100 km of study site). During winter there was significant contribution from the long distance sources located in western Asia, northwestern Pakistan, Rajasthan and Punjab provinces of India. Coal used in thermal power plants at Panipat (in the northwestern side) and Faridabad (in the southeastern side), local industries, soil erosion and biomass burning may be major contributing factors for SO₂ during summer. The study establishes that the transport sector may not be the major source of ambient SO₂ in Delhi.     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.     

Traffic aerosols (18 nm particle size 18 μm) source apportionment during the winter period

In November 2004–January 2005, a micro orifice uniform deposit impactor (MOUDI) and a Nanometer (nanometer)-MOUDI were used in the center of Taiwan to measure particle size (18 nm particle size 18 μm) distributions of atmospheric aerosols at a traffic site during the winter period. The average Mass in Media Aerodynamic Diameter (MMAD) of suspended particles is 0.99 μm this study. As for the ultra fine and nanometer (nanometer) particle mode, the composition order for these major ions species was SO₄²⁻ NH₄⁺ NO₃⁻ Mg²⁺ Ca²⁺ Na⁺ K⁺ Cl⁻. An ion Chromatography (DIONEX-100) was used to analyze major anion species, Cl⁻, NO₃⁻, SO₄²⁻ and cation species, NH₄⁺Na⁺, K⁺, Ca²⁺Mg²⁺. Their concentrations were also extracted from various particles size modes (nanometer (nanometer), ultra fine, fine and coarse). The results obtained in this study also indicated that the average portions for the major ionic species (SO₄²⁻, NH₄⁺ and Mg²⁺) in the nanometer (nanometer), ultra fine, fine and coarse particulate modes are about 34%, 37%, 63% and 30%, respectively at this traffic sampling site during the winter period.     

Annual and decadal variation in chemical composition of rain water at all the ten GAW stations in India

Spatial variation of long term annual precipitation volume weighted concentrations of major chemical constituents (SO₄ ^?2, NO₃ ^?, Cl^?, NH₄ ⁺, Ca⁺², Mg⁺², Na⁺ and K⁺ ) at all the ten Global Atmospheric Watch (GAW) stations in India for the period from 1981 to 2012 is studied in this paper. Ionic abundance and balance is studied as well. The range of long term annual mean pH at ten stations was 5.25?±?0.82 to 6.91?±?0.76, lowest at Mohanbari and highest at Jodhpur. The long term annual mean pH for the period 1981–2012 showed decreasing trend at all the stations (significant at 5 % level). Decadal mean pH among ten stations for 1981–1990, 1991–2000 and 2001–2012 ranged between 7.31 to 5.76, 7.45 to 4.92 and 6.16 to 4.77 respectively and showed decreasing trend at all the stations during 1981–1990 to 2001–12. The percentage occurrence of acidic pH (<5.65) at ten stations ranged from 3 to 72 %, lowest at Jodhpur and highest at Mohanbari and it increased from 1981–1990 to 2001–2012 almost at all the stations. Temporal variation of annual mean values of nssSO₄ ^?2, NO₃ ^?, Ca⁺² and pH for the study period were attempted. Variation of nss K (non sea salt Potassium) at all the stations was studied to assess the biomass burning contribution in different regions. Non-marine (terrestrial) contribution dominated for majority of ionic constituents at most of the stations. However marine contribution was found to be dominant for Mg at Port Blair and Minicoy. Also sea salt fraction of SO₄ was higher than terrestrial at Minicoy. Sources of measured ionic constituents in rain water are assessed through correlation analysis. The concentrations of all the ionic species were lowest at Kodaikanal, a high altitude hill top station and the total ionic mass was 136.0 μeq/l. Jodhpur, an arid station not only had highest concentrations of Ca⁺², SO₄ ^?2 and K⁺ but also had highest total ionic content (1051.8 μeq/l) among all the stations. At Srinagar, Jodhpur, Allahabad, Nagpur and Pune stations Ca⁺² was the dominant cation while dominant anion was NO₃ ^? for Srinagar, Allahabad, and Nagpur and Cl^? for Jodhpur and Pune; at Mohanbari NO₃ ^? and Ca⁺²; at Visakhapatnam, Port Blair and Minicoy Na⁺ and Cl^? were abundant. Temporal variation had shown an increasing trend for nssSO₄ ^?2 and NO₃ ^? and obviously decreasing trend for pH at all the stations. However, Ca⁺² showed a decreasing trend at all the stations except at Port Blair. With the exception of Pune and Jodhpur stations, nssK showed a decreasing trend at all the stations revealing decreasing influence of soil/biomass burning over Indian GAW stations. Negative correlation of pH with SO₄ ^?2 was found to be weak compared to NO₃ ^–.     

In-cloud scavenging of gases and aerosols at a mountain site in Central Switzerland

An in-cloud scavenging case study of the major ions (NH₄ ⁺, SO₄ ^2- and NO₃ ^-) determining the cloudwater composition at a mountain site (1620 m.a.s.l.) is presented. A comparison between in-cloud measurements of the cloudwater composition, liquid water content, gas concentrations and aerosol concentrations and pre-cloud gas and aerosol concentrations yields the following results. Cloudwater concentrations resulted from scavenging of about half of the available NH₃, aerosol NH₄ ⁺, aerosol NO₃ ^-, and aerosol SO₄ ^2-. Approximately a third of the SO₂ was scavenged by the cloudwater and oxidized to SO₄ ^2-. Cloud acidity during the first two hours of cloud interception (pH 3.24) was determined mostly by the scavenged gases (NH₃, SO₂, and HNO₃); aerosol contributions to the acidity were found to be small. Observations of gas and aerosol concentrations at three elevations prior to several winter precipitation events indicated that NH₃ concentrations are typically half (12–80 %) of the total (gas and aerosol) N (-III) concentrations. HNO₃ typically is present at much lower concentrations (1–55 %) than aerosol NO₃ ^-. Concentrations of SO₂ are a substantial component of total sulfur, with concentrations averaging 60 % (14–76 %) of the total S (IV and VI).     

Rainwater chemistry and bulk atmospheric deposition in a tropical semiarid ecosystem: the Brazilian Caatinga

We assessed the rainwater chemistry, the potential sources of its main inorganic components and bulk atmospheric deposition in a rural tropical semiarid region in the Brazilian Caatinga. Rainfall samples were collected during two wet seasons, one during an extremely dry year (2012) and one during a year with normal rainfall (2013). According to measurements of the main inorganic ions in the rainwater (H⁺, Na⁺, NH₄ ⁺, K⁺, Ca²⁺, Mg²⁺, Cl^?, NO₃ ^?, and SO₄ ^2?), no differences were observed in the total ionic charge between the two investigated wet seasons. However, Ca²⁺, K⁺, NH₄ ⁺ and NO₃ ^? were significant higher in the wetter year (p < 0.05) which was attributed to anthropogenic activities, such as organic fertilizer applications. The total ionic contents of the rainwater suggested a dominant marine contribution, accounting for 76 % and 58 % of the rainwater in 2012 and 2013, respectively. The sum of the non-sea-salt fractions of Cl^?, SO₄ ^2?, Mg²⁺, Ca²⁺ and K⁺ were 19 % and 33 % in 2012 and 2013, and the nitrogenous compounds accounted for 2.8 % and 6.0 % of the total ionic contents in 2012 and 2013, respectively. The ionic ratios suggested that Mg²⁺ was probably the main neutralizing constituent of rainwater acidity, followed by Ca²⁺. We observed a low bulk atmospheric deposition of all major rainwater ions during both wet seasons. Regarding nitrogen deposition, we estimated slightly lower annual inputs than previous global estimates. Our findings contribute to the understanding of rainfall chemistry in northeastern Brazil by providing baseline information for a previously unstudied tropical semiarid ecosystem.     

Water-soluble inorganic ions of size-differentiated atmospheric particles from a suburban site of Mexico City

During the MILAGRO campaign, March 2006, eight-stage cut impactors were used to sample atmospheric particles at Tecámac (T1 supersite), towards the northeast edge of the Mexico City Metropolitan Area, collecting fresh local emissions and aged pollutants produced in Mexico City. Particle samples were analyzed to determine total mass concentrations of Ca²⁺, Mg²⁺, NH₄ ⁺, K⁺, Cl^?, SO₄ ^2?, and NO₃ ^?. Average concentrations were 22.1 ± 7.2 μg m^?3 for PM₁₀ and 18.3 ± 6.2 μg m^?3 for PM_1.8. A good correlation between PM₁₀ and PM_1.8, without influence from wind patterns, indicates that local emissions are more important than the city’s pollution transported to the site, despite the fact that Tecámac is just 40 km away from Mexico City. A lack of diurnal patterns in the PM_2.5/PM_1.8 ratio supports this conclusion. The inorganic composition of particles suggests that vehicles, soil resuspension, and industries are the main pollutant sources. Finally, the particles were found to be neutralized, in agreement with observations in the Mexico City Metropolitan Area.     

Characterization of water-soluble inorganic ions in size-segregated aerosols in coastal city,Xiamen

The samples of water-soluble inorganic ions (WSIs), including anions (F^?, Cl^?, SO₄^2?, NO₃^?) and cations (NH₄⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺) in 8 size-segregated particle matter (PM), were collected using a sampler (with 8 nominal cut-sizes ranged from 0.43 to 9.0 μm) from October 2008 to September 2009 at five sites in both polluted and background regions of a coastal city, Xiamen. The results showed that particulate matters in the fine mode (PM_2.1, Dp < 2.1 μm) comprised large part of mass concentrations of aerosols, which accounted for 45.56–51.27%, 40.04–60.81%, 42.02–60.81%, and 40.46–57.07% of the total particulate mass in spring, summer, autumn, and winter, respectively. The water-soluble ionic species in the fine mode at five sampling sites varied from 15.33 to 33.82 (spring), 14.03 to 28.06 (summer), 33.47 to 72.52 (autumn), and 48.39 to 69.75 μg m^? 3 (winter), respectively, which accounted for 57.30 ± 6.51% of the PM_2.1 mass concentrations. Secondary pollutants of NH₄⁺, SO₄^2? and NO₃^? were the dominant contributors of WSIs, which suggested that pollutants from anthropogenic activities, such as SO₂, NOx were formed in aerosols by photochemical reactions. The size distributions of Na⁺, Cl^?, SO₄^2? and NO₃^? were bimodal, peaking at 0.43–0.65 μm and 3.3–5.8 μm. Although some ions, such as NH₄⁺ presented bimodal distributions, the coarse mode was insignificant compared to the fine mode. Ca²⁺ and Mg²⁺ exhibited unimodal distributions at all sampling sites, peaking at 2.1–3.3 μm, while K⁺ having a bimodal distributions with a major peak at 0.43–0.65 μm and a minor one at 3.3–4.7 μm, were used in most of samples. Seasonal and spatial variations in the size-distribution profiles suggested that meteorological conditions (seasonal patterns) and sampling locations (geographical patterns) were the main factors determining the formation of secondary aerosols and characteristics of size distributions for WSIs.