Nitrogen and sulfur species in Antarctic aerosols at Mawson,Palmer Station,and Marsh (King George Island)

High volume bulk aerosol samples were collected continuously at three Antarctic sites: Mawson (67.60° S, 62.50° E) from 20 February 1987 to 6 January 1992; Palmer Station (64.77° S, 64.06° W) from 3 April 1990 to 15 June 1991; and Marsh (62.18° S, 58.30° W) from 28 March 1990, to 1 May 1991. All samples were analyzed for Na⁺, SO ₄ ^2– , NO ₃ ^– , methanesulfonate (MSA), NH ₄ ⁺ ,²¹⁰Pb, and⁷Be. At Mawson for which we have a multiple year data set, the annual mean concentration of each species sometimes vary significantly from one year to the next: Na⁺, 68–151 ng m^–3; NO ₃ ^– , 25–30 ng m^–3; nss SO ₄ ^2– , 81–97 ng m^–3; MSA, 19–28 ng m^–3; NH ₄ ⁺ , 16–21 ng m^–3;²¹⁰Pb, 0.75–0.86 fCi m^–3. Results from multiple variable regression of non-sea-salt (nss) SO ₄ ^2– with MSA and NO ₃ ^– as the independent variables indicates that, at Mawson, the nss SO ₄ ^2– /MSA ratio resulting from the oxidation of dimethylsulfide (DMS) is 2.80±0.13, about 13% lower than our earlier estimate (3.22) that was based on 2.5 years of data. A similar analysis indicates that the ratio at Palmer is about 40% lower, 1.71±0.10, and more comparable to previous results over the southern oceans. These results when combined with previously published data suggest that the differences in the ratio may reflect a more rapid loss of MSA relative to nss SO ₄ ^2– during transport over Antarctica from the oceanic source region. The mean²¹⁰Pb concentrations at Palmer and Marsh and the mean NO ₃ ^– concentration at Palmer are about a factor of two lower than those at Mawson. The²¹⁰Pb distributions are consistent with a²¹⁰Pb minimum in the marine boundary layer in the region of 40°–60° S. These features and the similar seasonalities of NO ₃ ^– and²¹⁰Pb at Mawson support the conclusion that the primary source regions for NO ₃ ^– are continental. In contrast, the mean concentrations of MSA, nss SO ₄ ^2– , and NH ₄ ⁺ at Palmer are all higher than those at Mawson: MSA by a factor of 2; nss SO ₄ ^2– by 10%; and NH ₄ ⁺ by more than 50%. However, the factor differences exhibit substantial seasonal variability; the largest differences generally occur during the austral summer when the concentrations of most of the species are highest. NH ₄ ⁺ /(nss SO ₄ ^2– +MSA) equivalent ratios indicate that NH₃ neutralizes about 60% of the sulfur acids during December at both Mawson and Palmer, but only about 30% at Mawson during February and March.     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

A Long Term Study on Chemical Composition of Rainwater at Dayalbagh, a Suburban Site of Semiarid Region

Rainwater samples were collected for the monsoon period of 1988 and 1991–1996 at Dayalbagh (Agra), a suburban site situated in semiaridregion. The mean pH was 7.01 ±1.03 well above 5.6, which is the reference pH. Concentration of Ca²⁺ was observed to be highest followed by Mg²⁺, NH₄ ⁺,SO₄ ^2–, Cl^–,NO₃ ^–, Na⁺, F^– and K⁺. The ratios of SO₄ ^2– + NO₃ ^– andCa²⁺ + Mg²⁺ (TA/TC) have been considered as indicatorfor acidity. In the Agra region ratio of TA/TC is quite below 1.0 indicating alkaline nature of rainwater. The lowest value of 0.24 was observed in 1991 likely due to the lowest rain depth of the decade. The highest value of 0.54 was observed in 1996, a year with a large rain depth and increase in line (vehicular traffic) and area sources (population growth). Good correlation between Ca²⁺ and NO₃ ^–,Ca²⁺ and SO₄ ^2– andSO₄ ^2– and NO₃ ^–,indicates that wind carried dust and soil play a significant role in neutralization of precipitation acidity.     

Chemical Composition of Wet Precipitation in Irbid, Jordan

Rainwater samples were collected in Irbid city using 24 hour sampling periods from December 1996 to April 1998. All samples were analyzed for major cations (Na⁺, K⁺, Ca²⁺ and Mg²⁺), major anions (Cl^–, NO₃ ^– and SO₄ ^2–) and pH. High levels of Ca²⁺ and SO₄ ^2– were observed. Together, Ca²⁺ and SO₄ ^2– made up more than 52.4% of the total ion mass, while Ca²⁺ alone contributed over 39.0% of the total cation. The majority of the rain samples collected had pH values higher than 5.6. The average pH was 6.4±0.9. High values of pH are attributed to the neutralization by natural alkaline local dusts which contain large fractions of calcite. Correlation and mineralogical analyses indicated that Ca²⁺, K⁺ and fractions of Na⁺, SO₄ ^2– and Mg²⁺ are of crustal origin. Results of the present study suggested that the atmospheric composition in the city is strongly influenced by natural sources rather than anthropogenic.     

Particle-size distribution of inorganic water soluble ions in the venezuelan savannah atmosphere during burning and nonburning periods

The results presented are the first complete analysis of inorganic soluble ions in a tropical savannah region. Atmospheric particles were collected in six rural Venezuelan savannah sites. Concentrations and size distribution of NO₃ ^–, SO₄ ^2-, CI^–, PO₄ ^3-, NH₄ ⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺ were determined in samples collected with Hi Vol samplers equipped with five-stage cascade impactors. Concentrations were higher in the dry season, with a maximum during the burning periods. Using Na⁺ as a reference, the results show a deficit of Cl^– and, with the exception of Mg²⁺, an enrichment of all other ions with respect to marine aerosols. Significant variations were observed in particle-size distribution between different periods. Various pairs of ions present similar size distributions: SO₄ ^2- and NH₄ ⁺; Cl^– and Na⁺; PO₄ ^3- and K⁺; Ca²⁺, Mg²⁺ and NO₃ ^–; indicating that the ions were produced by the same source and/or were involved in similar atmospheric processes. Possible primary sources, the gas-to-particle atmospheric process, environmental implication of long-range transport of nutrients during dry seasons, etc., are discussed.     

Trends in chemical composition of precipitation in Nanjing, China, during 1992–2003

In this study, variations of the chemical composition of precipitation in Nanjing, China, over a 12-year period (1992–2003) are presented. The average annual concentration of pH value was 5.15, ranging from 4.93 to 5.36, and there was no significant trend in the acidity of precipitation. SO₄²⁻, Cl⁻ and NO₃⁻ were the main anions, while Ca²⁺, NH₄⁺ and Mg²⁺ were the main cations. The concentrations of these main ions were very high compared to those reported in many other areas around the world. Most of the ions came from anthropogenic and crustal sources. High correlations were found among dust-derived cations Ca²⁺, Mg²⁺and K⁺, between Cl⁻ and SO₄²⁻, between Cl⁻ and NH₄⁺ and between acidic anions and dust-derived cations, such as SO₄²⁻ and Ca²⁺, SO₄²⁻ and K⁺, Cl⁻ and Ca²⁺, Cl⁻ and K⁺, F⁻ and Mg²⁺ and F⁻ and K⁺. A significant decreasing trend was observed in concentration of SO₄²⁻ because of the abatement strategies for SO₂ emissions and energy policy change, while a significant increasing trend was found in the contribution of NO₃⁻ to acidification due to the rapidly growing number of motor vehicles. A significant decreasing trend was found in dust-derived cation Ca²⁺ due to more stringent controls of industrial dust emissions and rapid urbanization reducing the amount of open land, while the contribution of NH₄⁺ to neutralization increased relatively.     

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.     

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO₄ ^2–,Cl^–, F^–, NO₃ ^–, K⁺, Na⁺,NH₄ ⁺, Ca²⁺ and Mg²⁺ were determined in 11 size bins from 0.07 m to >25.5 m. The near-source size distributions showed major modes at 0.5m (SO₄ ^2–, H⁺,NH₄ ⁺); 0.2 m and 5.0 m (Cl^–) and 2.0–5.0 m(F^–). K⁺ and Na⁺ mirrored the SO₄ ^2– size-resolvedconcentrations closely, suggesting that these were transported primarily asK₂SO₄ and Na₂SO₄ in acidic solution, while Mg²⁺ andCa²⁺ presented modes in both <1 m and >1 m particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO₄ ^2–, Cl^–, F^–,H⁺, Na⁺, K⁺ and Mg²⁺ were observed around the 10 m particle diameter in this dust. The volcanic SO₄ ^2– flux leaving the craterwas 0.07 kg s^–1.     

Characteristics of ionic components in precipitation in Kitakyushu City,Japan

Precipitation samples were collected by filtrating bulk sampler in Kitakyushu City, Japan, from January 1988 to December 1990. Volume weighted annual mean of pH was 4.93, but the pH distribution indicated that most probable value lay in the range pH 6.0–6.4. Volume weighted annual mean concentrations of major ionic components were as follows; SO ₄ ^2– : 84.2, NO ₃ ^– : 28.1, Cl^–: 86.3, NH ₄ ⁺ : 45.5, Ca²⁺: 63.3, Mg²⁺: 27.0, K⁺: 3.4, Na⁺: 69.0 µ eq l^–1. The highest concentrations of these ionic components were observed in winter and the lowest occurred in the rainy season. The ratio of ex-SO ₄ ^2– /NO ₃ ^– exhibited the lowest ratio in summer, and the highest ratio in winter. Good correlations were obtained between Cl^– and Na⁺, ex-SO ₄ ²⁺ and ex-Ca²⁺, NO ₃ ^– and ex-Ca²⁺, and NH ₄ ⁺ and ex-SO ₄ ^2– , respectively. However, no correlation between Cl^– and Na⁺ with Ca²⁺ was observed. The relationship of H⁺ with (ex-SO ₄ ^2– + NO ₃ ^– ) - (ex-Ca²⁺ + NH ₄ ⁺ ) indicated positive correlation.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

Measurements of gas and aerosol for two weeks in northern China during the winter–spring period of 2000, 2001 and 2002

Intensive measurements of gas and aerosol for 2 weeks were carried out at Qingdao (gas and aerosol in 2000, 2001 and 2002), Fenghuangshan (gas and aerosol in 2000 and 2001), and Dalian (aerosol in 2002) in the winter–spring period. High SO₂ episodes were observed on 18 January 2000 at both Qingdao and Fenghuangshan. According to back trajectory calculations and analysis of gaseous species, high SO₂ episodes were caused by local pollution and transport.Nitrate, sulfate and ammonium were the major species in PM_2.5. Mass fractions of NO₃⁻, nss-SO₄²⁻ and NH₄⁺ at Qingdao in 2002 were 10%, 12% and 5.5% for PM_2.5, respectively, which were higher than that of nss-Ca²⁺ (1%). Chemical compositions observed at Dalian and Fenghuangshan were similar to those at Qingdao. The mass ratio of nss-SO₄²⁻/SO₂ at Qingdao in winter was low (< 1.2), indicating that sulfate was probably produced by the slow oxidation of SO₂ in the gas phase and/or was transported from outside of Qingdao in winter. The equivalent ratio of NH₄⁺ to nss-SO₄²⁻ was 1.39, suggesting that ammonium sulfate was one of the major chemical compositions in PM_2.5. The NO₃⁻/SO₄²⁻ ratio at Qingdao was higher than that at remote places in East Asia. Gas and aerosol data obtained at Fenghuangshan were similar to data at Qingdao, suggesting that emissions from small cities may have a great influence on pollution in northern China.     

Determination of inorganic ions and trace elements in total suspended particles at three urban zones in the Mexico City Metropolitan Area and one rural site

Inorganic ions and trace metals in total suspended particles were measured during the period 2006–2007 at four sites; three urban sites in the Mexico City Metropolitan Area (MCMA) and one nearby rural site in the state of Morelos. SO₄²⁻, NO₃⁻, Cl⁻ and NH₄⁺ ions were analyzed by ion chromatography; Na⁺, K⁺, Ca²⁺ and Mg²⁺ by flame atomic absorption spectroscopy, and Al, Cd, Cr, Mn, Pb and V by an atomic absorption spectrometer with a graphite furnace attachment. The results indicated that SO₄²⁻ was the most abundant ion. All trace elements except Mn and V showed statistically significant differences between sampling sites. Pearson's correlation applied to all data showed a high correlation among SO₄²⁻, NO₃⁻ and NH₄⁺, indicating a common anthropogenic origin. In addition, the correlation observed between Ca²⁺ and Al indicated a crustal origin, as supported by the enrichment factors. Over the total sampling period, significant differences in particles and trace metals were found between sites and meteorological seasons. To gain a better insight into the origin of trace metals and major inorganic ions, a Principal Component Analysis was applied to the results for six trace metal and eight inorganic ions.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

Chemical characteristics of wet precipitation at an urban site of Guangzhou, South China

The pH variation and chemical characteristics of rainwater were investigated from January 2006 to December 2006 at an urban site of Guangzhou, South China. The rainwater was typically acidic with a volume-weighted mean pH value of 4.49, which ranged from 3.52 to 6.28. The volume-weighted mean equivalent concentration of components followed the order: SO₄²⁻ > Ca²⁺ > Cl⁻ > NH₄⁺ > Na⁺ > NO₃⁻ > K⁺ > Mg²⁺ > F⁻, indicating that SO₄²⁻, Cl⁻ and NO₃⁻ were the main anions, while Ca²⁺ and NH₄⁺, were the main cations. Ca²⁺ and NH₄⁺ were major neutralization constituents of the precipitation. Furthermore, correlation analysis and principal component analysis method were performed to identify possible common sources of major ions. Sources of the major ions were assessed based on enrichment factor method.     

Ambient air dry deposition and ionic species analysis by using various deposition collectors in Shalu, central Taiwan

This study describes the chemical composition of dry deposition collected at a highway traffic site in central Taiwan during daytime and nighttime periods by using a dry deposition plate (DDP) and water surface sampler (WSS). In addition, the characterization for mass and water-soluble species of total suspended particulate (TSP), both PM_2.5 and PM₁₀, was studied at the study site from August 22 to November 30, 2006. Dry deposition fluxes of ambient air particulates and inorganic species (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃⁻ and SO₄²⁻) were analyzed by Ion Chromatography (DIONEX-100).Results of the particulate dry deposition fluxes and mass concentrations are higher in the water surface sampler with respect to the dry deposition plate used in this study. Statistical results also showed the average dry deposition flux of the ionic species (Na⁺, NH₄⁺, K⁺, Cl⁻, NO₃⁻ and SO₄²⁻) obtained by the DDP and WSS displayed significant differences. Also, the average concentrations of Mg²⁺ and, Ca²⁺ were statistically the same at this study site.     

Studies on Intercorrelation between Ions Co-Occurring in Precipitation in the Gdańsk-Sopot-Gdynia Tricity (Poland)

The paper presents monitoring results and environmental pollution assessment for the Gdask-Sopot-Gdynia Tricity (Poland), based onanalysis of precipitation. Precipitation samples were collected over a period of 12 months (January–December 1998) at ten locations in the Tricity. The following selected ions were determined in the samples:SO₄ ^2–, F^–, Cl^–, NO₃ ^–,PO₄ ^3–, NH₄ ⁺, Na⁺,Mg²⁺, Ca²⁺, K⁺. The results were subjected to full statistical evaluation. Values of the parameters determined were correlated with each other. An attempt was made to explain co-occurrences of certain ions and the significance of their mutual effects. Pollutant concentrations and loads in precipitation were also correlated with data on wind direction and temperature in the region.Deposition of pollutants was very high in spring due to the prevailing air circulation patterns and low temperatures. Analysis of the correlations between co-occurring ions confirmed the significant impact of the location (sea coast) on the composition of rain water. Ionic ratios in rainwater were similar to those observed for sea salt samples. In addition, heavy traffic was most probably responsible for high concentrations of various forms of nitrogen and sulphates in the vicinity of major highways.     

A three-dimensional model of the global ammonia cycle

Using a three-dimensional (3-D) transport model of the troposphere, we calculated the global distributions of ammonia (NH₃) and ammonium (NH ₄ ⁺ ), taking into account removal of NH₃ on acidic aerosols, in liquid water clouds and by reaction with OH. Our estimated global 10°×10° NH₃ emission inventory of 45 Tg N-NH₃ yr^– provides a reasonable agreement between calculated wet NH ₄ ⁺ deposition and measurements and of measured and modeled NH ₄ ⁺ in aerosols, although in Africa and Asia especially discrepancies exist.NH₃ emissions from natural continental ecosystems were calculated applying a canopy compensation point and oceanic NH₃ emissions were related to those of DMS (dimethylsulfide). In many regions of the earth, the pH found in rain and cloud water can be attributed to acidity derived from NO, SO₂ and DMS emissions and alkalinity from NH₃. In the remote lower troposphere, sulfate aerosols are calculated to be almost neutralized to ammonium sulfate (NH₄)₂SO₄, whereas in the middle and upper troposphere, according to our calculations, the aerosol should be more acidic, as a result of the oxidation of DMS and SO₂ throughout the troposphere and removal of NH₃ on acidic aerosols at lower heights. Although the removal of NH₃ by reaction with the OH radical is relatively slow, the intermediate NH₂ radical can provide a substantial annual N₂O source of 0.9 _–0.4 ^+0.9 Tg, thus contributing byca. 5% to estimated global N₂O production. The oxidation by OH of NH₃ from anthropogenic sources accounts for 10% of the estimated total anthropogenic sources of N₂O. This source was not accounted for in previous studies, and is mainly located in the tropics, which have high NH₃ and OH concentrations. Biomass burning plumes, containing high NO _x and NH₃ concentrations provide favourable conditions for gas phase N₂O production. This source is probably underestimated in this model study, due to the coarse resolution of the 3-D model, and the rather low biomass burning NH₃ and NO _x emissions adopted. The estimate depends heavily on poorly known concentrations of NH₃ (and NO _x ) in the tropics, and uncertainties in the rate constants of the reactions NH₂ + NO₂ N₂O + H₂O (R4), and NH₂ + O₃ NH₂O + O₂ (R7).     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.