Rapid change in nitrate and sulfate concentrations observed in early stage of precipitation and their deposition processes

The concentrations of H⁺, nitrate (NO₃ ^-), and sulfate (SO₄ ^2-) in rainwater and their temporal changes were analyzed on the basis of continuous observation from 1 July 1991 to 30 June 1992 at a suburb of Nagoya, Japan. The yearly average for pH was 4.4. In general, an increasing pH with increase in precipitation amount was observed for rain events. Relatively high pH rainwater was sometimes observed at the beginning of rainfall, even though high concentrations of NO₃ ^- and SO₄ ^2- were involved. The high pH values were considered to be caused by the neutralization process with particulate matter containing cations. The yearly averaged ratio of equivalent concentration of nitrate to sulfate (N/S) in rainwater was 0.58. In the early stage of rain, the N/S value was usually more than 1.0 due to the difference of scavenging process between NO₃ ^- and SO₄ ^2-. High values of N/S ranging from 5 to 10 were found under the atmospheric conditions of calm winds and low humidity, during which it is possible that atmospheric particles float for a long time in the air before a rain event. The adsorption of NO₃ ^- in the early stage of rainfall by particulate matter was suggested from the difference in scavenging processes of NO₃ ^- and SO₄ ^2-. A possible scavenging process, called limb cloud scavenging, is presented to explain the interaction of particles and nitrate ions at the early stage of rain. In limb cloud scavenging, the repeated migration of cloud particles or raindrops between the inside and outside of clouds increases the absorption of ions to a highly condensed level, thus increasing the N/S value of rainwater. The influence of global scale seasonal phenomena with large amounts of particulates, such as typhoons or Asian dust storms, was also studied.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

Chemical character of precipitation and related particles and trace gases in the North and South of China

Rainwater samples were collected at four sites, including Beijing and Mazhuang Town in the north of China, Shenzhen and Mangdang Mountain in the south of China. Character of atmospheric particles and gases were also measured at Mazhuang Town and Mangdang Mountain. Both of Beijing and Shenzhen are urban sites; Mazhuang Town and Mangdang Mountain are rural and remote sites respectively. The atmospheric pollution at rural plain site in the north of China was more serious than that at remote mountain site in the south of China. At Beijing, Mazhuang Town, Shenzhen and Mangdang Mountain the average pH values in rainwater were 6.02, 5.97, 4.72 and 4.81, respectively and the concentrations of total ions in rainwater were 1454, 1125, 187 and 191 μeq/l, respectively. While the acidity of the rain was higher in the south than that in the north, the rainwater in the north of China was more severely polluted than that in the south. The major acidic ion in the rainwater is SO₄^2-, and NH₄⁺ is the most important neutralizing ion in rainwater at the four sites, followed by Ca²⁺. The amounts of organic acid in precipitation were compared with other sites in the world. The ratios of organic acid to total free acid in rainwater at Mangdang Mountain was 13.8% and the influence of organic acid on acidity of rainwater at mountain site in the south of China is more important. The variation of atmospheric particles, gases and components in rainwater and cloud-fog water during special rain and cloud-fog events was discussed. The importance of washout process varied with atmospheric species. The impacts of rainfall, rain duration time and wind speed on wash-out process were estimated by regression analysis.     

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.     

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.     

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).     

Solubility of HOCl in water and aqueous H2SO4 to stratospheric temperatures

Henry's law constants K_H (mol kg^–1 atm^–1) for the reaction HOCl_(g)=HOCl_(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H₂SO₄ (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg^–1 atm^–1] of HOCl in aqueous H₂SO₄ are given by: ln(H*)=6.4946–mH₂SO₄(–0.04107+54.56/T)–5862 (1/T_o–1/T) where T(K) is temperature and T_o=298.15K. The activity coefficient of HOCl in aqueous H₂SO₄ has a simple Setchenow-type dependence upon H₂SO₄ molality.     

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.     

Chemical compositions of wet precipitation and anthropogenic influences at a developing urban site in southeastern China

A comprehensive study on the chemical compositions of wet precipitation was carried out from January 2004 to December 2004 in Jinhua, southeastern China's Zhejiang Province. All samples were analyzed for pH, electrical conductivity and major ions (F⁻, Cl⁻, NO₃⁻, SO₄²⁻, K⁺, Na⁺, Ca²⁺, Mg²⁺ and NH₄⁺). The rainwater was typically acidic with a volume-weighted mean pH of 4.54, which ranged from 3.64 to 6.76. SO₄²⁻ and NO₃⁻ were the main anions, while NH₄⁺ and Ca²⁺ were the main cations. The concentrations of these major ions were generally higher compared to those reported in other parts of the world, but much lower than those in northern China.Wet deposition fluxes of major ions showed pronounced seasonal variations with maximum in spring and minimum in autumn. Significant correlations were found in soil-derived species among Ca²⁺, Mg²⁺ and K⁺ and sea-salt species between Na⁺ and Cl⁻. Other relatively good correlations were also observed between Ca²⁺ and SO₄^2-, Mg²⁺ and SO₄^2-, Mg²⁺ and NO₃⁻, Mg²⁺ and Cl⁻. Principal component analysis was also performed on individual precipitation to find possible sources of the major ionic species. Varimax rotated four components accounting for 85.9% of the total variance, and were interpreted as acid and alkaline pollutants, sea spray and mixed source, soil and acid/neutralization. Calculation of enrichment factors for rainwater components relative to soil and seawater indicated that Ca²⁺ and K⁺ mainly originated from the terrestrial source, and SO₄^2- and NO₃⁻ were mostly attributed for the anthropogenic activities in the study area. In general, the results suggested that precipitation chemistry is strongly influenced by anthropogenic sources rather than natural and marine sources. The pollutants in rainwater were mainly derived from long distance transport, local industry and traffic sources.     

Fog and rain water chemistry at Mt. Fuji: A case study during the September 2002 campaign

Measurements of fog and rain water chemistry at the summit of Mt. Fuji, the highest peak in Japan, as well as at Tarobo, the ESE slope of Mt. Fuji in September 2002. The pH of fog and rain water sampled at Mt. Fuji varied over a range of 4.0–6.8. Acidic fogs (pH < 5.0) were observed at the summit when the air mass came from the industrial regions on the Asian continent. The ratio of [SO₄²⁻]/[NO₃⁻] in the fog water was lower at Tarobo than at the summit. High concentrations of Na⁺ and Cl⁻ were determined in the rain water sampled at the summit, possibly because of the long-range transport of sea-salt particles raised by a typhoon through the middle troposphere. The vertical transport of sea-salt particles would influence the cloud microphysical properties in the middle troposphere. Significant loss of Mg²⁺ was seen in the rain water at the summit. The concentrations of peroxides in the fog and rain water were relatively large (10–105 μM). The potential capacity for SO₂ oxidation seems to be strong from summer to early autumn at Mt. Fuji. The fog water peroxide concentrations displayed diurnal variability. The peroxide concentrations in the nighttime were significantly higher than those in the daytime.     

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.     

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.     

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.     

Effects of Rainwater Iron and Hydrogen Peroxide on Iron Speciation and Phytoplankton Growth in Seawater near Bermuda

Rainwater is a major source of dissolved iron to much of the world's oceans, including regions where iron may be a limiting nutrient for marine phytoplankton primary production. Rainwater iron is therefore potentially important in regulating global photosynthetic uptake of CO₂, and hence climate. Two rainwater addition bioassay experiments (2% rain) conducted at the Bermuda Atlantic Time-series Station (BATS) during March 2000 using 50 or 100 nM FeCl₂ or FeCl₃ in synthetic rain (pH 4.5 H₂SO₄) showed an increase in chlorophyll a 50% greater than controls after three days. Addition of 20 μM hydrogen peroxide, a typical rainwater concentration at BATS, completely removed the chlorophyll a increase with both forms of iron additions, suggesting stimulation of phytoplankton growth by rainwater iron can be limited by rainwater H₂O₂. In laboratory experiments using Gulf Stream seawater, iron-enriched (100 nM Fe(III)) synthetic rain was mixed with seawater in a 5% rain 95% seawater ratio. Dissolved iron concentrations increased two times above concentrations predicted based on dilution alone. The increase in soluble iron probably resulted from release from seawater particles and was maintained for more than 24 hours. No increase was observed in controls that did not have iron added to the synthetic rain, or with synthetic rainwater containing both added iron and H₂O₂. The increase in iron concentration above that predicted by dilution indicates rain may have a larger effect on seawater iron concentrations than that calculated for rainwater iron addition alone.     

Spatial prediction model and its application to chemistry of atmospheric precipitation in Jordan

This study is concerned with the spatial variability of some wet atmospheric precipitation parameters such as; pH, conductivity (EC). The study also depicts the spatial variability of some ions (cations and anions) of atmospheric precipitation in Jordan such as, Ca²⁺, Mg²⁺, Na⁺ and K⁺, HCO₃⁻, Cl⁻, NO₃⁻ and SO₄²⁻. The basis of the work is to establish a relationship through the cumulative semivariogram technique between the distance ratios and the spatial dependence structure of the chemical composition of atmospheric precipitation. All semivariogram models are constructed in this study in order to understand the behavior of the spatial distribution. The spatial distributions of rainwater parameters show differences from station to station which is expressed in terms of angle, where the larger the angle the weaker the correlation. The semivariogram (SV) models are constructed to show the variation of the rainfall chemistry in Jordan. The SV models show weak correlation between mountain and leeside mountain stations, i.e. mountain and desert stations. On the other hand, good correlations are observed when transferring from south to north of the country. The larger is the found angle, the weaker is the correlation. For most of the SV model the correlation is found to be very weak between desert and mountainous locality. The Standard Regional Dependence Factor (SRDF) is used for prediction of the distribution of rain fall parameters. It shows the relative error between observed and predicted values of rainwater parameters. The overall regional relative error between the observed and estimated concentrations remains less than 15%.     

Sulfur dioxide plume dispersion and subsequent absorption by coniferous forests: Field measurements and model calculations

A Forest SO₂ Absorption Model (ForSAM) was developed to simulate (1) SO₂ plume dispersion from an emission source, (2) subsequent SO₂ absorption by coniferous forests growing downwind from the source. There are three modules: (1) a buoyancy module, (2) a dispersion module, and (3) a foliar absorption module. These modules were used to calculate hourly abovecanopy SO₂ concentrations and in-canopy deposition velocities, as well as daily amounts of SO₂ absorbed by the forest canopy for downwind distances to 42 km. Model performance testing was done with meteorological data (including ambient SO₂ concentrations) collected at various locations downwind from a coal-burning power generator at Grand Lake in central New Brunswick, Canada. Annual SO₂ emissions from this facility amounted to about 30,000 tonnes. Calculated SO₂ concentrations were similar to those obtained in the field. Calculated SO₂ deposition velocities generally agreed with published values.Notation c air parcel cooling parameter (non-dimensional) - E foliar absorption quotient (non-dimensional) - f areal fraction of foliage free from water (non-dimensional) - f _w SO₂ content of air parcel - h height of the surface layer (m) - H height of the convective mixing layer (m) - H _stack stack height (m) - k time level - k _drag coefficient of drag on the air parcel (non-dimensional) - K _z eddy viscosity coefficient for SO₂ (m²·s^–1) - L Monin-Obukhov length scale (m) - L _A single-sided leaf area index (LAI) - n degree-of-sky cloudiness (non-dimensional) - N number of parcels released with every puff (non-dimensional) - PAR photosynthetically active radiation (W m^–2) - Q emission rate (kg s^–2) - r _b diffusive boundary-layer resistance (s m^–1) - r _c canopy resistance (s m^–1) - r _cuticle cuticular resistance (s m^–1) - r _m mesophyllic resistance (s m^–1) - r _s stomatal resistance (s m^–1) - r _exit smokestack exit radius (m) - R normally distributed random variable with mean of zero and variance of t (s) - u _* frictional velocity scale, (m s^–1) - v lateral wind vector (m s^–1) - v _d SO₂ dry deposition velocity (m s^–1) - VCD water vapour deficit (mb) - z _can mean tree height (m) - Z zenith position of the sun (deg) - environmental lapse rate (°C m^–1) - dry adiabatic lapse rate (0.00986°C m^–1) - von Kármán's constant (0.04) - _B vertical velocities initiated by buoyancy (m s^–1) - canopy extinction coefficient (non-dimensional) - ()a denotes ambient conditions - ()can denotes conditions at the top of the forest canopy - ()h denotes conditions at the top of the surface layer - ()H denotes conditions at the top of the mixed layer - ()s denotes conditions at the canopy surface - ()p denotes conditions of the air parcels     

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.     

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。     

Spatial, Temporal and Interannual Variability of Methanesulfonate and Non-Sea-Salt Sulfate in Rainwater in the Southern Indian Ocean (Amsterdam, Crozet and Kerguelen Islands)

Methanesulfonate (MS^–) and non-sea-salt sulfate (nss-SO ₄ ^2– ), two of the major oxidation products of atmospheric dimethylsulfide (DMS), have been continuously measured in rainwater at three remote islands in the Southern Indian Ocean: Amsterdam since 1991, Crozet since 1992, and Kerguelen since 1993. The annual volume weighted mean (VWM) concentrations of nss-SO ₄ ^2– in rainwater were 3.19, 3.04 and 4.57 eq l^–1 at Amsterdam, Crozet, and Kerguelen, respectively while the VWM of MS^– were 0.24, 0.15 and 0.30 eq l^–1, respectively. At all three islands, MS^– presented a well-distinguished seasonal variation with a maximum during summer whereas the seasonal variation of nss-SO ₄ ^2– was less pronounced, possibly due to the increased anthropogenic influence during the winter period. Furthermore, MS^– presented significant interannual variations, in particular at Amsterdam and Crozet, which is closely related to the sea-surface temperature (SST) anomalies). Finally, the nss-SO ₄ ^2– deposition at Crozet Island presented a decreasing interannual trend, reflecting probably reductions in sulfur emissions from Southern Africa. On the contrary no interannual tendency was observed in the nss-SO ₄ ^2– concentrations at Amsterdam Island, indicating that the biogeochemical sulfur cycle at this area is mainly influenced by biogenic emissions.     

Meteorology and haze structure during AGASP-II,Part 1: Alaskan Arctic flights, 2–10 April 1986

The second Arctic Gas and Aerosol Sampling Program (AGASP-II) was conducted across the Alaskan and Canadian Arctic in April 1986, to study the in situ aerosol, and the chemical and optical properties of Arctic haze. The NOAA WP-3D aircraft, with special instrumentation added, made six flights during AGASP-II. Measurements of wind, pressure, temperature, ozone, water vapor, condensation nuclei (CN) concentration, and aerosol scattering extinction (b_sp) were used to determine the location of significant haze layers. The measurements made on the first three flights, over the Arctic Ocean north of Barrow and over the Beaufort Sea north of Barter Island, Alaska are discussed in detail in this report of the first phase of AGASP II. In the Alaskan Arctic the WP-3D detected a large and persistent region of haze between 960 and 750 mb, in a thermally stable layer, on 2, 8, and 9 April 1986. At its most dense, the haze contained CN concentrations >10,000 cm^–3 and b_sp of 80×10^–6 m^–1 suggesting active SO₂ to H₂SO₄ gas-to-particle conversion. Calculations based upon observed SO₂ concentrations and ambient relative humidities suggest that 10⁴–10⁵ small H₂SO₄ droplets could have been produced in the haze layers. High concentrations of sub-micron H₂SO₄ droplets were collected in haze. Ozone concentrations were 5–10 ppb higher in the haze layers than in the surrounding troposphere. Outside the regions of haze, CN concentrations ranged from 100 to 400 cm^–3 and b_sp values were about (20–40)×10^–6 m^–1. Air mass trajectories were computed to depict the air flow upwind of regions in which haze was observed. In two cases the back trajectories and ground measurements suggested the source to be in central Europe.