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.     

Long-term characterization of major water-soluble inorganic ions in PM<Subscript>10</Subscript> in coastal site on the Japan Sea

PM₁₀ samples were collected over three years at Monzenmachi, the Japan Sea coast, the Noto Peninsula, Ishikawa, Japan from January 17, 2001 to December 18, 2003, using a high volume air sampler with quartz filters. The concentrations of the water-soluble inorganic ions in PM₁₀ were determined with using ion chromatography. By analyzing the characteristics of these, the evidences were found that the Asian outflow had an obviously influence on the air quality at our study site. The results were as follows: the secondary pollutants SO₄²⁻, NO₃⁻ and NH₄⁺ were the primary water-soluble inorganic ions at our study site. The monthly mean concentrations of SO₄²⁻, NH₄⁺, NO₃⁻ and Ca²⁺ have prominent peak in spring due to the strong influence of the Asian continent outflow—these according to backward air trajectory analysis, the maximum of which were 6.09 for nss-SO₄²⁻ in May, 2.87 for NO₃⁻ and 0.68 μg m⁻³ for nss-Ca²⁺ in April, respectively. Comparable to similar data reported from various points around East Asia, it had the characteristics of a polluted coastal area at our study site. The concentration of nss-Ca²⁺ in PM₁₀ drastically increased when the Asian dust invaded, the mean value during the Asian dust days(AD) was 0.86 μg m⁻³, about 4 times higher than those of normal days (NAD). Meanwhile, the mean concentrations of nss-SO₄²⁻, NO₃⁻ and NH₄⁺ in AD periods were higher than those in NAD periods which were 5.87, 1.76 and 1.82 μg m⁻³, respectively, it is due to the interaction between dust and secondary particles during the long-range transport of dust storms. Finally, according to the source apportionment with positive matrix factorization (PMF) method in this study, the major source profiles of PM₁₀ at our study site were categorized as (1) marine salt, (2) secondary sulfate, (3) secondary nitrate and (4) crustal source.     

Hoarfrost and rime chemistry in Poland—An introductory analysis from meteorological perspective

Hoarfrost and rime analysis was based on the collection of samples between 2003 and 2006 from 8 sites, which represent both lowland (northern) and mountainous (southern) parts of Poland. On the other hand 4 of these sites belong to “urban” and 4 to “rural” category. pH, conductivity, SO₄²⁻, NO₃⁻, Cl⁻, H⁺, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺ have been determined in order to study the chemistry of hoarfrost and rime. Higher total inorganic ionic content (TIC) in hoarfrost and rime (2.46 meq·l⁻¹ and 1.23 meq·l⁻¹ respectively) was observed when compared with precipitation (0.37 meq·l⁻¹). Large variability of TIC and chemical composition of individual samples were typical at each of the measurement sites depending on emission patterns, atmospheric conditions and local terrain topography. Higher concentrations of both hoarfrost and rime occurred in southern (mountainous) rather than in northern (lowland) part of Poland which can be explained by worse pollutant dispersion conditions in the south. The surprisingly low hoarfrost concentrations in urban coastal stations in the area of the Bay of Gdansk were attributed to the cleaning effect of nocturnal breeze-type circulation, best pronounced in cool part of the year. Due to relatively high pollutant concentration and long duration, hoarfrost and rime are at least significant factors in environmental processes in different ecosystems in Poland.     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Rainfall chemistry: long range transport versus below cloud scavenging. A two-year study at an inland station (Opme, France)

The present study investigates the chemical composition of wet atmospheric precipitation samples on a daily and an intra-event timescales in Opme, an experimental meteorological station located near Clermont-Ferrand, France. The samples have been collected from November 2005 to October 2007. A total of 217 rainwater samples, integrated for 24 h, were collected and analyzed for pH, conductivity, Na⁺, K⁺, Mg²⁺, NH₄⁺, Ca²⁺, Cl⁻, NO₃⁻ , SO₄²⁻ , PO₄³⁻ and HCO₃⁻. The composition of the rainwater collected appeared to be controlled by the following potential sources: neutralisation process (association among calcium, ammonium with nitrate and sulphate), marine and terrestrial sources. In order to determine the role of long-range transport, the integrated events were classified according to four origins of air-masses: (1) West, (2) North and East, (3) South including Iberian and Italian Peninsulae and (4) local. This analysis allows identifying the source areas of the different association of elements defined. Although calcium is always dominant, total content of rainfall is variable and neutralisation process can be more or less efficient and specific. Rainout (long-range transport) and washout (below-cloud scavenging) were investigated through intra-event measurements of chemical species. Four rain-events have been selected according to the four classes of origins of air-masses. It appears that the first fractions are responsible for an important part of the chemical content of the whole event. Terrestrial species, locally emitted, induce the neutralisation process of acid species. Local meteorological conditions, such as wind’s speed and direction, play an important role as they could provoke recharges of the below cloud air column during the event.     

Acid rain and alkalization in southwestern China: chemical and strontium isotope evidence in rainwater from Guiyang

A comprehensive study on the chemical compositions of rainwater was carried out from June 2007 to December 2008 in Guiyang, a city located on the acid rain control zone of southwest China. All samples were analyzed for pH, major anions (F⁻, Cl⁻, NO₃⁻, SO₄²⁻), major cations (K⁺, Na⁺, Ca²⁺, Mg²⁺, NH₄⁺), Sr²⁺ and Sr isotope. The pH increase is due to the result of neutralization caused by the alkaline dust which contain large amount of CaCO₃. It was observed that Ca²⁺ was the most abundant cation with a volume-weighted mean (VWM) value of 217.6 μeq/L (52.7–1928 μeq/L), accounting for 66% (39%–88%) of the total cations. SO₄²⁻ was the most abundant anion with VWM value of 237.8 μeq/L (49.6-1643 μeq/L). SO₄²⁻ and NO₃⁻ were dominant among the anions, accounting for 66%–97% of the total measured anions. The Sr concentrations vary from 0.01 to 0.92 μmol/L, and strontium isotopic ratios vary in the range of 0.707684–0.710094, with an average of 0.708092. The elements ratios and the ⁸⁷Sr/⁸⁶Sr ratios showed that the solutes of rainwater mainly come from weathering of carbonate and secondary dust input. Moreover, urbanization results in the calcium-rich dust increased and the high concentrations of alkaline ions (mainly Ca²⁺) have played an important role to neutralize the acidity of rainwater, leading to the increase of arithmetic pH mean value by 0.5 units since 2002. It is worth noting that the emission of SO₂ and NO_x from the automobile exhaust is increasing and is becoming another important precursor of acid rain now.     

Black carbon and chemical characteristics of PM<Subscript>10</Subscript> and PM<Subscript>2.5</Subscript> at an urban site of North India

The concentrations of PM₁₀, PM_2.5 and their water-soluble ionic species were determined for the samples collected during January to December, 2007 at New Delhi (28.63° N, 77.18° E), India. The annual mean PM₁₀ and PM_2.5 concentrations (± standard deviation) were about 219 (± 84) and 97 (±56) μgm⁻³ respectively, about twice the prescribed Indian National Ambient Air Quality Standards values. The monthly average ratio of PM_2.5/PM₁₀ varied between 0.18 (June) and 0.86 (February) with an annual mean of ∼0.48 (±0.2), suggesting the dominance of coarser in summer and fine size particles in winter. The difference between the concentrations of PM₁₀ and PM_2.5, is deemed as the contribution of the coarse fraction (PM_10−2.5). The analyzed coarse fractions mainly composed of secondary inorganic aerosols species (16.0 μgm⁻³, 13.07%), mineral matter (12.32 μgm⁻³, 10.06%) and salt particles (4.92 μgm⁻³, 4.02%). PM_2.5 are mainly made up of undetermined fractions (39.46 μgm⁻³, 40.9%), secondary inorganic aerosols (26.15 μgm⁻³, 27.1%), salt aerosols (22.48 μgm⁻³, 23.3%) and mineral matter (8.41 μgm⁻³, 8.7%). The black carbon aerosols concentrations measured at a nearby (∼300 m) location to aerosol sampling site, registered an annual mean of ∼14 (±12) μgm⁻³, which is significantly large compared to those observed at other locations in India. The source identifications are made for the ionic species in PM₁₀ and PM_2.5. The results are discussed by way of correlations and factor analyses. The significant correlations of Cl⁻, SO₄²⁻, K⁺, Na⁺, Ca²⁺, NO₃⁻ and Mg²⁺ with PM_2.5 on one hand and Mg²⁺ with PM₁₀ on the other suggest the dominance of anthropogenic and soil origin aerosols in Delhi.     

Chemical characterization and multivariate analysis of atmospheric PM<Subscript>2.5</Subscript> particles

The new European Council Directive (PE-CONS 3696/07) frames the inhalable (PM₁₀) and fine particles (PM_2.5) on priority to chemically characterize these fractions in order to understand their possible relation with health effects. Considering this, PM_2.5 was collected during four different seasons to evaluate the relative abundance of bulk elements (Cl, S, Si, Al, Br, Cu, Fe, Ti, Ca, K, Pb, Zn, Ni, Mn, Cr and V) and water soluble ions (F⁻, Cl⁻, NO₂ ⁻, NO₃ ⁻, SO₄ ²⁻, Na⁺, NH₄ ⁺, Ca²⁺ and Mg²⁺) over Menen, a Belgian city near the French border. The air quality over Menen is influenced by industrialized regions on both sides of the border. The most abundant ionic species were NO₃ ⁻, SO₄ ²⁻ and NH₄ ⁺, and they showed distinct seasonal variation. The elevated levels of NO₃ ⁻ during spring and summer were found to be related to the larger availability of the NO_x precursor. The various elemental species analyzed were distinguished into crustal and anthropogenic source categories. The dominating elements were S and Cl in the PM_2.5 particles. The anthropogenic fraction (e.g. Zn, Pb, and Cu) shows a more scattered abundance. Furthermore, the ions and elemental data were also processed using principal component analysis and cluster analysis to identify their sources and chemistry. These approach identifies anthropogenic (traffic and industrial) emissions as a major source for fine particles. The variations in the natural/anthropogenic fractions of PM_2.5 were also found to be a function of meteorological conditions as well as of long-range transport of air masses from the industrialized regions of the continent. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Rain-aerosol coupling in the tropical atmosphere of Southeast Asia: distribution and scavenging ratios of major ionic species

Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10⁻⁵ ± 2.8 × 10⁻⁵ s⁻¹ and 1.9 × 10⁻⁴ ± 1.6 × 10⁻⁵ s⁻¹, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH₄ ⁺, Cl⁻, SO₄ ²⁻, and NO₃ ⁻ were found to be higher than those of Na⁺, K⁺, and Ca²⁺ of oceanic and crustal origins. This enrichment implied that gaseous species NH₃, HCl, and HNO₃ could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.     

Cloud/Fog Water Chemistry at a High Elevation Site in South Korea

Cloud/fog water samples were collected at Daekwanreung (840 m msl), a ridge site, in South Korea, from March 2002 to September 2003, by using a Caltech type, self fabricated active strand cloud water collector. The pH, electrical conductivity and major ion concentrations were analyzed. The cloud water pH ranged from 3.6 to 6.8 with an average of 5.2, which was close to the atmospheric neutral point. However, the pH calculated from average concentrations of H+ was 4.7, indicating the cloud/fog water was weakly acidified. SO₄ ²⁻, NO₃ ⁻ and NH₄ ⁺ are predominant ions of which average concentrations were 203.1, 128.1, and 211.7 μeq⋅L⁻¹, respectively. Samples were categorized into four groups by applying 48-hour back trajectory analysis, using the HYbrid Single-Particle Largrangian Integrated Trajectory (HYSPLIT) model. Chemical compositions for the four cases significantly differed from each other. For air masses transported from the East Sea (group E), sea salt concentrations, including Na⁺, Cl⁻ Mg²⁺, were relatively high. Principal acidifying pollutants, such as NO₃ ⁻ and nss-SO₄ ²⁻, significantly increased in the case of air masses transported from the Northeast Asian continent through North Korea (group N) and air masses from the Seoul metropolitan area (group W). However, the mean pH of group N was the highest while the mean pH of group W was the lowest. This suggests that most NO₃ ⁻ and nss-SO₄ ²⁻ in cloud/fog water was neutralized by ammonia and calcium compounds under the influence of air masses transported from Northeast Asia. N/S ratio for the group W was significantly higher than those for the other three groups, suggesting nitrogen species transported from the Seoul metropolitan area contributed to acidification of cloud/fog water at Daekwanreung. Principle Component analysis (PCA) was applied to the cloud/fog water data for presenting characteristics in the four different categories.     

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.     

Factors Influencing Nitrogen Speciation in Coastal Rainwater

Rainwater was collected from 129 rain events between February 2002 and August 2003 and analyzed for ammonium (NH₄⁺), nitrate (NO₃⁻), organic nitrogen (ON) and free amino acids (AA). Inorganic nitrogen (NO₃⁻ + NH₄⁺) was the dominant form of N representing 85% of total nitrogen based on volume-weighted averages. The remainder of the N occurred as organic nitrogen species of which free amino acids contribute approximately 17%. A significant, and in some cases the majority (> 75%), of the remaining ON could be accounted for by macromolecular uncharacterized humic like substances. This has important ramifications with respect to the long range transport of atmospheric ON because humic materials are recalcitrant and therefore may travel long distances from their source. There was a distinct seasonality to the N speciation data with maximum concentrations of NH₄⁺, ON and AA occurring in the spring. Air-mass back trajectory analysis indicates there is a strong anthropogenic component to the NO₃⁻, NH₄⁺ and AA signal but not ON. There was a strong positive correlation between amino acid concentrations and ammonium which suggests they have similar sources and sinks in rainwater. Finally, large episodic additions of NH₄⁺ and AA during tropical events could significantly impact short term bioavailable N budgets in estuaries impacted by these storms. Approximately three times as much NH₄⁺ and AA were deposited during Hurricane Isabel (317 μ moles ⋅ m⁻² and 84 μ moles ⋅ m⁻² respectively) compared to the mean impact of average summertime rain events at this location.     

Long-term measurements of atmospheric PM<Subscript>2.5</Subscript> and its chemical composition in rural Korea

Long-term measurements of ambient particulate matter less than 2.5 μm in diameter (PM_2.5) and its chemical compositions were performed at a rural site in Korea from December 2005 to August 2009. The average PM_2.5 concentration was 31 μg m⁻³ for the whole sampling period, and showed a slightly downward annual trend. The major components of PM_2.5 were organic carbon, SO₄²⁻, NO₃⁻, and NH₄⁺, which accounted for 55 % of total PM_2.5 mass on average. For the top 10 % of PM_2.5 samples, anionic constituents and trace elements clearly increased while carbonaceous constituents and NH₄⁺ remained relatively constant. Both Asian dust and fog events clearly increased PM_2.5 concentrations, but affected its chemical composition differently. While trace elements significantly increased during Asian dust events, NO₃⁻, NH₄⁺ and Cl were dramatically enhanced during fog events due to the formation of saturated or supersaturated salt solution. The back-trajectory based model, PSCF (Potential Source Contribution Function) identified the major industrial areas in Eastern China as the possible source areas for the high PM_2.5 concentrations at the sampling site. Using factor analysis, soil, combustion processes, non-metal manufacture, and secondary PM_2.5 sources accounted for 77 % of the total explained variance.     

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.     

Precipitation Chemistry and Wet Deposition in Kruger National Park, South Africa

The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H₂SO₄) and organic acids (18%). Most of the H₂SO₄ component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS⋅ha⁻¹⋅yr⁻¹ and 2.8 kgN⋅ha⁻¹⋅yr⁻¹, respectively. The N deposition was mainly in the form of NH₄ ⁺. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.     

Chemical composition of rain water and influence of airmass trajectories at a rural site in an ecological sensitive area of Western Ghats (India)

Samples of rain water were collected during monsoon season (June to September) of 2006 and 2007 at Hudegadde, a rural site located in an ecological sensitive area of Western Ghats. The collected samples were analyzed for pH, conductivity and major ions. At this site, rainwater pH varied from 4.20 to 7.39 with 5.65 as volume weighed mean. The observed mean was slightly lower than the average pH reported at most of the Indian continental sites. Monthly variation showed that average pH of rain water was the lowest during September (end of monsoon) and the highest during July (peak of monsoon). Overall, marine sources had dominating influence at this site. However, significant influence of anthropogenic and crustal sources from local as well as inter-continental regions was also noticed. As compared to NO₃⁻, higher concentration of SO₄²⁻ was noticed which might be due to contribution from industrial activities responsible for SO₂ emission. At this site, influence of five types of airmass trajectories was noticed i.e. i) C.I.O. (Central part of Indian Ocean)-when air masses blown from Maldives and nearby region of central Indian ocean. These airmasses had higher concentrations of nss Ca²⁺ which did not show any adverse impact on the pH; ii) N.W.I.O.(North-West Indian Ocean)-when airmasses travelled from oceanic region close to north-east Africa. These airmassses had higher concentrations of nss sulphate and nitrate and gave rise to acid rain; iii) S.W.I.O. (South -West Indian Ocean)- when airmasses came from southern part of Indian ocean (close to Mauritius). During these airmasses, rain water samples had almost equal ratio of nss SO₄²⁻ and nss Ca²⁺ similar to N.W.I.O but very low NO₃⁻ ; iv) Gulf-when airmasses were observed coming from Gulf region. Although these airmasses contributed only 2% of the total number of samples but carried high amount of nss SO₄²⁻ which gave rise to acid rain. The second lowest pH was observed during these airmasses which might be due to very high nssSO₄²⁻/nssCa²⁺ ratios; v) N.W.I.O. + S.W.I.C. (North-West Indian Ocean+South-West Indian Continental)- when airmasses originated from north-west Indian Ocean travelling towards south continental part of India and then arriving to the site. During these airmasses, samples showed typical influence of urban activities having high concentrations of nss SO₄²⁻ and NO₃⁻ leading to the lowest pH of rain water.     

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.     

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.     

Comparison of collection methods to determine atmospheric deposition in a rural Mediterranean site (NE Spain)

Wet-only, dry-only, bulk deposition and deposition of sedimentary particles and gases deposited after the last rain (DAR) were collected weekly at La Castanya station in the Montseny mountains (NE Spain, 41°46′N, 2°21′E) from February 2009 to July 2010. These samples were analysed for pH, alkalinity, and the concentrations of major ions (Cl^?, NO₃ ^?, SO₄ ^2?, Na⁺, K⁺, Ca²⁺, Mg²⁺, NH₄ ⁺). Significant differences were observed between bulk and wet-only precipitation, with an enrichment of ions associated to coarse particles in bulk deposition. The comparison between wet and dry fluxes revealed that the removal of compounds at Montseny occurred mainly by wet deposition, which accounted for 74 % of total deposition. The dry flux was characterised by the predominance of K⁺, Ca²⁺ and Mg²⁺, which are related to coarse particles. Bulk collection methods at Montseny were considered representative of total atmospheric deposition, since bulk deposition plus DAR accounted for 97 % of total deposition measured with wet and dry-only collection devices. Thus, bulk deposition collectors can be recommended for deposition networks at remote sites (lacking electricity connection) in environments, where coarse particles are a predominant fraction of the aerosol mass.