Seasonal and annual trends of carbonaceous species of PM<Subscript>10</Subscript> over a megacity Delhi,India during 2010–2017

PM₁₀ samples were collected to characterize the seasonal and annual trends of carbonaceous content in PM₁₀ at an urban site of megacity Delhi, India from January 2010 to December 2017. Organic carbon (OC) and elemental carbon (EC) concentrations were quantified by thermal-optical transmission (TOT) method of PM₁₀ samples collected at Delhi. The average concentrations of PM₁₀, OC, EC and TCA (total carbonaceous aerosol) were 222?±?87 (range: 48.2–583.8 μg m^?3), 25.6?±?14.0 (range: 4.2–82.5 μg m^?3), 8.7?±?5.8 (range: 0.8–35.6 μg m^?3) and 54.7?±?30.6 μg m^?3 (range: 8.4–175.2 μg m^?3), respectively during entire sampling period. The average secondary organic carbon (SOC) concentration ranged from 2.5–9.1 μg m^?3 in PM₁₀, accounting from 14 to 28% of total OC mass concentration of PM₁₀. Significant seasonal variations were recorded in concentrations of PM₁₀, OC, EC and TCA with maxima during winter and minima during monsoon seasons. In the present study, the positive linear trend between OC and EC were recorded during winter (R²?=?0.53), summer (R²?=?0.59) and monsoon (R²?=?0.78) seasons. This behaviour suggests the contribution of similar sources and common atmospheric processes in both the fractions. OC/EC weight ratio suggested that vehicular emissions, fossil fuel combustion and biomass burning could be the major sources of carbonaceous aerosols of PM₁₀ at the megacity Delhi, India. Trajectory analysis indicates that the air mass approches to the sampling site is mainly from Indo Gangetic plain (IGP) region (Uttar Pradesh, Haryana and Punjab etc.), Thar desert, Afghanistan, Pakistan and surrounding areas.     

Carbonaceous and inorganic species in PM<Subscript>10</Subscript> during wintertime over Giridih,Jharkhand (India)

Ambient concentrations of organic carbon (OC), elemental carbon (EC) and water soluble inorganic ionic components (WSIC) of PM₁₀ were studied at Giridih, Jharkhand, a sub-urban site near the Indo Gangatic Plain (IGP) of India during two consecutive winter seasons (November 2011–February 2012 and November 2012–February 2013). The abundance of carbonaceous and water soluble inorganic species of PM₁₀ was recorded at the study site of Giridih. During winter 2011–12, the average concentrations of PM₁₀, OC, EC and WSIC were 180.2?±?46.4; 37.2?±?6.2; 15.2?±?5.4 and 18.0?±?5.1 μg m^?3, respectively. Similar concentrations of PM₁₀, OC, EC and WSIC were also recorded during winter 2012–13. In the present case, a positive linear trend is observed between OC and EC at sampling site of Giridih indicates the coal burning, as well as dispersed coal powder and vehicular emissions may be the source of carbonaceous aerosols. The principal components analysis (PCA) also identifies the contribution of coal burning? +?soil dust, vehicular emissions?+?biomass burning and seconday aerosol to PM₁₀ mass concentration at the study site. Backward trajectoy and potential source contributing function (PSCF) analysis indicated that the aerosols being transported to Giridih from upwind IGP (Punjab, Haryana, Uttar Pradesh and Bihar) and surrounding region.     

Particulate morphology and elemental characteristics: variability at middle Indo-Gangetic Plain

Airborne particulates were monitored at an urban location of middle Indo-Gangetic Plain (IGP) and subsequently analyzed for particulate diversity and mixing states. Exceptionally high particulate loadings were found both in case of coarser (PM₁₀: 157.5 ± 102.9 μgm^?3, n = 46) and finer particulates (PM_2.5: 92.5 ± 49.8 μgm^?3). Based on particulate morphology and elemental composition, five different clusters of particulates namely tarball, soot, sulphur-rich, aluminosilicate and mineral species were found to dominate. Soot particles (0.1–5 μm) were found to be partly coated, having voids filled by coating material without being completely engulfed. A specific type of amorphous, carbonaceous spherules was evident in wintertime fine particulates signifying emissions from biomass burning and wild fire. Traces of S, Na and Ca were found associated with carbonaceous agglomerates suggesting its metal scavenging behavior. Particle laden filters were further processed for metallic and water soluble ionic species to constitute aerosol composition. Coarser particulates were characterized with higher metallic species (9.2–17.8 %), mostly of crustal origin (Ca: 5.5 %; Fe: 1.6 %; Zn: 1.3 % and Na: 3.8 %) while PM_2.5 also revealed their association with metallic components (6.0–14.9 %) having Ca (4.6 %), Fe (0.9 %) and K (0.8 %) as principle constituents. Ca, Na and NH₄ ⁺ found to generate chloride and sulphate salts thus affecting particulate hygroscopicity. Elevated fractions of NO₃ ^? and K⁺ in PM_2.5 signified contribution of biomass burning while presence of Cl^? with carbonaceous aerosols having traces of Si and K denoted contribution of farming and burning practices. Black carbon aerosol exhibited significant seasonal variability (6.9?21.9 μgm^?3) which support larger association of carbonaceous aerosols in particle micrograph.     

Seasonal characteristics and sources of carbonaceous components and elements of PM10 (2010–2019) in Delhi,India

In this study we present the seasonal chemical characteristics and potential sources of PM₁₀ at an urban location of Delhi, India during 2010?2019. The concentrations of carbonaceous aerosols [organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) and water insoluble organic carbon (WIOC)] and elements (Al, Fe, Ti, Cu, Zn, Mn, Pb, Cr, F, Cl, Br, P, S, K, As, Na, Mg, Ca, B, Ni, Mo, V, Sr, Zr and Rb) in PM₁₀ were estimated to explore their possible sources. The annual average concentration (2010–2019) of PM₁₀ was computed as 227?±?97 µg m^?3 with a range of 34?734 µg m^?3. The total carbonaceous aerosols in PM₁₀ was accounted for 22.5% of PM₁₀ mass concentration, whereas elements contribution to PM₁₀ was estimated to be 17% of PM₁₀. The statistical analysis of OC vs. EC and OC vs. WSOC of PM₁₀ reveals their common sources (biomass burning and/or fossil fuel combustion) during all the seasons. Enrichment factors (EFs) of the elements and the relationship of Al with other crustal metals (Fe, Ca, Mg and Ti) of PM₁₀ indicates the abundance of mineral dust over Delhi. Principal component analysis (PCA) extracted the five major sources [industrial emission (IE), biomass burning?+?fossil fuel combustion (BB?+?FFC), soil dust, vehicular emissions (VE) and sodium and magnesium salts (SMS)] of PM₁₀ in Delhi, India. Back trajectory and cluster analysis of airmass parcel indicate that the pollutants approaching to Delhi are mainly from Pakistan, IGP region, Arabian Sea and Bay of Bengal.

     

Assessment of PM<Subscript>2.5</Subscript> chemical compositions in Delhi: primary vs secondary emissions and contribution to light extinction coefficient and visibility degradation

Haze-fog conditions over northern India are associated with visibility degradation and severe attenuation of solar radiation by airborne particles with various chemical compositions. PM_2.5 samples have been collected in Delhi, India from December 2011 to November 2012 and analyzed for carbonaceous and inorganic species. PM₁₀ measurements were made simultaneously such that PM_10–2.5 could be estimated by difference. This study analyzes the temporal variation of PM_2.5 and carbonaceous particles (CP), focusing on identification of the primary and secondary aerosol emissions, estimations of light extinction coefficient (b_ext) and the contributions by the major PM_2.5 chemical components. The annual mean concentrations of PM_2.5, organic carbon (OC), elemental carbon (EC) and PM_10–2.5 were found to be 153.6 ± 59.8, 33.5 ± 15.9, 6.9 ± 3.9 and 91.1 ± 99.9 μg m^?3, respectively. Total CP, secondary organic aerosols and major anions (e.g., SO₄ ^2? and NO₃ ^?) maximize during the post-monsoon and winter due to fossil fuel combustion and biomass burning. PM_10–2.5 is more abundant during the pre-monsoon and post-monsoon. The OC/EC varies from 2.45 to 9.26 (mean of 5.18 ± 1.47), indicating the influence of multiple combustion sources. The b_ext exhibits highest values (910 ± 280 and 1221 ± 371 Mm^?1) in post-monsoon and winter and lowest in monsoon (363 ± 110 and 457 ± 133 Mm^?1) as estimated via the original and revised IMPROVE algorithms, respectively. Organic matter (OM =1.6 × OC) accounts for ~39 % and ~48 % of the b_ext, followed by (NH₄)₂SO₄ (~21 % and ~24 %) and EC (~13 % and ~10 %), according to the original and revised algorithms, respectively. The b_ext estimates via the two IMPROVE versions are highly correlated (R² = 0.95, root mean square error = 38 % and mean bias error = 28 %) and are strongly related to visibility impairment (r = ?0.72), mostly associated with anthropogenic rather than natural PM contributions. Therefore, reduction of CP and precursor gas emissions represents an urgent opportunity for air quality improvement across Delhi.     

Biogenic hydrogen sulphide emissions and non-sea sulfate aerosols over the Indian Sundarban mangrove forest

Temporal variations in atmospheric hydrogen sulphide concentrations and its biosphere-atmosphere exchanges were studied in the World’s largest mangrove ecosystem, Sundarbans, India. The results were used to understand the possible contribution of H₂S fluxes in the formation of atmospheric aerosol of different size classes (e.g. accumulation, nucleation and coarse mode). The mixing ratio of hydrogen sulphide (H₂S) over the Sundarban mangrove atmosphere was found maximum during the post-monsoon season (October to January) with a mean value of 0.59?±?0.02 ppb and the minimum during pre-monsoon (February to May) with a mean value of 0.26?±?0.01 ppb. This forest acted as a perennial source of H₂S and the sediment-air emission flux ranged between 1213?±?276 μg S m^?2 d^?1(December) and 457?±?114 μg S m^?2 d^?1 (August) with an annual mean of 768?±?240 μg S m^?2d^?1. The total annual emissions of H₂S from the Indian Sundarban were estimated to be 1.2?±?0.6 Tg S. The accumulation mode of aerosols was found to be more enriched with non-sea salt sulfate with an average loading of 5.74 μg m^?3 followed by the coarse mode (5.18 μg m^?3) and nucleation mode (1.18 μg m^?3). However, the relative contribution of Non-sea salt sulfate aerosol to total sulfate aerosol was highest in the nucleation mode (83%) followed by the accumulation (73%) and coarse mode (58%). Significant positive relations between H₂S flux and different modes of NSS indicated the likely link between H₂S, a dominant precursor for the non-sea salt sulfate, and non-sea sulfate aerosol particles. An increase in H₂S emissions from the mangrove could result in an increase in enhanced NSS in aerosol and associated cloud albedo, and a decrease in the amount of incoming solar radiation reaching the Sundarban mangrove forest.     

Precipitation chemistry and ozone and sulfate concentrations in the ocean atmosphere observed by multi-year cruising in East Asia and West Oceania (35°N–35°S, 100–135°E) in August and September

A comprehensive study on the chemistry of deposition and the concentration of tropospheric ozone and particulate sulfate in the ocean atmosphere was carried out for the data sets in 1990’s. It is important to study the atmospheric situation over the past years as well as the latest, especially in the East Asian region where emission amount of anthropogenic air pollutants have increased year by year due to rapid economic growth. The survey was conducted for 5 years in East Asia and West Oceania (35°N–35°S, 100–135°E) in August and September in 1990’s. The purpose of the survey was to study and understand the chemistry of deposition and the concentration of tropospheric ozone and particulate sulfate in the ocean atmosphere comprehensively in one project. Rainfall over the ocean was insufficiently neutralized. Gas and aerosol over the ocean were mature, i.e., well-mixed, during the period of the transportation. The characteristic latitudinal dependence was observed in the tropospheric ozone concentration, namely, higher in the southern hemisphere and lower in the northern hemisphere (approximately 25 ppb in the 10–40°S region and 5–15 ppb in the 20–40°N region). On the other hand, high concentrations of tropospheric ozone of over 30 ppb were observed in the northern hemisphere, which was attributable to the long-range transportation. The TSP concentration was approximately under the level of 40 μg m^?3 irrespectively of the latitude; in contrast, the nss-SO₄ ^2- concentration showed a clear latitudinal dependence, i.e., higher in the northern hemisphere and lower in the southern hemisphere. The background levels of the nss-SO₄ ^2- concentration were approximately 0.5 μg m^?3 in the 10–40°S region and 2–3 μg m^?3 and 4–5 μg m^?3 in the 0–20°N and 20–40°N regions, respectively.     

Stable carbon and nitrogen isotopic characteristics of PM2.5 and PM10 in Delhi,India

This study presents the chemical composition (carbonaceous and nitrogenous components) of aerosols (PM_2.5 and PM₁₀) along with stable isotopic composition (δ¹³C and δ¹⁵N) collected during winter and the summer months of 2015–16 to explore the possible sources of aerosols in megacity Delhi, India. The mean concentrations (mean?±?standard deviation at 1σ) of PM_2.5 and PM₁₀ were 223?±?69 µg m^?3 and 328?±?65 µg m^?3, respectively during winter season whereas the mean concentrations of PM_2.5 and PM₁₀ were 147?±?22 µg m^?3 and 236?±?61 µg m^?3, respectively during summer season. The mean value of δ¹³C (range: ??26.4 to ??23.4‰) and δ¹⁵N (range: 3.3 to 14.4‰) of PM_2.5 were ??25.3?±?0.5‰ and 8.9?±?2.1‰, respectively during winter season whereas the mean value of δ¹³C (range: ??26.7 to ??25.3‰) and δ¹⁵N (range: 2.8 to 11.5‰) of PM_2.5 were ??26.1?±?0.4‰ and 6.4?±?2.5‰, respectively during the summer season. Comparison of stable C and N isotopic fingerprints of major identical sources suggested that major portion of PM_2.5 and PM₁₀ at Delhi were mainly from fossil fuel combustion (FFC), biomass burning (BB) (C-3 and C-4 type vegitation), secondary aerosols (SAs) and road dust (SD). The correlation analysis of δ¹³C with other C (OC, TC, OC/EC and OC/WSOC) components and δ¹⁵N with other N components (TN, NH₄⁺ and NO₃^?) are also support the source identification of isotopic signatures.

     

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

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

     

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

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

Characterization of chemical properties of atmospheric aerosols over Anmyeon (South Korea), a super site under Global Atmosphere Watch

This paper reports aerosol chemical properties for the first time over a Korean Global Atmosphere Watch (GAW) supersite, Anmyeon (36°32′N; 126° 19′E), during 2003–2004 period. Total suspended Particulates (TSP) showed significant seasonal variation with consistent higher mass concentrations during spring season (average of up to 230?±?190 μg/m³). PM₁₀ also followed similar trend with higher concentrations during spring (average of up to 170?±?130 μg/m³) and showed reduced concentrations during summer. PM_2.5 showed a significant increase during summer (average of up to 60?±?25 μg/m³), which could be due to the influx of fine mode sea salt aerosols associated with the Changma front (summer monsoon). Chemical composition analysis showed enhanced presence of acidic fractions, majorly contributed by sulphates (SO ₄ ^2- ) and nitrates (NO ₃ ^- ) in TSP, PM₁₀ and PM_2.5 during different seasons. Enhanced presence of Calcium (Ca²⁺) was observed during sand storm days during spring. The high correlation obtained on matrix analysis between crustal ions and acidic ions suggests that the ionic compositions over the site are mainly contributed by terrestrial sources of similar origin. The neutralization factors has been estimated to find the extend of neutralization of acidicity by main basic components, and found to have higher value for Ammonium (up to 1.1) in different seasons, indicating significant neutralization of acidic components over the region by NH ₄ ⁺ . Back trajectory analysis has been performed during different seasons to constrain the possible sources of aerosol origin and the results are discussed in detail.     

Influence of the atmospheric conditions on PM<Subscript>10</Subscript> concentrations in Poznań, Poland

This study investigates atmospheric conditions’ influence on the mean and extreme characteristics of PM₁₀ concentrations in Poznań during the period 2006–2013. A correlation analysis was carried out to identify the most important meteorological variables influencing the seasonal dynamics of PM₁₀ concentrations. The highest absolute correlation values were obtained for planetary boundary layer height (r = ?0.57), thermal (daily minimum air temperature: r = ?0.51), anemological (average daily wind speed: r = ?0.37), and pluvial (precipitation occurrence: r = ?0.36) conditions, however the highest correlations were observed for temporal autocorrelations (1 day lag: r = 0.70). As regulated by law, extreme events were identified on the basis of daily threshold value i.e. 50 μg m^?3. On average, annually there are approximately 71.3 days anywhere in the city when the threshold value is exceeded, 46.6 % of those occur in winter. Additionally, 83.7 % of these cases have been found to be continuous episodes of a few days, with the longest one persisting for 22 days. The analysis of the macro-scale circulation patterns led to the identification of an easy-to-perceive seasonal relations between atmospheric fields that favour the occurrence of high PM₁₀ concentration, as well as synoptic situations contributing to the rapid air quality improvement. The highest PM₁₀ concentrations are a clear reaction to a decrease in air temperature by over 3 °C, with simultaneous lowering of PBL height, mean wind speed (by around 1 m s^?1) and changing dominant wind directions from western to eastern sectors. In most cases, such a situation is related to the expansion of a high pressure system over eastern Europe and weakening of the Icelandic Low. Usually, air quality conditions improve along with an intensification of westerlies associated with the occurrence of low pressure systems over western and central Europe. Opposite relations are distinguishable in summer, when air quality deterioration is related to the inflow of tropical air masses originating over the Sahara desert.     

Observed particle sizes and fluxes of Aeolian sediment in the near surface layer during sand-dust storms in the Taklamakan Desert

Monitoring, modeling and predicting the formation and movement of dust storms across the global deserts has drawn great attention in recent decades. Nevertheless, the scarcity of real-time observations of the wind-driven emission, transport and deposition of dusts has severely impeded progress in this area. In this study, we report an observational analysis of sand-dust storm samples collected at seven vertical levels from an 80-m-high flux tower located in the hinterland of the great Taklamakan Desert for ten sand-dust storm events that occurred during 2008–2010. We analyzed the vertical distribution of sandstorm particle grain sizes and horizontal sand-dust sediment fluxes from the near surface up to 80 m high in this extremely harsh but highly representative environment. The results showed that the average sandstorm grain size was in the range of 70 to 85 μm. With the natural presence of sand dunes and valleys, the horizontal dust flux appeared to increase with height within the lower surface layer, but was almost invariant above 32 m. The average flux values varied within the range of 8 to 14 kg m^?2 and the vertical distribution was dominated by the wind speed in the boundary layer. The dominant dust particle size was PM₁₀₀ and below, which on average accounted for 60–80 % of the samples collected, with 0.9–2.5 % for PM_0–2.5, 3.5–7.0 % for PM_0–10, 5.0–14.0 % for PM_0–20 and 20.0–40.0 % for PM_0–50. The observations suggested that on average the sand-dust vertical flux potential is about 0.29 kg m^?2 from the top of the 80 m tower to the upper planetary boundary layer and free atmosphere through the transport of particles smaller than PM₂₀. Some of our results differed from previous measurements from other desert surfaces and laboratory wind-dust experiments, and therefore provide valuable observations to support further improvement of modeling of sandstorms across different natural environmental conditions.     

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

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

A semi-continuous measurement of gaseous ammonia and particulate ammonium concentrations in PM<Subscript>2.5</Subscript> in the ambient atmosphere

Ammonia has a short residence time in the atmosphere and rapidly neutralizes acid gases that occur near its source, requiring a rapid measurement system for ammonia and particulate ammonium concentrations to better understand their sources, temporal variation of ammonia emissions, and the formation of secondary ammonium aerosols. A semi-continuous measurement system, consisting of a diffusion scrubber, a particle growth chamber, an air-liquid separator, and a fluorescent detector, was developed to determine both gaseous ammonia (NH₃) and particulate ammonium (NH ₄ ⁺ ) in PM_2.5 in the ambient atmosphere of Gwangju, South Korea, during the months of March, April, July, and September of 2007. During the sampling periods, the average concentrations of ammonia and ammonium were found to be 2.33?±?1.29 μg/m³ and 1.89?±?0.99 μg/m³, respectively. Although the average gaseous ammonia concentration was highest in March, the particulate ammonium concentration was higher during the warmer season, reaching 2.08?±?1.07 μg/m³ and 2.32?±?0.94 μg/m³ in April and July, respectively, while only 1.68?±?0.61 μg/m³ in March and 1.24?±?0.99 μg/m³ in September. It is proposed that the higher availability of acid species during the warmer months produced a significant amount of particulate ammonium sulfate. Diurnal fluctuation of ammonia and ammonium during the warmer months showed that their peak time occurred at approximately 10:00 am. Both ammonia and ammonium concentrations were better correlated during the warmer months than during the cooler months. Further, the data suggest that the ammonia and ammonium were measured under well dispersed conditions, and multiple sources contributed to the ammonia at the sampling site.     

Ionic and elemental composition of PM<Subscript>2.5</Subscript> aerosols over the Caribbean Sea in the Tropical Atlantic

To characterize atmospheric particulate matter equal or less than 2.5 μm in diameter (PM_2.5) over the Tropical Atlantic Ocean, aerosol sampling was carried out in Puerto Rico during August and September, 2006. Aerosols were analyzed by ion chromatography for water-soluble inorganic and organic ions (including Na⁺, NH₄ ⁺, Mg²⁺, Ca²⁺, K⁺, Cl^?, SO₄ ^2?, NH₄ ⁺, F^?, methanesulfonate (MSA), and oxalate), by inductive coupled plasma mass spectrometry (ICPMS) for trace elements (Al, Fe, Zn, Mn, Cu, Ni, V, Pb, Cr, Sb, Co, Sc, Cd), and by scanning electron microscopy for individual aerosol particle composition and morphology. The results show that the dominant cations in aerosols were Na⁺, (mean: 631 ng m^?3), accounting for 63.8 % of the total cation and NH₄ ⁺ (mean: 164 ng m^?3), accounting for 13.8 % of the total cation measured in this study. The main inorganic anions were Cl^? (576 ng m^?3, 54.1 %) and SO₄ ^2? (596 ng m^?3, 38.0 %). The main organic anion was oxalate (18 ng m^?3). Crustal enrichment factor calculations identified 62 % of the trace elements measured (Cu, Ni, V, Co, Al, Mn, Fe, Sc, and Cr) with crustal origin. Single particle analysis demonstrated that 40 % of the aerosol particles examined were Cl^? rich particles as sodium chloride from seawater and 34 % of the total particles were Si-rich particles, mainly in the form of aluminosilicates from dust material. Based on the combination of air-mass trajectories, cluster analysis and principal component analysis, the major sources of these PM_2.5 particles include marine, Saharan dust and biomass burning from West Africa; however, volcanic emissions from the Soufriere Hills in Montserrat had significant impact on aerosol composition in this region at the time of sample collection.     

Organosulfates – A New Component of Humic-Like Substances in Atmospheric Aerosols?

Ion trap mass spectrometry (ITMS) was used to obtain further qualitative information about the chemical composition of humic-like substances (HULIS) in atmospheric particulate matter. Particles ≤10 μm (PM₁₀) were collected on quartz fiber filters for 24 h in the region of Basel (Switzerland) and extracted with water. HULIS were separated from inorganic salts by size exclusion chromatography (SEC) and detected by electrospray ionization in the negative ion mode (ESI(−)). Series of consecutive fragment ion spectra (MSⁿ) were recorded by ITMS. Full scan mass spectra of the extracts showed a mass distribution pattern characteristic for HULIS. Different molecular ions were selected from this pattern for further fragmentations. Among them the molecular ion m/z 299 was considered as representative and intensively studied. Many MS² and MS³ fragment spectra contained a fragment m/z 97 and a neutral loss of 80 u. Time-of-flight (TOF) MS and deuterium exchange experiments identified m/z 97 as hydrogen sulfate. MS² and MS³ fragment spectra supported the existence of sulfate covalently bound to HULIS. The fragmentation behavior of sulfated HULIS could be confirmed by model compounds.     

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

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

The impacts of urbanization on air quality over the Pearl River Delta in winter: roles of urban land use and emission distribution

In this study, ideal but realistic numerical experiments are performed to explore the relative effects of changes in land use and emission distribution on air quality in the Pearl River Delta (PRD) region in winter. The experiments are accomplished using the Lagrangian particle transport and dispersion model FLEXPART coupled with the Weather Research and Forecasting model under different scenarios. Experiment results show that the maximum changes in daily mean air pollution concentration (as represented by SO₂ concentration) caused by land use change alone reaches up to 2?×?10^?6 g m^?3, whereas changes in concentrations due to the anthropogenic emission distribution are characterized by a maximum value of 6?×?10^?6 g m^?3. Such results reflect that, although the impacts of land use change on air quality are non-negligible, the emission distribution exerts a more significant influence on air quality than land use change. This provides clear implications for policy makers to control urban air pollution over the PRD region, especially for the urban planning in spatial arrangements for reasonable emissions.     

Characteristics of carbonaceous particles in Beijing during winter and summer 2003

Campaigns were conducted to measure Organic Carbon (OC) and Elemental Carbon (EC) in PM2.5 during winter and summer 2003 in Beijing. Modest differences of PM2.5 and PM10 mean concentrations were observed between the winter and summer campaigns. The mean PM2.5/PM10 ratio in both seasons was around 60%, indicating PM2.5 contributed significantly to PM10. The mean concentrations of OC and EC in PM2.5 were 11.2±7.5 and 6.0±5.0μg m-3 for the winter campaign, and 9.4±2.1 and 4.3±3.0 μg m-3 for the summer campaign, respectively. Diurnal concentrations of OC and EC in PM2.5 were found high at night and low during the daytime in winter, and characterized by an obvious minimum in the summer afternoon. The mean OC/EC ratio was 1.87±0.09 for winter and Z39±0.49 for summer. The higher OC/EC ratio in summer indicates some formation of Secondary Organic Carbon (SOC). The estimated SOC was 2.8 μg m-3 for winter and 4.2μg m-3 for summer.