Simulating the fine and coarse inorganic particulate matter concentrations in a polluted megacity

A three dimensional chemical transport model (PMCAMx) is applied to the Mexico City Metropolitan Area (MCMA) in order to simulate the chemical composition and mass of the major PM₁ (fine) and PM_1–10 (coarse) inorganic components and determine the effect of mineral dust on their formation. The aerosol thermodynamic model ISORROPIA-II is used to explicitly simulate the effect of Ca, Mg, and K from dust on semi-volatile partitioning and water uptake. The hybrid approach is applied to simulate the inorganic components, assuming that the smallest particles are in thermodynamic equilibrium, while describing the mass transfer to and from the larger ones. The official MCMA 2004 emissions inventory with improved dust and NaCl emissions is used. The comparison between the model predictions and measurements during a week of April of 2003 at Centro Nacional de Investigacion y Capacitacion Ambiental (CENICA) “Supersite” shows that the model reproduces reasonably well the fine mode composition and its diurnal variation. Sulfate predicted levels are relatively uniform in the area (approximately 3 μg m^?3), while ammonium nitrate peaks in Mexico City (approximately 7 μg m^?3) and its concentration rapidly decreases due to dilution and evaporation away from the urban area. In areas of high dust concentrations, the associated alkalinity is predicted to increase the concentration of nitrate, chloride and ammonium in the coarse mode by up to 2 μg m^?3 (a factor of 10), 0.4 μg m^?3, and 0.6 μg m^?3 (75%), respectively. The predicted ammonium nitrate levels inside Mexico City for this period are sensitive to the physical state (solid versus liquid) of the particles during periods with RH less than 50%.     

Simulating chemistry–aerosol–cloud–radiation–climate feedbacks over the continental U.S. using the online-coupled Weather Research Forecasting Model with chemistry (WRF/Chem)

The chemistry–aerosol–cloud–radiation–climate feedbacks are simulated using WRF/Chem over the continental U.S. in January and July 2001. Aerosols can reduce incoming solar radiation by up to ?9% in January and ?16% in July and 2-m temperatures by up to 0.16 °C in January and 0.37 °C in July over most of the continental U.S. The NO₂ photolysis rates decrease in July by up to ?8% over the central and eastern U.S. where aerosol concentrations are high but increase by up to 7% over the western U.S. in July and up to 13% over the entire domain in January. Planetary boundary layer (PBL) height reduces by up to ?23% in January and ?24% in July. Temperatures and wind speeds in July in big cities such as Atlanta and New York City reduce at/near surface but increase at higher altitudes. The changes in PBL height, temperatures, and wind speed indicate a more stable atmospheric stability of the PBL and further exacerbate air pollution over areas where air pollution is already severe. Aerosols can increase cloud optical depths in big cities in July, and can lead to 500–5000 cm^?3 cloud condensation nuclei (CCN) at a supersaturation of 1% over most land areas and 10–500 cm^?3 CCN over ocean in both months with higher values over most areas in July than in January, particularly in the eastern U.S. The total column cloud droplet number concentrations are up to 4.9 × 10⁶ cm^?2 in January and up to 11.8 × 10⁶ cm^?2 in July, with higher values over regions with high CCN concentrations and sufficient cloud coverage. Aerosols can reduce daily precipitation by up to 1.1 mm day^?1 in January and 19.4 mm day^?1 in July thus the wet removal rates over most of the land areas due to the formation of small CCNs, but they can increase precipitation over regions with the formation of large/giant CCN. These results indicate potential importance of the aerosol feedbacks and an urgent need for their accurate representations in current atmospheric models to reduce uncertainties associated with climate change predictions.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Water-soluble organic compounds at a mountain-top site in Colorado,USA

Water extracts of atmospheric particulate matter (PM_2.5) collected at the Storm Peak Laboratory (SPL) (3210 MSL, 40.45° N, 106.74° W) were analyzed for a wide variety of polar organic compounds. The unique geographical character of SPL allows for extended observations/sampling of the free tropospheric interface. Under variable meteorological conditions between January 9th and January14th 2007, the most abundant compounds were levoglucosan (9–72 ng m^?3), palmitic acid (10–40 ng m^?3) and succinic acid (18–27 ng m^?3). Of 84 analytes included in the GC–MS method, over 50 individual water extractable polar organic compounds (POC) were present at concentrations greater than 0.1 ng m^?3. During a snow event (Jan. 11th–13th), the concentrations of several presumed atmospheric transformation compounds (dicarboxylic acids) were reduced. Lower actinic flux, reduced transport distance, and ice crystal scavenging may explain this variability. Diurnal averages over the sampling period revealed a higher total concentration of water extractable POC at night, 211 ng m^?3 (105–265 ng m^?3), versus day, 160 ng m^?3 (137–205 ng m^?3), which suggests a more aged nighttime aerosol character. This may be due to the increased daytime convective mixing of local primary emissions from the Yampa Valley. XAD resin extracts revealed a gas-phase partitioning of several compounds, and analysis of cloud water collected at this site in 2002 revealed a similar compound abundance trend. Levoglucosan, a wood smoke tracer was generally found to be the most abundant compound in both aerosol and cloud water samples. Variations in meteorological parameters and local/regional transport analysis play an important interpretive role in understanding these results.     

On the contribution of black carbon to the composite aerosol radiative forcing over an urban environment

This paper discusses the extent of Black Carbon (BC) radiative forcing in the total aerosol atmospheric radiative forcing over Pune, an urban site in India. Collocated measurements of aerosol optical properties, chemical composition and BC were carried out for a period of six months (during October 2004 to May 2005) over the site. Observed aerosol chemical composition in terms of water soluble, insoluble and BC components were used in Optical Properties of Aerosols and Clouds (OPAC) to derive aerosol optical properties of composite aerosols. The BC fraction alone was used in OPAC to derive optical properties of BC aerosols. The aerosol optical properties for composite and BC aerosols were separately used in SBDART model to derive direct aerosol radiative forcing due to composite and BC aerosols. The atmospheric radiative forcing for composite aerosols were found to be +35.5, +32.9 and +47.6 Wm^?2 during post-monsoon, winter and pre-monsoon seasons, respectively. The average BC mass fraction found to be 4.83, 6.33 and 4 μg m^?3 during the above seasons contributing around 2.2 to 5.8% to the total aerosol load. The atmospheric radiative forcing estimated due to BC aerosols was +18.8, +23.4 and +17.2 Wm^?2, respectively during the above seasons. The study suggests that even though BC contributes only 2.2–6% to the total aerosol load; it is contributing an average of around 55% to the total lower atmospheric aerosol forcing due to strong radiative absorption, and thus enhancing greenhouse warming.     

Link between aerosol optical,microphysical and chemical measurements in an underground railway station in Paris

Measurements carried out in Paris Magenta railway station in April–May 2006 underlined a repeatable diurnal cycle of aerosol concentrations and optical properties. The average daytime PM₁₀ and PM_2.5 concentrations in such a confined space were approximately 5–30 times higher than those measured in Paris streets. Particles are mainly constituted of dust, with high concentrations of iron and other metals, but are also composed of black and organic carbon. Aerosol levels are linked to the rate at which rain and people pass through the station. Concentrations are also influenced by ambient air from the nearby streets through tunnel ventilation. During daytime approximately 70% of aerosol mass concentrations are governed by coarse absorbing particles with a low Angström exponent (～0.8) and a low single-scattering albedo (～0.7). The corresponding aerosol density is about 2 g cm^?3 and their complex refractive index at 355 nm is close to 1.56–0.035 i. The high absorption properties are linked to the significant proportion of iron oxides together with black carbon in braking systems. During the night, particles are mostly submicronic, thus presenting a greater Angström exponent (～2). The aerosol density is lower (1.8 g cm^?3) and their complex refractive index presents a lower imaginary part (1.58–0.013 i), associated to a stronger single-scattering albedo (～0.85–0.90), mostly influenced by the ambient air. For the first time we have assessed the emission (deposition) rates in an underground station for PM₁₀, PM_2.5 and black carbon concentrations to be 3314 ± 781(?1164 ± 160), 1186 ± 358(?401 ± 66) and 167 ± 46(?25 ± 9) μg m^?2 h^?1, respectively.     

Determination of aerosol yields from 3-methylcatechol and 4-methylcatechol ozonolysis in a simulation chamber

Secondary Organic Aerosol (SOA) formation during the ozonolysis of 3-methylcatechol (3-methyl-1,2-dihydroxybenzene) and 4-methylcatechol (3-methyl-1,2-dihydroxybenzene) was investigated using a simulation chamber (8 m³) at atmospheric pressure, room temperature (294 ± 2 K) and low relative humidity (5–10%). The initial mixing ratios were as follows (in ppb): 3-methylcatechol (194–1059), 4-methylcatechol (204–1188) and ozone (93–531). The ozone and methylcatechol concentrations were followed by UV photometry and GC–FID (Gas chromatography–Flame ionization detector), respectively and the aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted methylcatechol concentrations assuming a particle density of 1.4 g cm^?3. The aerosol formation yield increases as the initial methylcatechol concentration increases, and leads to aerosol yields ranging from 32% to 67% and from 30% to 64% for 3-methylcatechol and 4-methylcatechol, respectively. Y is a strong function of M_o and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. These data are comparable to those published in a recent study on secondary organic aerosol formation from catechol ozonolysis. To our knowledge, this work represents the first investigation of SOA formation from the ozone reaction with methylcatechols.     

Impact of particle emissions of new laser printers on modeled office room

In this study, we present how an indoor aerosol model can be used to characterize particle emitter and predict influence of the source on indoor air quality. Particle size-resolved emission rates were quantified and the source’s influence on indoor air quality was estimated by using office model simulations. We measured particle emissions from three modern laser printers in a flow-through chamber. Measured parameters were used as input parameters for an indoor aerosol model, which we then used to quantify the particle emission rates. The same indoor aerosol model was used to simulate the effect of the particle emission source inside an office model. The office model consists of a mechanically ventilated empty room and the particle source. The aerosol from the ventilation air was a filtered urban background aerosol. The effect of the ventilation rate was studied using three different ventilation ratios 1, 2 and 3 h^?1. According to the model, peak emission rates of the printers exceeded 7.0 × 10⁸ s^?1 (2.5 × 10¹² h^?1), and emitted mainly ultrafine particles (diameter less than 100 nm). The office model simulation results indicate that a print job increases ultrafine particle concentration to a maximum of 2.6 × 10⁵ cm^?3. Printer-emitted particles increased 6-h averaged particle concentration over eleven times compared to the background particle concentration.     

Concentrations and sources of carbonaceous aerosol in the atmosphere of Summit,Greenland

High-volume PM_2.5 samples were collected at Summit, Greenland for approximately six months from late May through December of 2006. Filters were composited and analyzed for source tracer compounds. The individual organic compounds measured at Summit are orders of magnitude smaller than concentrations measured at other sites, including locations representative of remote oceanic, and remote and urban continental aerosol. The measured tracers were used to quantify the contribution of biomass burning (0.6–0.9 ng C m^?3), vegetative detritus (0.3–0.9 ng C m^?3), and fossil fuel combustion (0.1–0.8 ng C m^?3) sources, 4% of OC total, to atmospheric organic carbon concentrations at the remote location of Summit, Greenland. The unapportioned organic carbon (96%) during the early summer period correlates well with the fraction of water soluble organic carbon, indicating secondary organic aerosol as a large source of organic carbon, supported by the active photochemistry occurring at Summit. To the author's knowledge, this paper represents the first source apportionment results for the polar free troposphere.     

Sensitivity of shortwave radiative fluxes to the vertical distribution of aerosol single scattering albedo in the presence of a desert dust layer

The aim of this work is to quantify the sensitivity of shortwave radiative fluxes to changes in the vertical distribution of aerosol absorption, taken into account through the aerosol Single Scattering Albedo (SSA). The case study represents a real atmospheric situation with a desert dust layer (DDL) in the mid troposphere over an urban Boundary Layer (BL) observed at Rome on 20 June 2007. A moderately high aerosol optical depth (AOD), 0.292 at 550 nm, and low Ångström exponent of 0.30 were measured. The observed case was reconstructed with a radiative transfer model, in which the SSA of the boundary layer aerosols was varied from that of a highly absorbing aerosol type (urban) to a highly scattering one (clear marine). The SSA of the DDL is determined keeping fixed the measured SSA of the whole atmospheric column. The simulations show notable changes in the surface and top of the atmosphere (TOA) diffuse fluxes depending on the boundary layer aerosol properties. The aerosol radiative forcing (ARF) at the surface changes by 6–19 W m^?2, depending on the solar zenith angle, when urban or clean marine particles are included in the boundary layer. The ARF differences observed at TOA are between 1 and 5 W m^?2 when urban and clean marine aerosol types in the BL are respectively used, showing a smaller dependency on the solar zenith angle than at the surface.     

Elevated nitrogen isotope ratios of tropical Indian aerosols from Chennai: Implication for the origins of aerosol nitrogen in South and Southeast Asia

To better understand the origins of aerosol nitrogen, we measured concentrations of total nitrogen (TN) and its isotope ratios (δ¹⁵N) in tropical Indian aerosols (PM₁₀) collected from Chennai (13.04°N; 80.17°E) on day- and night-time basis in winter and summer 2007. We found high δ¹⁵N values (+15.7 to +31.2‰) of aerosol N (0.3–3.8 μg m^?3), in which NH₄⁺ is the major species (78%) with lesser contribution from NO₃^? (6%). Based on the comparison of δ¹⁵N in Chennai aerosols with those reported for atmospheric aerosols from mid-latitudes and for the particles emitted from point sources (including a laboratory study), as well as the δ¹⁵N ratios of cow-dung samples (this study), we found that the atmospheric aerosol N in Chennai has two major sources; animal excreta and bio-fuel/biomass burning from South and Southeast Asia. We demonstrate that a gas-to-particle conversion of NH₃ to NH₄HSO₄ and (NH₄)₂SO₄ and the subsequent exchange reaction between NH₃ and NH₄⁺ are responsible for the isotopic enrichment of ¹⁵N in aerosol nitrogen.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

Inferring episodic atmospheric iron fluxes in the Western South Atlantic

Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S–62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m^?2 day^?1 (October 29th–November 15th, 2003); 5.83–1586 nmolFe m^?2 day^?1 (February 15th–March 6th, 2004) and 4.73–586 nmolFe m^?2 day^?1(October 21st–November 5th, 2005).     

Seasonal variations of monosaccharide anhydrides in PM1 and PM2.5 aerosol in urban areas

The concentrations of monosaccharide anhydrides (levoglucosan, mannosan, galactosan) in PM1 and PM2.5 aerosol samples were measured in Brno and ?lapanice in the Czech Republic in winter and summer 2009. 56 aerosol samples were collected together at both sites to investigate the different sources that contribute to aerosol composition in studied localities. Daily PM1 and PM2.5 aerosol samples were collected on pre-fired quartz fibre filters.The sum of average atmospheric concentration of levoglucosan, mannosan and galactosan in PM1 aerosol in ?lapanice and Brno during winter was 513 and 273 ng m^?3, while in summer the sum of average atmospheric concentration of monosaccharide anhydrides (MAs) was 42 and 38 ng m^?3, respectively. The sum of average atmospheric concentration of MAs in PM1 aerosol formed 71 and 63% of the sum of MA concentration in PM2.5 aerosol collected in winter in ?lapanice and Brno, whereas in summer the sum of average atmospheric concentration of MAs in PM1 aerosol formed 45 and 43% of the sum of MA concentration in PM2.5 aerosol in ?lapanice and Brno, respectively.In winter, the sum of MAs contributed significantly to PM1 mass ranging between 1.37% and 2.67% of PM1 mass (Brno – ?lapanice), while in summer the contribution of the sum of MAs was smaller (0.28–0.32%). Contribution of the sum of MAs to PM2.5 mass is similar both in winter (1.37–2.71%) and summer (0.44–0.55%).The higher concentrations of monosaccharide anhydrides in aerosols in ?lapanice indicate higher biomass combustion in this location than in Brno during winter season. The comparison of levoglucosan concentration in PM1 and PM2.5 aerosol shows prevailing presence of levoglucosan in PM1 aerosol both in winter (72% on average) and summer (60% on average).The aerosol samples collected in ?lapanice and Brno in winter and summer show comparable contributions of levoglucosan, mannosan and galactosan to the total amount of monosaccharide anhydrides in both aerosol size fractions. Levoglucosan was the most abundant monosaccharide anhydride with a relative average contribution to the total amount of MAs in the range of 71–82% for PM1 aerosols and 52–79% for PM2.5 aerosols.     

Carbonaceous and inorganic composition in long-range transported aerosols over northern Japan: Implication for aging of water-soluble organic fraction

To better understand the influence of sources and atmospheric processing on aerosol chemical composition, we collected atmospheric particles in Sapporo, northern Japan during spring and early summer 2005 under the air mass transport conditions from Siberia, China and surrounding seas. The aerosols were analyzed for inorganic ions, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and the major water-soluble organic compound classes (i.e., dicarboxylic acids and sugars). SO₄^2? is the most abundant inorganic constituent (average 44% of the identified inorganic ion mass) followed by NH₄⁺ (21%) and NO₃^? (13%). Concentrations of OC, EC, and WSOC ranged from 2.0–16, 0.24–2.9, and 0.80–7.9 μg m^?3 with a mean of 7.4, 1.0, and 3.1 μg m^?3, respectively. High OC/EC ratios (range: 3.6–19, mean: 8.7) were obtained, however WSOC/OC ratios (0.23–0.69, 0.44) do not show any significant diurnal changes. These results suggest that the Sapporo aerosols were already aged, but were not seriously affected by local photochemical processes. Identified water-soluble organic compounds (diacids + sugars) account for <10% of WSOC. Based on some marker species and air mass back trajectory analyses, and using stable carbon isotopic compositions of shorter-chain diacids (i.e., C₂–C₄) as photochemical aging factor of organic aerosols, the present study suggests that a fraction of WSOC in OC is most likely influenced by aerosol aging, although the OC loading in aerosols may be more influenced by their sources and source regions.     

Mineral aerosols from western India: Temporal variability of coarse and fine atmospheric dust and elemental characteristics

Size-segregated aerosol samples (PM_2.5 and PM₁₀) were collected during Jan–Dec-2007 from a high-altitude site located in a semi-arid region (Mt. Abu, 24.6 °N, 72.7 °E, 1680 m asl) in order to asses the temporal variability in the abundance of atmospheric mineral dust and its elemental composition over western India. The mass concentrations of fine (PM_2.5) and coarse (PM_10–2.5) mode aerosols varied from 1.6 to 46.1 and 2.3 to 102 μg m^?3 respectively over the annual seasonal cycle; with dominant and uniform contribution of mineral dust (60–80%) in the coarse mode relative to large temporal variability (11–75%) observed in the fine mode. The coarse mass fraction shows a characteristic increase with the wind speed during summer months (Mar to Jun); whereas fine aerosol mass and its elemental composition exhibit conspicuous temporal pattern associated with north-easterlies during wintertime (Oct–Feb). The Fe/Al weight ratio in PM_2.5 ranges from 0.5 to 1.0 during winter months. The relative enrichment of Fe in fine mode, compared to the crustal ratio of 0.44, is attributed to the down-wind advective transport of combustion products derived from large-scale biomass burning, industrial and automobile emission sources located in the Indo-Gangetic Plain (northern India). In contrast, Ca/Al and Mg/Al weight ratios show relative enrichment of Ca and Mg in the coarse mode; indicating their dominant contribution from carbonate minerals. This has implication to efficient neutralization of atmospheric acidic species (SO₄^2? and NO₃^?) by mineral dust over western India.     

Spectroscopic study of organic coatings on fine particles,exposed to ozone and simulated sunlight

This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C^?1 O₃ ppm^?1 in the region 290–358 nm and by 1.0 absorption units ng-C^?1 O₃ ppm^?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.     

Biogenic emission of dimethylsulfide (DMS) from the North Yellow Sea,China and its contribution to sulfate in aerosol during summer

Seawater, atmospheric dimethylsulfide (DMS) and aerosol compounds, potentially linked with DMS oxidation, such as methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄^2?) were determined in the North Yellow Sea, China during July–August, 2006. The concentrations of seawater and atmospheric DMS ranged from 2.01 to 11.79 nmol l^?1 and from 1.68 to 8.26 nmol m^?3, with average values of 6.20 nmol l^?1 and 5.01 nmol m^?3, respectively. Owing to the appreciable concentration gradient, DMS accumulated in the surface water was transferred into the atmosphere, leading to a net sea-to-air flux of 6.87 μmol m^?2 d^?1 during summer. In the surface seawater, high DMS values corresponded well with the concurrent increases in chlorophyll a levels and a significant correlation was observed between integrated DMS and chlorophyll a concentrations. In addition, the concentrations of MSA and nss-SO₄^2? measured in the aerosol samples ranged from 0.012 to 0.079 μg m^?3 and from 3.82 to 11.72 μg m^?3, with average values of 0.039 and 7.40 μg m^?3, respectively. Based on the observed MSA, nss-SO₄^2? and their ratio, the relative biogenic sulfur contribution was estimated to range from 1.2% to 11.5%, implying the major contribution of anthropogenic source to sulfur budget in the study area.     

Altitude distribution of aerosols over Southeast Arabian Sea coast during pre-monsoon season: Elevated layers,long-range transport and atmospheric radiative heating

Every year, during the pre-monsoon period (March–May), a pronounced increase in aerosol optical depth (AOD) is observed over the eastern Arabian Sea, which is attributed to the transport of continental aerosols. This paper presents the altitude distribution of tropospheric aerosols, characteristics of elevated aerosol layers and aerosol radiative heating of the atmosphere during the pre-monsoon season over Trivandrum (8.5°N, 77°E), a station located at the southwest coast of Indian peninsula which is covered by the eastern Arabian Sea plume. Altitude profiles of aerosol backscatter coefficient (β_a) and linear depolarization ratio (LDR) reveal two distinct aerosol layers persisting between 0–2 km and 2–4 km. The layer at 2–4 km, which contributes about 25% of the AOD during polluted conditions, contains significant amount of non-spherical aerosols. This layer is prominent only when the advection of dry airmass occurs from the northern parts of the Indian subcontinent and northern Arabian Sea. Role of long-range transport in the development of this aerosol layer is further confirmed using latitude–altitude cross-section of β_a observed by CALIPSO. Aerosol content in the layer below 2 km is large when advection of air occurs from the north and east Arabian Sea and is significantly small when it occurs from the southwest Arabian Sea or Indian Ocean. During the highly polluted conditions, aerosols tend to increase the diurnal mean atmospheric radiative heating rate by ～0.8 K day^?1 at 500 m and 0.3 K day^?1 at 3 km, which are about 80% and 30% of the respective radiative heating in the aerosol-free atmosphere.     

Quantitative chemical composition and characteristics of aerosols over western India: One-year record of temporal variability

One-year quantitative chemical data set consisting of water-soluble constituents (NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₃^?, SO₄^2? and HCO₃^?), crustal and trace elements (Al, Fe, Ca, Mg, K, Mn, Zn, Pb) and carbonaceous species (OC, EC) in ambient aerosols, collected over an urban site located in a high-dust semi-arid region of western India, reveals excellent linear relationship (r² = 0.92; slope = 0.96 ± 0.05) between gravimetrically assessed TSP (total suspended particulates) and chemically analyzed aerosol mass. The TSP abundance ranging from 60 to 250 μg m^?3, over a period of 12 months (January–December), is dominated by mineral dust (～70%); whereas contribution from sea-salts, anthropogenic and carbonaceous species exhibits significant temporal variability depending upon the wind regimes. The mineral dust is enriched in Ca, Mg and Fe with respect to upper continental crust (UCC); whereas Zn and Pb exhibit a characteristic anthropogenic source and high enrichment factors. The carbonaceous species show significant seasonality; with dominance of OC (range: 4.6–28 μg m^?3; average: 12.8 μg m^?3; SD: 6.8) and minor contribution from EC (range: 0.3–4.4 μg m^?3; average: 2.4 μg m^?3; SD: 1.4). The observed concentrations are significantly lower than those reported for the metro cities in South Asia but the OC/EC ratios (range: 4.3–35; average: 8.3; SD: 5.7) are significantly higher than the characteristic ratio (～2–4) reported for the urban atmosphere. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and climate change. This study could also be useful in understanding the physical and optical aerosol properties documented from the same site and thus, in validating regional climate models.