Measurements of isoprene-derived organosulfates in ambient aerosols by aerosol time-of-flight mass spectrometry-part 2: temporal variability and formation mechanisms

Organosulfate species have recently gained attention for their potentially significant contribution to secondary organic aerosol (SOA); however, their temporal behavior in the ambient atmosphere has not been probed in detail. In this work, organosulfates derived from isoprene were observed in single particle mass spectra in Atlanta, GA during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Real-time measurements revealed that the highest organosulfate concentrations occurred at night under a stable boundary layer, suggesting gas-to-particle partitioning and subsequent aqueous-phase processing of the organic precursors played key roles in their formation. Further analysis of the diurnal profile suggests possible contributions from multiple production mechanisms, including acid-catalysis and radical-initiation. This work highlights the potential for additional SOA formation pathways in biogenically influenced urban regions to enhance the organic aerosol burden.     

Evidence for the existence of organosulfates from beta-pinene ozonolysis in ambient secondary organic aerosol

The formation of organosulfates from the gas-phase ozonolysis of beta-pinene in the presence of neutral or acidic sulfate particles was investigated in a series of indoor aerosol chamber experiments. The organosulfates were analyzed using high-performance liquid chromatography (LC) coupled to electrospray ionization-time-of-flight mass spectrometry (MS) in parallel to ion trap MS. Organosulfates were only found in secondary organic aerosol from beta-pinene ozonolysis in the presence of acidic sulfate seed particles. One of the detected organosulfates also occurred in ambient aerosol samples that were collected at a forest site in northeastern Bavaria, Germany. beta-Pinene oxide, an oxidation product in beta-pinene/O3 and beta-pinene/NO3 reactions, is identified as a possible precursor for the beta-pinene-derived organosulfate. Furthermore, several nitroxy-organosulfates originating from monoterpenes were found in the ambient samples. These nitroxy-organosulfates were only detected in the nighttime samples, suggesting a role for nighttime chemistry in their formation. Their LC/MS chromatographic peak intensities suggest that they represent an important fraction of the organic mass in ambient aerosols, especially at night.     

Hydroxycarboxylic acid-derived organosulfates: synthesis, stability, and quantification in ambient aerosol

Organosulfates have been proposed as contributors to aerosol growth and have been detected in both chamber and atmospheric aerosol samples. We present a simple method for the synthesis of quantitative analytical standards of two small hydroxycarboxylic acid-derived organosulfates, glycolic and lactic acid sulfate. Additionally, we discuss the stability of hydroxycarboxylic acid-derived organosulfates and their previously proposed sulfate hemiacetal isomers in commonly used solvents for filter extraction. The hydroxycarboxylic acid-derived organosulfates were found to be stable under acidic conditions comparable to those found in ambient aerosol. By using synthesized standards, quantitative organosulfate concentrations were measured from ambient particulate matter (PM(2.5)) collected in urban locations in the United States, Mexico City, and Pakistan. Lactic acid sulfate and glycolic acid sulfate concentrations ranged 0.4-3.8 ng/m(3) and 1.9-11.3 ng/m(3), respectively. We propose that glycolic acid sulfate represents an important tracer for atmospheric processes that form organosulfates in ambient particulate matter.     

Formation and stability of atmospherically relevant isoprene-derived organosulfates and organonitrates

Isoprene is the precursor for number of alcohol, organosulfate, and organonitrate species observed in ambient secondary organic aerosol (SOA). Recent laboratory and field work has suggested that isoprene-derived epoxides may be crucial intermediates that can explain the existence of these compounds in SOA. To confirm this hypothesis, the specific hydroxy epoxides observed in gas phase isoprene photooxidation experiments (as well as several other related species) were synthesized and the bulk phase aqueous reactions of these species in the presence of sulfate and nitrate were studied via nuclear magnetic resonance (NMR) techniques. The results indicate that both primary and tertiary organosulfates and organonitrates are efficiently formed from the potential SOA reactions of isoprene-derived epoxides. However, the tertiary organonitrates are shown to undergo rapid nucleophilic substitution reactions (in which nitrate is substituted for by water or sulfate) over the whole range of SOA pH, while the tertiary organosulfates are found to undergo a much slower acid-dependent hydrolysis reaction. The primary organonitrates and organosulfates under study were found to be stable against nucleophilic substitution reactions, even at low pH. This finding provides a potential explanation for the fact that organosulfates are more commonly detected in ambient SOA than are organonitrates.     

Isoprene epoxydiols as precursors to secondary organic aerosol formation: acid-catalyzed reactive uptake studies with authentic compounds

Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NO(x) conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7-6.4% for β-IEPOX and 3.4-5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C(5)-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NO(x), isoprene-dominated regions influenced by the presence of acidic aerosols.     

Effect of acidity on secondary organic aerosol formation from isoprene

The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is closely correlated to increasing aerosol acidity (R2 = 0.979). Direct chemical evidence for acid-catalyzed particle-phase reactions was obtained from the SOA chemical analyses. Aerosol mass concentrations for the 2-methyltetrols, as well as the newly identified sulfate esters, both of which serve as tracers for isoprene SOA in ambient aerosols, increased significantly with enhanced aerosol acidity. Aerosol acidities, as measured in nmol of H+ m(-3), employed in the present study are in the same range as those observed in tropospheric aerosol collected from the eastern U.S.     

A field-based approach for deterimining ATOFMS instrument sensitities to ammonium and nitrate

Aerosol time-of-flight mass spectrometry (ATOFMS) instruments measure the size and chemical composition of individual particles in real-time. ATOFMS chemical composition measurements are difficult to quantify, largely because the instrument sensitivities to different chemical species in mixed ambient aerosols are unknown. In this paper, we develop a field-based approach for determining ATOFMS instrument sensitivities to ammonium and nitrate in size-segregated atmospheric aerosols, using tandem ATOFMS-impactor sampling. ATOFMS measurements are compared with collocated impactor measurements taken at Riverside, CA, in September 1996, August 1997, and October 1997. This is the first comparison of ion signal intensities from a single-particle instrument with quantitative measurements of atmospheric aerosol chemical composition. The comparison reveals that ATOFMS instrument sensitvities to both NH4+ and NO3- decline with increasing particle aerodynamic diameter over a 0.32-1.8 microm calibration range. The stability of this particle size dependence is tested overthe broad range of fine particle concentrations (PM1.8) = 17.6 +/- 2.0-127.8 +/- 1.8 microg m(-3)), ambient temperatures (23-35 degrees C), and relative humidity conditions (21-69%), encountered during the field experiments. This paper describes a potentially generalizable methodology for increasing the temporal and size resolution of atmospheric aerosol chemical composition measurements, using tandem ATOFMS-impactor sampling.     

A case study of urban particle acidity and its influence on secondary organic aerosol

Size-resolved indicators of aerosol acidity, including H+ ion concentrations (H+Aer) and the ratio of stoichiometric neutralization are evaluated in submicrometer aerosols using highly time-resolved aerosol mass spectrometer (AMS) data from Pittsburgh. The pH and ionic strength within the aqueous particle phase are also estimated using the Aerosol Inorganics Model (AIM). Different mechanisms that contribute to the presence of acidic particles in Pittsburgh are discussed. The largest H+Aer loadings and lowest levels of stoichiometric neutralization were detected when PM1 loadings were high and dominated by SO4(2-). The average size distribution of H+Aer loading shows an accumulation mode at Dva approximately 600 nm and an enhanced smaller mode that centers at Dva approximately 200 nm and tails into smaller sizes. The acidity in the accumulation mode particles suggests that there is generally not enough gas-phase NH3 available on a regional scale to completely neutralize sulfate in Pittsburgh. The lack of stoichiometric neutralization in the 200 nm mode particles is likely caused by the relatively slow mixing of gas-phase NH3 into SO2-rich plumes containing younger particles. We examined the influence of particle acidity on secondary organic aerosol (SOA) formation by comparing the mass concentrations and size distributions of oxygenated organic aerosol (00A--surrogate for SOA in Pittsburgh) during periods when particles are, on average, acidic to those when particles are bulk neutralized. The average mass concentration of ODA during the acidic periods (3.1 +/- 1.7 microg m(-3)) is higher than that during the neutralized periods (2.5 +/- 1.3 microg m(-3)). Possible reasons for this enhancement include increased condensation of SOA species, acid-catalyzed SOA formation, and/or differences in air mass transport and history. However, even if the entire enhancement (approximately 0.6 microg m(-3)) can be attributed to acid catalysis, the upperbound increase of SOA mass in acidic particles is approximately 25%, an enhancement that is much more moderate than the multifold increases in SOA mass observed during some lab studies and inferred in SO2-rich industrial plumes. In addition, the mass spectra of OOA from these two periods are almost identical with no discernible increase in relative signal intensity at larger m/z's (>200 amu), suggesting that the chemical nature of SOA is similar during acidic and neutralized periods and that there is no significant enhancement of SOA oligomer formation during acidic particle periods in Pittsburgh.     

Real-time, single-particle measurements of oligomers in aged ambient aerosol particles

Unique high mass negative ions in the -200 to -400 mass/charge range with repetitive spacings of 12, 14, and 16 units, representative of oligomeric species, have been detected in single ambient submicrometer aerosol particles using real-time single-particle mass spectrometry during the Study of Organic Aerosols field campaign conducted in Riverside, CA (SOAR) in August and November 2005. These oligomer-containing particles represented 33-40% of the total detected particles and contained other indicators of aging including oxidized organic carbon, amine, nitrate, and sulfate ion markers. Overall, the highest mass oligomeric patterns were observed in small acidic 140-200 nm particles in the summer. Also during the summer, increased oligomer intensities were observed when the particles were heated with a thermodenuder. We hypothesize that heat removed semivolatile species, thereby increasing particle acidity, while concentrating the oligomeric precursors and accelerating oligomer formation. Differences in oligomer behavior with respect to particle size and heating can be attributed to seasonal differences in photochemical oxidation, the relative amount of ammonium, and particle acidity.     

Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2-ol (MBO) in the Atmosphere

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.     

Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra

Real-time measurements of submicrometer aerosol were performed using an Aerodyne aerosol mass spectrometer (AMS) during three weeks at an urban background site in Zurich (Switzerland) in January 2006. A hybrid receptor model which incorporates a priori known source composition was applied to the AMS highly time-resolved organic aerosol mass spectra. Three sources and components of submicrometer organic aerosols were identified: the major component was oxygenated organic aerosol (OOA), mostly representing secondary organic aerosol and accounting on average for 52-57% of the particulate organic mass. Radiocarbon (14C) measurements of organic carbon (OC) indicated that approximately 31 and approximately 69% of OOA originated from fossil and nonfossil sources, respectively. OOA estimates were strongly correlated with measured particulate ammonium. Particles from wood combustion (35-40%) and 3-13% traffic-related hydrocarbon-like organic aerosol (HOA) accounted for the other half of measured organic matter (OM). Emission ratios of modeled HOA to measured nitrogen oxides (NOx) and OM from wood burning to levoglucosan from filter analyses were found to be consistent with literature values.     

Formation of aerosol particles from reactions of secondary and tertiary alkylamines: characterization by aerosol time-of-flight mass spectrometry

In ambient field studies conducted with aerosol time-of-flight mass spectrometry (ATOFMS), individual particle mass spectra commonly contain ion peaks at mass/charge (m/z) 86, 101, 102, and 118. Particles with mass spectra containing these peaks show a strong correlation with high relative humidity and low temperatures. In an effort to identify these peaks, a series of smog chamber studies were conducted probing the chemistry of secondary and tertiary alkylamines. Specifically, in separate studies, trimethylamine, di- and triethylamine, and di- and tripropylamine were reacted in a 1 m3 Teflon outdoor smog chamber with naturally occurring levels of gas phase oxidants in ambient air. The aerodynamic sizes and individual mass spectra of the resulting aerosol particles were acquired continuously using aerosol time-of-flight mass spectrometry (ATOFMS). Both oxidation and acid-base reactions between amines and acids commonly present in the atmosphere (i.e., nitric and sulfuric acid) appear to play roles in the formation and chemistry of organic nitrogen-containing particle phase species. Ion peaks in the individual particle mass spectra indicate the presence of alkyl ammonium salts, as well as other tentatively identified organic N-containing compounds formed by oxidation processes. Also, for the first time, tertiary alkylamine-N-oxides have been identified as alkylamine oxidation products in the aerosol particle phase. Smog chamber reactions involving triethylamine produce ATOFMS mass spectra with similar ion peak combinations as those observed in the spectra of particles commonly detected in ambient and vehicular source characterization studies. The results of this study suggest that amine chemistry involving gas-to-particle conversion and photooxidation processes may play a significant role in particle formation in regions with high amine concentrations.     

Aqueous-phase secondary organic aerosol and organosulfate formation in atmospheric aerosols: a modeling study

We have examined aqueous-phase secondary organic aerosol (SOA) and organosulfate (OS) formation in atmospheric aerosols using a photochemical box model with coupled gas-phase chemistry and detailed aqueous aerosol chemistry. SOA formation in deliquesced ammonium sulfate aerosol is highest under low-NO(x) conditions, with acidic aerosol (pH = 1) and low ambient relative humidity (40%). Under these conditions, with an initial sulfate loading of 4.0 μg m(-3), 0.9 μg m(-3) SOA is predicted after 12 h. Low-NO(x) aqueous-aerosol SOA (aaSOA) and OS formation is dominated by isoprene-derived epoxydiol (IEPOX) pathways; 69% or more of aaSOA is composed of IEPOX, 2-methyltetrol, and 2-methyltetrol sulfate ester. 2-Methyltetrol sulfate ester comprises >99% of OS mass (66 ng m(-3) at 40% RH and pH 1). In urban (high-NO(x)) environments, aaSOA is primarily formed via reversible glyoxal uptake, with 0.12 μg m(-3) formed after 12 h at 80% RH, with 20 μg m(-3) initial sulfate. OS formation under all conditions studied is maximum at low pH and lower relative humidities (<60% RH), i.e., when the aerosol is more concentrated. Therefore, OS species are expected to be good tracer compounds for aqueous aerosol-phase chemistry (vs cloudwater processing).     

Identification of the mass spectral signature of organic aerosols from wood burning emissions

Throughout the winter months, the village of Roveredo, Switzerland, frequently experiences strong temperature inversions that contribute to elevated levels of particulate matter. Wood is used as fuel for 75% of the domestic heating installations in Roveredo, which makes it a suitable location to study wood burning emissions in the atmosphere in winter. An Aerodyne quadrupole aerosol mass spectrometer (Q-AMS) was used to characterize the composition of the submicrometer, non-refractory aerosol particles at this location during two field campaigns in March and December 2005. Wood burning was found to be a major source of aerosols at this location in winter. Organics dominated the composition of the aerosols from this source, contributing up to 85% of the total AMS measured mass during the afternoon and evening hours. Carbonaceous particle analysis showed that organic carbon composed up to 86% of the total carbon mass collected at evening times. Results from 14C isotope determination revealed that up to 94% of the organic mass came from non-fossil sources, which can be attributed mostlyto wood burning. The unique combination of off-line 14C isotope analysis and on-line aerosol mass spectrometry was used to identify periods during which organic mass was mainly from wood burning emissions and allowed for the identification of the AMS spectral signature of this source in the atmosphere. The identified ambient signature of wood burning was found to be very similar to the mass spectral signature obtained during the burning of chestnut wood samples in a small stove and also to the spectrum of levoglucosan. Particles from wood burning appeared to be composed of highly oxygenated organic compounds, and mass fragments 60, 73, and 137 have been suggested as marker fragments for wood burning aerosols. Mass fragment 44, which is used as a marker for oxygenated organic aerosols (OOA), contributed about 5% to the total organic signal from primary wood burning sources. The ratio of the organic mass emitted from wood burning to m/z 60 in Roveredo is 36. This ratio may be used to provide an estimate of the organic aerosol mass emitted from wood burning in other locations.     

Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber

Only a minor fraction of the total organic aerosol mass can be resolved on a molecular level. High molecular weight compounds in organic aerosols have recently gained much attention because this class of compound potentially explains a major fraction of the unexplained organic aerosol mass. These compounds have been identified with different mass spectrometric methods, and compounds with molecular masses up to 1000 Da are found in secondary organic aerosols (SOA) generated from aromatic and terpene precursors in smog chamber experiments. Here, we apply matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to SOA particles from two biogenic precursors, alpha-pinene and isoprene. Similar oligomer patterns are found in these two SOA systems, but also in SOA from trimethylbenzene, an anthropogenic SOA precursor. However, different maxima molecular sizes were measured for these three SOA systems. While oligomers in alpha-pinene and isoprene have sizes mostly below 600-700 Da, they grow up to about 1000 Da in trimethylbenzene-SOA. The final molecular size of the oligomers is reached early during the particle aging process, whereas other particle properties related to aging, such as the overall acid concentration or the oligomer concentration, increase continuously over a much longer time scale. This kinetic behavior of the oligomer molecular size growth can be explained by a chain growth kinetic regime. Similar oligomer mass patterns were measured in aqueous extracts of ambient aerosol samples (measured with the same technique). Distinct differences between summer and winter were observed. In summer a few single mass peaks were measured with much higher intensity than in winter, pointing to a possible difference in the formation processes of these compounds in winter and summer.     

Effects of meteorological conditions on aerosol composition and mixing state in Bakersfield,CA

Particle and meteorological instrumentation were used to characterize ambient atmospheric conditions, aerosol size distributions, aerosol mass concentrations, and single particle size and chemical composition in Bakersfield, CA for the period January 9, 1999 through January 28, 1999. The sampling period included four distinct meteorological periods of stagnation, clearing, haze, and rain. Particle number and mass concentrations were the highest during the stagnation episode when a heavy and extensive fog developed. Mass and number concentrations also approached these high levels during the haze period. Single particle size and composition data from an aerosol time-of-flight mass spectrometer (ATOFMS) are used to provide unique continuous information on the diversity in types of particles present, the effects of meteorology on particle size and composition, and the distribution of important chemical species within individual particles. Aerosol composition and mixing state are found to vary with meteorological conditions. Single particle data show that carbonaceous aerosol with secondary ammonium, nitrate, and sulfate dominate the aerosol concentration during a stagnation period with a dramatic composition shift occurring to sodium type particles during the haze period. The aerosol is internally mixed with respect to carbon, nitrate, sulfate, and ammonium during the stagnation period. The mixing state changes significantly over the haze period when much greater diversity in the associations of chemical species within individual particles occurs.     

Contribution of organosulfur compounds to organic aerosol mass

Organosulfates have been proposed as products of secondary organic aerosol formation. While organosulfates have been identified in ambient aerosol samples, a question remains as to the magnitude of their contribution to particulate organic mass. At the same time, discrepancies have been observed between total particulate sulfur measured by X-ray fluorescence (XRF) spectroscopy and sulfur present as inorganic sulfate measured by ion chromatography (IC) in fine particulate matter. These differences could be attributed to measurement bias and/or the contribution of other sulfur compounds, including organosulfates. Using the National Park Service IMPROVE PM(2.5) database, we examined the disparity between the sulfur and sulfate measurements at 12 sites across the United States to provide upper-bound estimates for the annual average contributions of organosulfates to organic mass. The data set consists of over 150?000 measurements. The 12 sites include Brigantine, NJ, Cape Cod, MA, Washington, DC, Chassahowitzka, FL, Great Smoky Mountains National Park, NC, Okefenokee, GA, Bondville, IL, Mingo, MO, Phoenix, AZ, San Gabriel, CA, Crater Lake National Park, OR, and Spokane, WA. These sites are representative of the different regions of the country: Northeast, Southeast, Midwest, Southwest and Northwest. We estimate that organosulfur compounds could comprise as much as 5-10% of the organic mass at these sites. The contribution varies by season and location and appears to be higher during warm months when photochemical oxidation chemistry is most active.     

Trimethylamine as precursor to secondary organic aerosol formation via nitrate radical reaction in the atmosphere

Amines in fine particulate matter have been detected and quantified during ambient studies of winter inversions in Logan, UT, using aerosol mass spectrometry. Amine-related compounds account for 0.5-6 microg m(-3) of fine particulate mass during some wintertime periods. The amine contributions sometimes show a clear diurnal pattern, reaching peak concentrations during the middle of the nightwhile decreasing during the morning and afternoon. Smog chamber reactions show that the reaction of tertiary amines with nitrate radical can account for this behavior in the atmosphere. The lower bound reaction rate of trimethylamine and nitrate radical is estimated at 4.4 x 10(-16) cm3/molecules/s with a conversion rate to the aerosol phase of approximately 65%. This suggests that amines could be a contributor to secondary organic aerosol formation in areas where nitrate radical is a significant player in oxidation chemistry.     

Using proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols

Proton-transfer-reaction mass spectrometry (PTR-MS) is a useful tool in ambient trace gas analysis, especially for the analysis of oxygenated volatile organic compounds (OVOC). Many OVOCs are produced during photooxidation of volatile organic compounds and contribute to both the gas phase and secondary organic aerosols (SOA). The inlet system of the PTR-MS instrument was modified to allow also for the measurement of the particulate phase of an aerosol with a high time resolution. The new inlet consists mainly of a denuder to strip off the gas phase, and a heater (120/150 degrees C) to vaporize the aerosol particles. This inlet system was tested with pinonic acid particles generated with a nebulizer and SOA particles formed during the photooxidation of 1,3,5-trimethylbenzene and alpha-pinene with NO(x) in a smog chamber. The performance of this new technique is discussed and the partitioning coefficients for the oxidation products are estimated.     

Temporal trends in atmospheric PM₂.₅, PM₁₀, elemental carbon, organic carbon, water-soluble organic carbon, and optical properties: impact of biomass burning emissions in the Indo-Gangetic Plain

The first simultaneous measurements and analytical data on atmospheric concentrations of PM(2.5), PM(10), inorganic constituents, carbonaceous species, and their optical properties (aerosol optical depth, AOD; absorption coefficient, b(abs); mass absorption efficiency, σ(abs); and single scattering albedo, SSA) from an urban site (Kanpur) in the Indo-Gangetic Plain are reported here. Significantly high aerosol mass concentration (>100 μg m(-3)) and AOD (> 0.3) are seen as a characteristic feature throughout the sampling period, from October 2008 to April 2009. The temporal variability in the mass fractions of carbonaceous species (EC, OC, and WSOC) is pronounced during October-January when emissions from biomass burning are dominant and OC is a major constituent (～30%) of PM(2.5) mass. The WSOC/OC ratio varies from 0.21 to 0.65, suggesting significant contribution from secondary organic aerosols (SOAs). The mass fraction of SO(4)(2-) in PM(2.5) (Av: 12.5%) exceeds that of NO(3)(-) and NH(4)(+). Aerosol absorption coefficient (@ 678 nm) decreases from 90 Mm(-1) (in December) to 20 Mm(-1) (in April), and a linear regression analysis of the data for b(abs) and EC (n = 54) provides a measure of the mass absorption efficiency of EC (9.6 m(2) g(-1)). In contrast, scattering coefficient (@ 678 nm) increases from 98 Mm(-1) (in January) to 1056 Mm(-1) (in April) and an average mass scattering efficiency of 3.0 ± 0.9 m(2) g(-1) is obtained for PM(10) samples. The highest b(scat) was associated with the dust storm event (April 17, 2009) over northern Iraq, eastern Syria, and southern Turkey; thus, resulting in high SSA (0.93 ± 0.02) during March-April compared to 0.82 ± 0.04 in October-February. These results have implications to large temporal variability in the atmospheric radiative forcing due to aerosols over northern India.