Characterization Of Organic Aerosol Research Articles

Organic Aerosol Characterization and Source Identification in Karachi, Pakistan

With its rapidly growing population and large industrial base, the megacity of Karachi, Pakistan, has been subjected to an increasing amount of ambient particulate matter (PM). Fine particulate matter (PM2.5) in Karachi was collected every 24 hours from January 8 to January 29, 2006. The samples were extracted and analyzed by gas chromatography-mass spectrometry (GC-MS) and ultra-performance liquid chromatography (UPLC) coupled with a triple quadrupole mass spectrometric detector (TQD) and time-of-flight (TOF) mass spectrometer. The daily PM2.5 levels ranged from 99.5 to 251.1 µg m–3 with a mean of 177.4 µg m–3, averaging 4–10-fold higher than the WHO guideline for 24-hour averaged PM2.5 (25 µg m–3). We found that the day-of-the-week variations of PM2.5 demonstrate Sundays have significantly lower concentrations (with a t-based confidence level of 95%), indicating that weekly behavioral patterns affect local PM2.5 concentrations. A significant negative correlation was found between the daily concentrations of levoglucosan, a biomass burning tracer, and the average daily temperatures (r = –0.589, p = 0.004), implicating heating as a major source of biomass burning emissions. Results indicate that polyaromatic hydrocarbons, hopanes, steranes, and alkanes are mainly emitted from fossil fuels and the combustion of carbonaceous materials. Organosulfates (OSs) and sulfonates were also quantified; significant correlations between OSs and sulfonates indicate a common source and/or similar formation mechanisms, while correlations with hopanes, steranes, and levoglucosan suggest their emission from primary sources such as fossil fuels and biomass burning. Qualitative analysis suggests the presence of a C6–C9 alkyl sulfate series. Through this study, the chemical composition and origin of the organic fraction of PM2.5 in Karachi has been evaluated for the first time, and the results indicate a strong anthropogenic influence on combustion emissions, particularly those from biomass and fossil fuel burning.

Application of ultrahigh-performance liquid chromatography–quadrupole time-of-flight mass spectrometry for the characterization of organic aerosol: Searching for naphthenic acids

Naphthenic acids (NAs) are naturally occurring constituents of hydrocarbon deposits (petroleum, oil sands bitumen, and crude oils), and present in any facilities that extract, process or use crude oil or bitumen for manufacturing. In the Athabasca oil sands region (AOSR) of Alberta, Canada, this diverse group of saturated acyclic, monocyclic, and polycyclic carboxylic acids is present in bitumen and in tailing ponds. Little is known about the occurrence of residual oil sands derived organic material, including NAs, in atmospheric particulate matter (PM). This work describes the optimization of an ultrahigh-performance liquid chromatography–quadrupole time-of-flight mass spectrometry (UPLC/QTOF-MS) method to characterize and identify classical NAs in atmospheric PM. Under the optimum conditions, analysis of the Sigma-Aldrich technical NA STD Mix showed the absence of saturated fatty acids, while branched and cyclic NAs isomers with carbon number ranged between 10 and 30, and Z families between 0 and −12 were detected. Higher molecular weight NAs representing compounds with carbon number ranging between 30 and 40 were identified in the analyzed PM samples collected in AOSR. In contrast, isomeric branched acyclic NAs were not detected in the background (PM-R) samples collected far from AOSR. Except for fatty acids (Z=0), other Z homologues were also not detectable or present at very low concentration in the analysed PM-R samples. Preliminary examination of NA profiles showed that the composition of NAs in PM collected in close proximity to surface mining operations is predominantly “refractory” high molecular weight branched NAs, differing from that collected closer to upgraders and tailings ponds. It is suspected that dust released from the mine faces and dry tailings in the AOSR are sources of NAs to atmosphere. Further samples should be examined to confirm findings. This preliminary study presents, to our knowledge, the first direct identification of branched acyclic and cyclic NAs in atmospheric PM.

Characterization of organic aerosol in Beijing by laser desorption ionization coupled with Fourier Transform Ion Cyclotron Resonance Mass spectrometry

In order to resolve the organic compositions in the atmospheric aerosol which is significant for understanding the formation mechanism of particulate matter and their harm for human health, a direct laser desorption ionization (LDI) coupled with Fourier Transform Resonance Mass (FT-ICR MS) was utilized for characterizing the aerosol particles collected in Beijing during winter. A lot of organic compounds can be detected by direct laser desorption ionization of the aerosol particular with different size collected on aluminum foil without complicated sample pretreatment process. In addition, semi quantification of the organic compounds can be achieved with solvent extraction procedure. It was found that the ubiquitous polycyclic aromatic hydrocarbons (PAHs) contaminants in the aerosol could serve as matrix, which helps the detection of many kinds of compounds including highly saturated amphiphilic long alkyl chain compounds (carbon number>16), like aliphatic amines in positive ion mode and organosulfates in negative ion mode. Based on the accurate mass measurement results, elemental compositions of over 1500 peaks in the mass spectrum were derived, and we categorized them into five groups according to their elemental compositions in order to provide helpful information for tracing the pollution source. It is demonstrated that abundant information about the organic components in the atmospheric aerosol can be provided by direct LDI FT-ICR MS method, and these information will largely facilitate further studies on origin and formation process of the aerosol.

Advances in Organic Aerosol Characterization: From Complex to Simple

ABSTRACT Air pollution is the “world largest single environmental health risk” (WHO, 2016). According to the World Health Organization, every year ambient air pollution leads to more than 3 million premature deaths, and 84% of the global population is exposed to atmospheric aerosol levels higher than the limits set to protect human health (WHO, 2016). One of the most abundant, and still less characterized components of atmospheric aerosol is organic aerosol (OA). In particular, OA sources, formation mechanisms, atmospheric ageing, and effects on climate and human health are still subject of research. OA is a mixture of thousands of chemical species, characterized by different physical, chemical, and toxicological properties. Such properties define the effects of OA, and particulate matter, on climate, air quality, and human health (Goldstein and Galbally, 2007). Traditional analytical techniques, based on the identification of single molecular species, describe only a limited fraction of OA mass, generally lower than 30% (Hallquist et al., 2009). During the last decade the use of bulk OA spectrometric analysis introduced simplified descriptions of OA. Such approaches depict OA as formed by a few components with different degrees of oxidation (Aerosol mass spectrometry - AMS) (Zhang et al., 2005), or as the sum of different organic functional groups, (Fourier transform infrared spectrometry - FTIR (Maria et al., 2003), or proton nuclear magnetic resonance spectrometry - H-NMR (Decesari et al., 2007)).

Technical Note: Development of chemoinformatic tools to enumerate functional groups in molecules for organic aerosol characterization

Abstract. Functional groups (FGs) can be used as a reduced representation of organic aerosol composition in both ambient and controlled chamber studies, as they retain a certain chemical specificity. Furthermore, FG composition has been informative for source apportionment, and various models based on a group contribution framework have been developed to calculate physicochemical properties of organic compounds. In this work, we provide a set of validated chemoinformatic patterns that correspond to (1) a complete set of functional groups that can entirely describe the molecules comprised in the α-pinene and 1,3,5-trimethylbenzene MCMv3.2 oxidation schemes, (2) FGs that are measurable by Fourier transform infrared spectroscopy (FTIR), (3) groups incorporated in the SIMPOL.1 vapor pressure estimation model, and (4) bonds necessary for the calculation of carbon oxidation state. We also provide example applications for this set of patterns. We compare available aerosol composition reported by chemical speciation measurements and FTIR for different emission sources, and calculate the FG contribution to the O : C ratio of simulated gas-phase composition generated from α-pinene photooxidation (using the MCMv3.2 oxidation scheme).

Sources and chemical characterization of organic aerosol during the summer in the eastern Mediterranean

Abstract. The concentration and chemical composition of non-refractory fine particulate matter (NR-PM1) and black carbon (BC) levels were measured during the summer of 2012 in the suburbs of two Greek cities, Patras and Athens, in an effort to better understand the chemical processing of particles in the high photochemical activity environment of the eastern Mediterranean. The composition of PM1 was surprisingly similar in both areas, demonstrating the importance of regional sources for the corresponding pollution levels. The PM1 average mass concentration was 9–14 μg m−3. The contribution of sulfate was around 38 %, while organic aerosol (OA) contributed approximately 45 % in both cases. PM1 nitrate levels were low (2 %). The oxygen to carbon (O : C) atomic ratio was 0.50 ± 0.08 in Patras and 0.47 ± 0.11 in Athens. In both cases PM1 was acidic. Positive matrix factorization (PMF) was applied to the high-resolution organic aerosol mass spectra obtained by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). For Patras, five OA sources could be identified: 19 % very oxygenated OA (V-OOA), 38 % moderately oxygenated OA (M-OOA), 21 % biogenic oxygenated OA (b-OOA), 7 % hydrocarbon-like OA (HOA-1) associated with traffic sources and 15 % hydrocarbon-like OA (HOA-2) related to other primary emissions (including cooking OA). For Athens, the corresponding source contributions were: V-OOA (35 %), M-OOA (30 %), HOA-1 (18 %) and HOA-2 (17 %). In both cities the major component was OOA, suggesting that under high photochemical conditions most of the OA in the eastern Mediterranean is quite aged. The contribution of the primary sources (HOA-1 and HOA-2) was important (22 % in Patras and 35 % in Athens) but not dominant.

Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

A simple QuEChERS-like extraction approach for molecular chemical characterization of organic aerosols: application to nitrated and oxygenated PAH derivatives (NPAH and OPAH) quantified by GC–NICIMS

An extraction procedure based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) approach has been developed and used for analysis of particle-bound nitrated and oxygenated PAH derivatives (NPAH and OPAH, respectively). Several analytical conditions, for example GC injection temperature and MS detection settings, were optimized. This analytical procedure enabled simultaneous GC-NICIMS quantification of 32 NPAH and 32 OPAH (or other oxygenated compounds), including typical components of secondary organic aerosol (SOA) formed by photooxidation of PAH (e.g. 2-formyl-trans-cinnamaldehyde and 6H-dibenzo[b,d]pyran-6-one). The QuEChERS-like approach was optimized, including the nature of the extraction solvent, the sorbent used for clean-up, and extraction time. The final extraction procedure was based on brief mechanical agitation (vortex mixing for 1.5min), with 7mL acetonitrile as solvent. Because dispersive solid-phase extraction (d-SPE) did not provide satisfactory results, SPE using SiO2 was selected for sample purification. Identical results were obtained when the QuEChERS-like and traditional pressurised solvent extraction (PLE) procedures were compared for analysis of fortified ambient air particle samples. The procedure was validated by analysis of two aerosol standard reference materials (NIST SRM 1649b (urban dust) and SRM 2787 (fine particulate matter, <10μm)). For numerous NPAH and OPAH, this is the first report of their quantification in both SRMs. Compared with other extraction methods, including PLE, the QuEChERS-like procedure resulted in increased productivity and reduced extraction cost. This paper shows that QuEChERS-like extraction procedures can be suitably adapted for molecular chemical characterization of aerosol samples and could be extended to other categories of compound.

Characterization of organic aerosol produced during pulverized coal combustion in a drop tube furnace

Abstract. Controlled bench scale pulverized coal combustion studies were performed, demonstrating that inorganic particles play a critical role as carriers of organic species. Two commonly-used aerosol mass spectrometry techniques were applied to characterize fine particle formation during coal combustion. It was found that the organic species in coal combustion aerosols have mass spectra similar to those generated by biomass combustion. Ambient measurements in Shanghai, China confirm the presence of these species in approximately 29–38% of the sampled particles. With the absence of major biomass sources in the Shanghai area, it is suggested that coal combustion may be the main source of these particles. This work indicates there is a significant potential for incorrect apportionment of coal combustion particles to biomass burning sources using widely adopted mass spectrometry techniques.

In situ submicron organic aerosol characterization at a boreal forest research station during HUMPPA-COPEC 2010 using soft and hard ionization mass spectrometry

Abstract. The chemical composition of submicron aerosol during the comprehensive field campaign HUMPPA-COPEC 2010 at Hyytiälä, Finland, is presented. The focus lies on online measurements of organic acids, which were achieved by using atmospheric pressure chemical ionization (APCI) ion trap mass spectrometry (IT-MS). These measurements were accompanied by aerosol mass spectrometry (AMS) measurements and Fourier transform infrared spectroscopy (FTIR) of filter samples, all showing a high degree of correlation. The soft ionization mass spectrometer alternated between gas-phase measurements solely and measuring the sum of gas and particle phase. The AMS measurements of C, H and O elemental composition show that the aerosol during the campaign was highly oxidized, which appears reasonable due to high and prolonged radiation during the boreal summer measurement period as well as the long transport times of some of the aerosol. In order to contrast ambient and laboratory aerosol, an average organic acid pattern, measured by APCI-IT-MS during the campaign, was compared to terpene ozonolysis products in a laboratory reaction chamber. Identification of single organic acid species remains a major challenge due to the complexity of the boreal forest aerosol. Unambiguous online species identification was attempted by the combinatorial approach of identifying unique fragments in the MS2 mode of standards, and then comparing these results with MS2 field spectra. During the campaign, unique fragments of limonene-derived organic acids (limonic acid and ketolimononic acid) and of the biomass burning tracer vanillic acid were detected. Other specific fragments (neutral loss of 28 Da) in the MS2 suggest the occurrence of semialdehydes. Furthermore, an approach to determine the average molecular weight of the aerosol is presented. The campaign average organic molecular weight was determined to be 300 g mol−1. However, a plume of aged biomass burning aerosol, arriving at Hyytiälä from Russia, contained organic compounds up to 800 Da (MWom&amp;amp;approx;450 g mol−1), showing that the average molecular weight can vary significantly. The high measurement frequency of both AMS and APCI-IT-MS enabled the partitioning of selected organic acids between gas and particle phase as a function of the total particulate mass to be quantified. Surprisingly high fractions of the higher molecular weight organic acids were observed to reside in the gas phase. These observations might be a consequence of large equilibration timescales for semi-solid boreal forest aerosol, as has been recently hypothesized by Shiraiwa and Seinfeld (2012).

Los Angeles Basin airborne organic aerosol characterization during CalNex

We report airborne organic aerosol (OA) measurements over Los Angeles carried out in May 2010 as part of the CalNex field campaign. The principal platform for the airborne data reported here was the CIRPAS Twin Otter (TO); airborne data from NOAA WP‐3D aircraft and Pasadena CalNex ground‐site data acquired during simultaneous TO flybys are also presented. Aerodyne aerosol mass spectrometer measurements constitute the main source of data analyzed. The increase in organic aerosol oxidation from west to east in the basin was sensitive to OA mass loading, with a greater spatial trend in O:C associated with lower mass concentration. Three positive matrix factorization (PMF) components (hydrocarbon‐like organic aerosol (HOA), semi‐volatile oxidized organic aerosol (SVOOA), and low volatility oxidized organic aerosol (LVOOA)) were resolved for the one flight that exhibited the largest variability in estimated O:C ratio. Comparison of the PMF factors with two optical modes of refractory black carbon (rBC)‐containing aerosol revealed that the coating of thinly coated rBC‐containing aerosol, dominant in the downtown region, is likely composed of HOA, whereas more thickly coated rBC‐containing aerosol, dominant in the Banning pass outflow, is composed of SVOOA and LVOOA. The correlation of water‐soluble organic mass to oxidized organic aerosol (OOA) is higher in the outflows than in the basin due to the higher mass fraction of OOA/OA in the outflows. By comparison, the average OA concentration over Mexico City MILAGRO (Megacity Initiative: Local and Global Research Observations) campaign was ∼7 times higher than the airborne average during CalNex.

Seasonal characteristics of submicrometer organic aerosols in urban Gwangju, Korea using an aerosol mass spectrometer

Chemical characterization of organic aerosol (OA) was conducted using an aerosol mass spectrometer (AMS) in urban Gwangju, Korea, during the fall (8/30/2011–9/19/2011), winter (12/19/2011–12/30/2011), spring (5/15/2012–5/24/2012), and summer (7/23/2012–8/6/2012). OA was found to be the most dominant component of non-refractory submicrometer particles, with an average concentration of 4.39 μg m−3. The oxygenated organic aerosol (OOA) content was higher than the hydrocarbon-like organic aerosol (HOA) content (68.1% versus 31.9%), and the less volatile-OOA (LV-OOA) content was higher than the semi-volatile OOA (SV-OOA) content (57.0% versus 43.0%). The seasonal data showed that both HOA and LV-OOA were abundant in winter due to the enhancement of the local OA source strength under strong temperature inversion and the frequent long-range transportation of aged air masses from polluted areas. The OA more than doubled when a northwest air mass occurred compared to the other air masses in winter, suggesting that the long-range transported organic species constitute more than 50% of the OA. Changes in the mixing height (i.e., dilution) and the strength of the HOA sources led to a pronounced diurnal pattern for the HOA in winter. A clear transition for the OA components was observed from winter to summer. In summer, LV-OOA became the most dominant component and increased in the afternoon in contrast to the HOA and SV-OOA. A bimodal size distribution of the OA was observed in all seasons due to multiple OA sources and aging. Optical properties of PM2.5 measured in the spring showed that the single scattering albedo (SSA) at 532 nm increased in the afternoon along with the LV-OOA. The HOA was better correlated with the light absorption coefficient than the light scattering coefficient, suggesting that the HOA included a significant amount of light absorbing organics and/or were produced at the same time as the light absorbing black carbon.

Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

Characterization of organic aerosol in fine particles in a mega-city of South China: Molecular composition, seasonal variation, and size distribution

A one-year-long observation on major organic compounds in PM2.5 was performed in a coastal mega-city in South China, Shenzhen, in order to gain information of their ambient concentration levels and the implications for sources. The compounds identified included alkanes, PAHs, hopanes, fatty acids and dicarboxylic acids, whose annual average concentrations during the year were 56.0, 14.8, 2.51, 253, and 25.2ngm−3, respectively. The seasonal molecular distributions of these organic compounds were discussed to explore their contributing sources in Shenzhen. Conclusively, alkanes and PAHs had the dominant source of fossil fuel combustion, although alkanes also had significant contribution from plant wax (~16%). The hopane series distributions further indicated that vehicle emissions were the dominant fossil fuel combustion source for PM2.5 in Shenzhen. Cooking emissions were inferred to be the most possible main source for fatty acids, while both primary and secondary origins were implied for azelaic acid, the dominant one in the dicarboxylic acids identified. Most of the organic compounds analyzed showed a size distribution pattern peaking at 0.32–0.56 or 0.56–1μm in the accumulation mode, except that the cooking-related organic acids showed implication of a coarse mode-dominated pattern.

A versatile and reproducible automatic injection system for liquid standard introduction: application to in-situ calibration

Abstract. The quantitation of trace organic compounds in ambient organic aerosol is difficult due to the chemical complexity of these mixtures, but is needed to provide insight into their sources and formation processes. Compound-level characterization of organic aerosols is typically performed through sample collection followed by gas or liquid chromatography. With these methods, introduction of liquid standards has long been used as an effective means of quantifying trace compounds, but automating this technique for use with in-situ instrumentation has not previously been achieved. Here we develop an automatic injection system (AutoInject) for the introduction of liquids into a custom collection and analysis cell for improved quantitation in chromatographic measurements. The system consists of chilled reservoirs containing liquid standards from which a sample loop is loaded and then injected into the cell. The AutoInject is shown to be reproducible over 106 injections with a relative standard deviation of 1.5%, and have negligible injection-to-injection carryover. A 6-port selector allows injection of different liquid standards separately or simultaneously. Additionally, automatic injection of multiple sample loops is shown to generate a linear multi-point calibration curve. Tests conducted in this work focus on use with the Thermal desorption Aerosol Gas chromatograph (TAG), but the flexibility of the system allows it to be used for a variety of applications.

Source characterization of organic aerosols using Monte Carlo source apportionment of PAHs at two South Asian receptor sites

Abstract The quantification of source contributions is of key importance for proposing environmental mitigation strategies for particulate organic matter. Organic molecular tracer analysis of polycyclic aromatic hydrocarbons (PAHs) and n -alkanes was conducted on a set of winter samples from two regional receptor sites in South Asia: the Island of Hanimaadhoo (the Republic of Maldives) and a mountain top near Sinhagad (W. India). Monte Carlo source apportionment (MCSA) techniques were applied to the observed PAH ratios using profiles of a representative range of regional combustion sources from the literature to estimate the relative source contributions from petroleum combustion, coal combustion and biomass burning. One advantage of this methodology is the combined use of the mean and standard deviation of the diagnostic ratios to calculate probability distribution functions for the fractional contributions from petroleum, coal and biomass combustion. The results of this strategy indicate a higher input from coal combustion at the Hanimaadhoo site (32–43 ± 21%) than the Sinhagad site (24–25 ± 18%). The estimated biomass contribution for Sinhagad (53 ± 22%) parallels previous radiocarbon-based source apportionment of elemental carbon at this location (54 ± 3%). In Hanimaadhoo, the MCSA results indicate 34 ± 20% biomass burning contribution compared to 41 ± 5% by radiocarbon apportionment of EC. While the MCSA based on PAH ratio diagnostic distributions are less precise than the radiocarbon-based apportionment, it provides additional information of the relative contribution of two subgroups, coal and petroleum combustion, within the overall contribution from fossil fuel combustion.

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/ z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/ z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/ z 44. Despite differences for three projects with ratios of m/ z 44 to m/ z 57 fragments less than 10, five projects showed a linear trend between the project-average m/ z 44 to m/ z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/ z 44 as a carboxylic acid group marker and m/ z 57 as an alkane group marker.

Functional group analysis by H NMR/chemical derivatization for the characterization of organic aerosol from the SMOCC field campaign

Abstract. Water soluble organic compounds (WSOC) in aerosol samples collected in the Amazon Basin in a period encompassing the middle/late dry season and the beginning of the wet season, were investigated by H NMR spectroscopy. HiVol filter samples (PM2.5 and PM&gt;2.5) and size-segregated samples from multistage impactor were subjected to H NMR characterization. The H NMR methodology, recently developed for the analysis of organic aerosol samples, has been improved by exploiting chemical methylation of carboxylic groups with diazomethane, which allows the direct determination of the carboxylic acid content of WSOC. The content of carboxylic carbons for the different periods and sizes ranged from 12% to 20% of total measured carbon depending on the season and aerosol size, with higher contents for the fine particles in the transition and wet periods with respect to the dry period. A comprehensive picture is presented of WSOC functional groups in aerosol samples representative of the biomass burning period, as well as of transition and semi-clean atmospheric conditions. A difference in composition between fine (PM2.5) and coarse (PM&gt;2.5) size fractions emerged from the NMR data, the former showing higher alkylic content, the latter being largely dominated by R-O-H (or R-O-R') functional groups. Very small particles (&lt;0.14 μm), however, present higher alkyl-chain content and less oxygenated carbons than larger fine particles (0.42–1.2 μm). More limited variations were found between the average compositions in the different periods of the campaign.

Comment on “On the use of anion exchange chromatography for the characterization of water soluble organic carbon” by H. Chang et al.

Comment on “On the use of anion exchange chromatography for the characterization of water soluble organic carbon” by H. Chang et al.

On-line analysis of organic components in fine and ultrafine particles by photoionization aerosol mass spectrometry.

A new method, photoionization aerosol mass spectrometry (PIAMS), is described for real-time analysis of organic components in airborne particles below approximately 300 nm in diameter. Particles are focused through an aerodynamic lens assembly into the mass spectrometer where they are collected on a probe in the source region. After a sufficient amount of sample has been collected, the probe is irradiated with a pulsed infrared laser beam to vaporize organic components, which are then softly ionized with coherent vacuum ultraviolet radiation at 118 nm (10.5 eV). Since the photon energy is close to the ionization energies of most organic compounds, fragmentation is minimized. Both aliphatic and aromatic compounds of atmospheric relevance are detected and quantified in the low- to midpicogram range. The photoionization signal intensity increases linearly with the amount of material sampled and is independent of particle size. The fragmentation induced by laser desorption is greater than that observed with thermal vaporization, suggesting that the internal energy imparted by the former is greater. Although some molecular fragmentation is observed, mass spectra from common sources of ambient organic aerosol are distinguishable and consistent with previous off-line measurements by gas chromatography/mass spectrometry. These results illustrate the potential of PIAMS for molecular characterization of organic aerosols in ambient and smog chamber measurements.