ORCID Profile
0000-0002-5715-9157
Current Organisation
University of York
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Publisher: Copernicus GmbH
Date: 29-04-2019
Publisher: American Chemical Society (ACS)
Date: 13-12-2011
DOI: 10.1021/ES202554C
Publisher: Copernicus GmbH
Date: 14-09-2022
Publisher: Copernicus GmbH
Date: 25-07-2016
Abstract: Abstract. Measurement techniques that provide molecular-level information are needed to elucidate the multiphase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS–MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS–MS after ionization with a custom-built nitrate chemical ionization (CI) source. This CI–IMS–MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field c aign in the forested SE US. The ambient IMS–MS signals are consistent with laboratory IMS–MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-D IMS–MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS–MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisionally induced dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the presence of the organosulfate functional group.
Publisher: Copernicus GmbH
Date: 26-10-2017
DOI: 10.5194/ACP-2017-994
Abstract: Abstract. Diameter growth factors (GF) of 100 nm haze particles at 85 % relative humidity and chemical characteristics were simultaneously monitored at Singapore in October 2015 during a pervasive wildfire haze episode, which was caused by peatland burning in Indonesia. Non-refractory submicron particles (NR-PM1) were dominated by organics (approximating 77.1 % in total mass), whereas sulfate was the most abundant inorganic constituent (11.7 % on average). A statistical analysis of the organic mass spectra showed that most of organics (36.0 % of NR-PM1 mass) were highly oxygenated. Diurnal variations of GF, number fraction of highly hygroscopic mode particles, mass fraction of sulfate, and mass fraction of oxygenated organics (OOA) synchronized well, peaking during daytime. The mean hygroscopicity parameter (κ) of haze particles was 0.189 ± 0.087, and mean κ values of organics were 0.157 ± 0.108 (κorg, bulk organics) and 0.287 ± 0.193 (κOOA, OOA), demonstrating the important roles of both sulfate and highly oxygenated organics in hygroscopic growth of wildfire haze particles. κorg was also affected by the water-soluble organic fraction to some extent. These results show the importance of secondary formation processes in promoting water uptake properties of wildfire haze particles, including both inorganic and organic species. Further detailed size-resolved as well as molecular level chemical information of organics will be necessary for more profound exploration of water uptake by wildfire haze particles in Equatorial Asia.
Publisher: Copernicus GmbH
Date: 16-08-2016
DOI: 10.5194/ACP-2016-719
Abstract: Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM/OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM/OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM/OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically-derived semivolatile species in the CMAQ model were highly water soluble, and expected to contribute to water soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night but, additional improvements in daytime organic aerosol are needed to close the model-measurement gap. By taking into account deviations from ideality, including both inorganic (when RH SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.
Publisher: Elsevier BV
Date: 10-2017
Publisher: Copernicus GmbH
Date: 03-09-2019
DOI: 10.5194/ACP-19-11105-2019
Abstract: Abstract. Indonesia contains large areas of peatland that have been drained and cleared of natural vegetation, making them susceptible to burning. Peat fires emit considerable amounts of carbon dioxide, particulate matter (PM) and other trace gases, contributing to climate change and causing regional air pollution. However, emissions from peat fires are uncertain, due to uncertainties in emission factors and fuel consumption. We used the Weather Research and Forecasting model with chemistry and measurements of PM concentrations to constrain PM emissions from Indonesian fires during 2015, one of the largest fire seasons in recent decades. We estimate primary PM2.5 (particles with diameters less than 2.5 µm) emissions from fires across Sumatra and Borneo during September–October 2015 were 7.33 Tg, a factor 3.5 greater than those in the Fire Inventory from NCAR (FINNv1.5), which does not include peat burning. We estimate similar dry fuel consumption and CO2 emissions to those in the Global Fire Emissions Database (GFED4s, including small fires) but PM2.5 emissions that are a factor of 1.8 greater, due to updated PM2.5 emission factors for Indonesian peat. Fires were responsible for an additional 3.12 Tg of secondary organic aerosol formation. Through comparing simulated and measured PM concentrations, our work provides independent support of these updated emission factors. We estimate peat burning contributed 71 % of total primary PM2.5 emissions from fires in Indonesia during September–October 2015. We show that using satellite-retrieved soil moisture to modify the assumed depth of peat burn improves the simulation of PM, increasing the correlation between simulated and observed PM from 0.48 to 0.56. Overall, our work suggests that peat fires in Indonesia produce substantially greater PM emissions than estimated in current emission inventories, with implications for the predicted air quality impacts of peat burning.
Publisher: Elsevier BV
Date: 03-2017
Publisher: Copernicus GmbH
Date: 15-10-2018
Publisher: Copernicus GmbH
Date: 29-04-2019
DOI: 10.5194/ACP-2019-323
Abstract: Abstract. Indonesia contains large areas of peatland which are being drained and cleared of natural vegetation, making them susceptible to burning. Peat fires emit considerable amounts of carbon dioxide, particulate matter (PM) and other trace gases, contributing to climate change and causing regional air pollution. However emissions from peat fires are uncertain due to uncertainties in emission factors and burn depth of peat. We used the Weather Research and Forecasting model with chemistry, and measurements of PM concentrations to constrain PM emissions from Indonesian fires during 2015, one of the largest fire seasons in recent decades. We estimate PM2.5 (particles with diameters less than 2.5 μm) emissions from fires across Sumatra and Borneo during September to October 2015 were 7.33 Tg, a factor 3.5 greater than those in Fire Inventory from NCAR (FINNv1.5), which does not include peat burning. We estimate similar dry fuel consumption and CO2 emissions to those in the Global Fire Emissions Database (GFED4s), but a factor 1.8 greater PM2.5 emissions, due to updated PM2.5 emission factors for Indonesian peat. Through comparing simulated and measured PM concentrations, our work provides an independent confirmation of these updated emission factors. We estimate peat burning contributes 71 % of total PM2.5 emissions from fire in Indonesia during September–October 2015. We show that using satellite-retrieved soil moisture to modify the assumed depth of peat burn improves the simulation of PM, increasing the correlation between simulated and observed PM from 0.48 to 0.56. Overall, our work suggests that peat fires in Indonesia produce substantially greater PM emissions than estimated in current emission datasets, with implications for the predicted air quality impacts of peat burning.
Publisher: Copernicus GmbH
Date: 15-10-2018
Publisher: Copernicus GmbH
Date: 23-10-2015
DOI: 10.5194/ACP-15-11807-2015
Abstract: Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O ( 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.
Publisher: IOP Publishing
Date: 09-2018
DOI: 10.1088/1757-899X/403/1/012004
Abstract: According to Decree of Semarang Mayor No. 22/2011, car free day activities is addressed to give clean air for facilitating citizens activities. This car free day event is held every Sunday in the morning in the city center of Semarang i.e. located at Simpang Lima square. This research is aimed at identifying the shifting of pollutant during car fee day event by comparing ambient air pollutant concentration represented by carbon monoxide during car free day event and non-car free day event. About 14 streets had been measured its ambient CO concentration during Saturday (non-car free day event) and Sunday (car free day event). We also modeled (using Caline4) the CO dispersion at the certain area on those streets to know the spatial distribution of concentration during those two events. The ambient CO concentration, in general, during car free day event were somewhat increase for certain roads. The emission load of vehicles emission during CFD event was 1.37 times of non-CFD event. Nevertheless, based on spatial distribution of ambient CO concentration at the area of roads of interest, its concentrations were below the ambient CO concentration standard (PP.41/99).
Publisher: Copernicus GmbH
Date: 10-03-2015
DOI: 10.5194/ACPD-15-7365-2015
Abstract: Abstract. A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 s les were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). C aign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 .7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0.2 μg m−3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.
Publisher: American Chemical Society (ACS)
Date: 06-10-2014
DOI: 10.1021/ES503142B
Abstract: Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0FD00080A
Abstract: We study the anthropogenic and biogenic contributions to organic aerosol.
Publisher: Proceedings of the National Academy of Sciences
Date: 03-04-2013
Abstract: Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO x = NO + NO 2 ) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NO x conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO x .
Publisher: Copernicus GmbH
Date: 21-04-2016
Abstract: Abstract. In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter s les were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). S le extracts were analyzed by gas chromatography–electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) ( ∼ 7 to ∼ 20 %). Isoprene-derived SOA tracers correlated with sulfate (SO42−) (r2 = 0.34, n = 117) but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO3 radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO2) (r2 = 0.26, n = 40) was weaker. Ozone (O3) correlated strongly with MAE/HMML-derived tracers (r2 = 0.72, n = 30) and moderately with 2-methyltetrols (r2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8EM00308D
Abstract: A developed non-thermal analytical method effectively resolves and quantifies major IEPOX-SOA components in PM 2.5 .
Publisher: Copernicus GmbH
Date: 04-06-2018
Abstract: Abstract. The diameter growth factor (GF) of 100 nm haze particles at 85 % relative humidity (RH) and their chemical characteristics were simultaneously monitored at Singapore in October 2015 during a pervasive wildfire haze episode that was caused by peatland burning in Indonesia. Non-refractory submicron particles (NR-PM1) were dominated by organics (OA approximating 77.1 % in total mass), whereas sulfate was the most abundant inorganic constituent (11.7 % on average). A statistical analysis of the organic mass spectra showed that most organics (36.0 % of NR-PM1 mass) were highly oxygenated. Diurnal variations of GF, number fractions of more hygroscopic mode particles, mass fractions of sulfate, and mass fractions of oxygenated organics (OOA) synchronized well, peaking during the day. The mean hygroscopicity parameter (κ) of the haze particles was 0.189 ± 0.087, and the mean κ values of organics were 0.157 ± 0.108 (κorg, bulk organics) and 0.266 ± 0.184 (κOOA, OOA), demonstrating the important roles of both sulfate and highly oxygenated organics in the hygroscopic growth of organics-dominated wildfire haze particles. κorg correlated with the water-soluble organic fraction insignificantly, but it positively correlated with f44 (fraction of the ion fragment at m∕z 44 in total organics) (R = 0.70), implying the oxygenation degree of organics could be more critical for the water uptake of organic compounds. These results further suggest the importance of sulfate and secondary organic aerosol formation in promoting the hygroscopic growth of wildfire haze particles. Further detailed size-resolved as well as molecular-level chemical information about organics is necessary for the profound exploration of water uptake by wildfire haze particles in equatorial Asia.
Publisher: Copernicus GmbH
Date: 26-04-2016
Abstract: Abstract. A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m∕z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15–33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ∼ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27–41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m∕z 75 is well correlated with the m∕z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The contribution of 91Fac to the total OA mass was significant (on average 22 % of OA mass) at the rural site only during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter s les collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass.
Publisher: Copernicus GmbH
Date: 29-04-2016
Publisher: Copernicus GmbH
Date: 19-12-2013
DOI: 10.5194/AMTD-6-11181-2013
Abstract: Abstract. The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was recently developed to provide long-term real-time continuous measurements of ambient non-refractory (i.e., organic, sulfate, ammonium, nitrate, and chloride) submicron particulate matter (NR-PM1). Currently, there are a limited number of field studies that evaluate the long-term performance of the ACSM against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011–2012. The collocated measurements included a second ACSM, continuous and integrated sulfate, nitrate, and ammonium measurements, as well as a semi-continuous Sunset organic carbon/elemental carbon (OC/EC) analyzer, continuous tapered element oscillating microbalance (TEOM), 24 h integrated Federal Reference Method (FRM) filters, and continuous scanning electrical mobility system-mixing condensation particle counter (SEMS-MCPC). Intercomparison of the two collocated ACSMs resulted in strong correlations (r2 0.8) for all chemical species, except chloride (r2 = 0.21) mass concentration for all chemical species agreed within ±27%, indicating that ACSM instruments are capable of stable and reproducible operation. Chemical constituents measured by the ACSM are also compared with those obtained from the continuous measurements from JST. Since the continuous measurement concentrations are adjusted to match the integrated filter measurements, these comparisons reflect the combined uncertainties of the ACSM, continuous, and filter measurements. In general, speciated ACSM mass concentrations correlate well (r2 0.7) with the continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Differences between ACSM mass concentrations and the filter-adjusted JST continuous data are 5–27%, 4–25%, and 34–51% for sulfate, ammonium, and nitrate, respectively. These comparisons are all close to the stated ±30% accuracy of the ACSM except for nitrate. These discrepancies could be due to positive biases in the ACSM nitrate concentrations from interferences at the NO+ (m/z 30) fragment ion and/or negative artifacts in the nitrate filter measurement (from volatilization of NH4NO3) are also possible. The organic matter OM/OC ratios derived from linear regression of ACSM OM vs. Sunset OC/EC analyzer are 4.18 ± 0.04 and 3.59 ± 0.02 for summer and fall, respectively. Linear correlations of the ACSM NR-PM1 plus EC with TEOM PM2.5 mass are strong (r2 0.7) with percentage difference of 19% and 80% during summer and fall, respectively. On the other hand, the ACSM NR-PM1 correlation with FRM PM1 is high (r2 0.8) with percentage difference of ±47% over three seasons. Correlation of ACSM NR-PM1 plus EC mass with SEMS-MCPC PM1 volume concentration results in an estimation of aerosol density of 1.61 g cm−3 for fall 2012 period. ACSM organic concentrations measured during this study were obtained using relative ionization efficiency (RIE) values observed in Aerodyne Aerosol Mass Spectrometer (AMS). Explicit calibration of the ACSM relative ionizations for ammonium, nitrate, and sulfate, during this study was shown to improve the comparisons between ACSM and collocated measurements for these species. The accuracy of the organic and total mass concentrations would likely also be improved if organic relative ionization efficiency values for the ACSM were available during this study. Laboratory calibrations of ACSM relative ionization efficiencies using organic particles of known composition are recommended for future studies.
Publisher: Copernicus GmbH
Date: 13-08-2015
Abstract: Abstract. A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 s les were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). C aign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m−3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.
Publisher: Copernicus GmbH
Date: 29-03-2018
Publisher: American Chemical Society (ACS)
Date: 20-04-2017
Publisher: Copernicus GmbH
Date: 19-01-2016
DOI: 10.5194/ACP-2015-983
Abstract: Abstract. In the southeastern U.S., substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter s les were collected at the Birmingham, Alabama (BHM) ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). S le extracts were analyzed by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) (~7 to ~20%). Isoprene-derived SOA tracers correlated with sulfate (SO42-) (r2 = 0.34, n = 117), but not with NOx. Moderate correlation between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (MAE/HMML)-derived SOA tracers and nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of NO3 radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO2) (r2 = 0.26, n = 40) was weaker. Ozone (O3) correlated strongly with MAE/HMML-derived tracers (r2 = 0.72, n = 30) and moderately with 2-methyltetrols (r2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA indicates that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm the reports that anthropogenic pollutants enhance isoprene-derived SOA formation.
Publisher: American Geophysical Union (AGU)
Date: 13-07-2022
DOI: 10.1029/2022JD036871
Abstract: Peatland fires in Southeast Asia are an important source of primary organic aerosol (POA). Chemical aging of POA in the atmosphere produces oxygenated POA (OPOA). The OPOA production influences optical and hygroscopic properties, modulating the regional climate. However, the roles of environmental parameters such as relative humidity (RH) on chemical aging of peatland burning particles have rarely been investigated. Utilizing the potential aerosol mass (PAM) reactor, we conducted laboratory experiments for POA aging of particles generated from smoldering combustions of surface peat, fern, and Acacia leaves. The corresponding experiments for secondary organic aerosol formation were also separately conducted. Properties and chemical compositions of the resulting particle were quantified by both the hygroscopic tandem differential mobility analyzer and time‐of‐flight aerosol chemical speciation monitor (ToF‐ACSM). Conversion of peat combustion from POA to OPOA was pronounced when RH in the PAM reactor was higher. Considering that previous electromicroscopic observations demonstrated that peat combustion POA is likely (semi)solid, we postulate that oxidation of fresh peatland burning particles is faster at an elevated RH due to reduced viscosity following hygroscopic growth. Hygroscopicity parameter ( κ ) of aged POA particles linearly correlated with the mass fraction of OPOA that was quantified by the ToF‐ACSM. The above results highlight the importance of simultaneously measuring the chemical aging and particle phase state of peatland burning POA for quantifying their climatic impacts.
Publisher: Copernicus GmbH
Date: 29-04-2016
DOI: 10.5194/AMT-2016-132
Abstract: Abstract. Measurement techniques that provide molecular-level information are needed to elucidate the multi-phase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS-MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS-MS after ionization with a custom build nitrate chemical ionization (CI) source. This CI-IMS-MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field c aign in the forested SE US. The ambient IMS-MS signals are consistent with laboratory IMS-MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-dimensional IMS-MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS-MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisional dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the presence of the organosulfate functional group.
Publisher: Copernicus GmbH
Date: 28-03-2022
DOI: 10.5194/EGUSPHERE-EGU22-9306
Abstract: & & We present results from an exploratory study investigating deep clustering of high-dimension mass spectrometry data. Field measurements were taken from aerosol filter s les collected at sites in multiple seasons in Beijing and Delhi. ~450 s les were analysed using ultra-high pressure liquid chromatography coupled with heated electrospray ionisation and Orbitrap mass spectrometry (UHPLC-HESI-Orbitrap MS), producing over 1000 molecular markers for each s le, each with a distinctive organic molecule and retention time. With far more dimensions than s les (i.e. more columns than rows), this dataset is not ideal for traditional nearest-neighbour clustering methods as the largest peaks dominate the signal, and nearest-neighbour distances blur as dimensionality increases.& & & & & br& We demonstrate the impact of deep clustering, using autoencoders to reduce data dimensionality. Autoencoders are a deep learning method using two linked neural networks to reduce data dimensionality. One & #8220 encoder& #8221 network reduces the data to a smaller latent space, while a second & #8220 decoder& #8221 network increases the dimensionality of the latent space back to the original dimensions of the dataset. The two networks are trained together to minimise loss of information, producing a clusterable latent space with similar information content as the original dataset but with far fewer dimensions.& & & & & br& We present comparisons of deep clustering and traditional hierarchical clustering to identify key molecules and features in the s le time series. We will also demonstrate the impact of prescaling the data, a common technique in the application of neural networks.& &
Publisher: Copernicus GmbH
Date: 29-03-2018
DOI: 10.5194/ACP-2018-217
Abstract: Abstract. Recurring transboundary haze from Indonesian wildfires in previous decades significantly elevated particulate matter (PM) concentrations in Southeast Asia. During that event on October 10 to 31, 2015, we conducted a real-time observation of non-refractory submicron PM (NR-PM1) in Singapore using an Aerodyne aerosol mass spectrometer. Simultaneously, we characterized carbonaceous components and organic aerosol (OA) tracers from fine PM (PM2.5) s les to support source apportionment of the online measurements. The real-time analysis demonstrated that OA accounted for approximately 80 % of NR-PM1 mass during the wildfire haze period. Source apportionment analysis applied to the OA mass spectra using multilinear-engine (ME-2) approach resulted in four factors: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), peat burning OA (PBOA), and oxygenated OA (OOA). The OOA can be considered as a surrogate of both secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), while the other factors are considered as surrogates of primary organic aerosol (POA). The OOA accounted for approximately 50 % of the total OA mass in NR-PM1, while POA subtypes from wildfires (BBOA and PBOA) contributed to approximately 30 % of the total OA mass. Our findings highlight the importance of atmospheric chemical processes, which likely include POA oxidation and SOA formation from oxidation of gaseous precursors, to the OOA concentration. As this research could not separately quantify the POA oxidation and SOA formation processes, further studies should attempt to investigate the contribution of gaseous precursors oxidation and POA aging to the OOA formation in wildfire plumes.
Publisher: American Chemical Society (ACS)
Date: 09-2016
Abstract: Atmospheric oxidation of isoprene under low-NOx conditions leads to the formation of isoprene hydroxyhydroperoxides (ISOPOOH). Subsequent oxidation of ISOPOOH largely produces isoprene epoxydiols (IEPOX), which are known secondary organic aerosol (SOA) precursors. Although SOA from IEPOX has been previously examined, systematic studies of SOA characterization through a non-IEPOX route from 1,2-ISOPOOH oxidation are lacking. In the present work, SOA formation from the oxidation of authentic 1,2-ISOPOOH under low-NOx conditions was systematically examined with varying aerosol compositions and relative humidity. High yields of highly oxidized compounds, including multifunctional organosulfates (OSs) and hydroperoxides, were chemically characterized in both laboratory-generated SOA and fine aerosol s les collected from the southeastern U.S. IEPOX-derived SOA constituents were observed in all experiments, but their concentrations were only enhanced in the presence of acidified sulfate aerosol, consistent with prior work. High-resolution aerosol mass spectrometry (HR-AMS) reveals that 1,2-ISOPOOH-derived SOA formed through non-IEPOX routes exhibits a notable mass spectrum with a characteristic fragment ion at m/z 91. This laboratory-generated mass spectrum is strongly correlated with a factor recently resolved by positive matrix factorization (PMF) of aerosol mass spectrometer data collected in areas dominated by isoprene emissions, suggesting that the non-IEPOX pathway could contribute to ambient SOA measured in the Southeastern United States.
Publisher: Copernicus GmbH
Date: 27-03-2017
Publisher: Elsevier BV
Date: 09-2019
Publisher: Copernicus GmbH
Date: 20-08-2015
DOI: 10.5194/ACPD-15-22379-2015
Abstract: Abstract. A yearlong near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia) and rural (Look Rock, Tennessee) site in the southeastern US using the Aerodyne aerosol chemical speciation monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (50–76 %) and inorganic sulfate (12–31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the one year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (OOA), isoprene-derived epoxydiol (IEPOX) OA (IEPOX-OA), and 91Fac OA (a factor dominated by a distinct ion at m/z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed 30–66 % of total OA mass. HOA was also observed during the entire year only at the urban site (15–24 % of OA mass). BBOA (15–33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly (∼ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27–41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m/z 75 is proposed as an additional marker for IEPOX-OA, as it is shown to correlate well with the m/z 82 ion shown to be associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The contribution of 91Fac to the total OA mass was quite low at the urban site (∼ 9 %), but was significant (21–23 %) at the rural site during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter s les collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass.
Publisher: Copernicus GmbH
Date: 23-10-2018
DOI: 10.5194/AMT-2018-326
Abstract: Abstract. The elemental composition of organic material in environmental s les – including atmospheric organic aerosol, dissolved organic matter, and other complex mixtures – provides insights into their sources and environmental processing. However, standard analytical techniques for measuring elemental ratios typically require large s le sizes (milligrams of material or more). Here we characterize a method for measuring elemental ratios in environmental s les, requiring only micrograms of material, using a Small Volume Nebulizer (SVN). The technique uses ultrasonic nebulization of s les to generate aerosol particles (100–300 nm diameter), which are then analyzed using an aerosol mass spectrometer (AMS). We demonstrate that the technique generates aerosol from complex organic mixtures with minimal changes to the elemental composition of the organic and that quantification is possible using internal standards (e.g., NH415NO3). S le volumes of 2–4 uL with total solution concentrations of at least 0.2–g/L form sufficient particle mass for elemental ratio measurement by the AMS, despite only a small fraction (~ 0.1 %) of the s le forming fine particles while the remainder end up as larger droplets. The method was applied to aerosol filter extracts from the field and laboratory, as well as to dissolved organic matter (DOM) from the North Pacific Ocean. In the case of aerosol particles, the mass spectra and elemental ratios from the SVN-AMS agree with those from online AMS s ling similarly, for DOM, the elemental ratios determined from the SVN-AMS agree with those determined using combustion analysis. The SVN-AMS provides a platform for the rapid quantitative analysis of the elemental composition of complex organic mixtures and non-refractory inorganic salts from microgram s les with applications that include analysis of aerosol extracts, and terrestrial and atmospheric dissolved organic matter.
Publisher: Copernicus GmbH
Date: 19-12-2013
Publisher: American Chemical Society (ACS)
Date: 20-01-2015
DOI: 10.1021/EZ500406F
Publisher: Copernicus GmbH
Date: 20-08-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2EA00074A
Abstract: Liquid chromatography coupled to electrospray ionisation high resolution mass spectrometry is an extremely powerful technique for both targeted and non-targeted analysis of organic aerosol.
Publisher: Copernicus GmbH
Date: 14-03-2019
Abstract: Abstract. The elemental composition of organic material in environmental s les – including atmospheric organic aerosol, dissolved organic matter, and other complex mixtures – provides insights into their sources and environmental processing. However, standard analytical techniques for measuring elemental ratios typically require large s le sizes (milligrams of material or more). Here we characterize a method for measuring elemental ratios in environmental s les, requiring only micrograms of material, using a small-volume nebulizer (SVN). The technique uses ultrasonic nebulization of s les to generate aerosol particles (100–300 nm diameter), which are then analyzed using an aerosol mass spectrometer (AMS). We demonstrate that the technique generates aerosol from complex organic mixtures with minimal changes to the elemental composition of the organic material and that quantification is possible using internal standards (e.g., NH415NO3). S le volumes of 2–4 µL with total solution concentrations of at least 0.2 g L−1 form sufficient particle mass for elemental ratio measurement by the AMS, despite only a small fraction (∼ 0.1 %) of the s le forming fine particles after nebulization (with the remainder ending up as larger droplets). The method was applied to aerosol filter extracts from the field and laboratory, as well as to the polysaccharide fraction of dissolved organic matter (DOM) from the North Pacific Ocean. In the case of aerosol particles, the mass spectra and elemental ratios from the SVN–AMS agree with those from online AMS s ling. Similarly, for DOM, the elemental ratios determined from the SVN–AMS agree with those determined using combustion analysis. The SVN–AMS provides a platform for the rapid quantitative analysis of the elemental composition of complex organic mixtures and non-refractory inorganic salts from microgram s les with applications that include analysis of aerosol extracts and terrestrial, aquatic, and atmospheric dissolved organic matter.
Publisher: Copernicus GmbH
Date: 27-03-2017
DOI: 10.5194/ACP-2017-136
Abstract: Abstract. The relationship between hygroscopic properties and chemical characteristics of Indonesian biomass burning (BB) particles, which are dominantly generated from peatland fires, was investigated using the humidified tandem differential mobility analyzer. In addition to peat, acacia (a popular species at plantation) and fern (a pioneering species after disturbance by fire) were used for experiments. Fresh Indonesian peat burning particles are almost non-hygroscopic (mean hygroscopicity parameter, κ
Publisher: American Chemical Society (ACS)
Date: 07-06-2019
Publisher: Copernicus GmbH
Date: 16-08-2016
Publisher: Copernicus GmbH
Date: 16-04-2015
Publisher: Copernicus GmbH
Date: 21-11-2018
DOI: 10.5194/ACP-18-16481-2018
Abstract: Abstract. Recurring transboundary haze from Indonesian wildfires in previous decades significantly elevated particulate matter (PM) concentrations in Southeast Asia. During that event on 10 to 31 October 2015, we conducted a real-time observation of non-refractory submicron PM (NR-PM1) in Singapore using an Aerodyne aerosol mass spectrometer. Simultaneously, we characterized carbonaceous components and organic aerosol (OA) tracers from fine PM (PM2.5) s les to support source apportionment of the online measurements. The real-time analysis demonstrated that OA accounted for approximately 80 % of NR-PM1 mass during the wildfire haze period. Source apportionment analysis applied to the OA mass spectra using the multilinear-engine (ME-2) approach resulted in four factors: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), peat burning OA (PBOA), and oxygenated OA (OOA). The OOA can be considered as a surrogate of both secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), while the other factors are considered as surrogates of primary organic aerosol (POA). The OOA accounted for approximately 50 % of the total OA mass in NR-PM1, while POA subtypes from wildfires (BBOA and PBOA) contributed to approximately 30 % of the total OA mass. Our findings highlight the importance of atmospheric chemical processes, which likely include POA oxidation and SOA formation from oxidation of gaseous precursors, to the OOA concentration. As this research could not separately quantify the POA oxidation and SOA formation processes, further studies should attempt to investigate the contribution of gaseous precursor oxidation and POA aging to the OOA formation in wildfire plumes.
Publisher: Copernicus GmbH
Date: 19-01-2016
Publisher: Copernicus GmbH
Date: 28-09-2017
DOI: 10.5194/ACP-17-11591-2017
Abstract: Abstract. The relationship between hygroscopic properties and chemical characteristics of Indonesian biomass burning (BB) particles, which are dominantly generated from peatland fires, was investigated using a humidified tandem differential mobility analyzer. In addition to peat, acacia (a popular species at plantation) and fern (a pioneering species after disturbance by fire) were used for experiments. Fresh Indonesian peat burning particles are almost non-hygroscopic (mean hygroscopicity parameter, κ 0.06) due to predominant contribution of water-insoluble organics. The range of κ spans from 0.02 to 0.04 (dry diameter = 100 nm, hereinafter) for Riau peat burning particles, while that for Central Kalimantan ranges from 0.05 to 0.06. Fern combustion particles are more hygroscopic (κ = 0. 08), whereas the acacia burning particles have a mediate κ value (0.04). These results suggest that κ is significantly dependent on biomass types. This variance in κ is partially determined by fractions of water-soluble organic carbon (WSOC), as demonstrated by a correlation analysis (R = 0.65). κ of water-soluble organic matter is also quantified, incorporating the 1-octanol–water partitioning method. κ values for the water extracts are high, especially for peat burning particles (A0 (a whole part of the water-soluble fraction): κ = 0.18, A1 (highly water-soluble fraction): κ = 0.30). This result stresses the importance of both the WSOC fraction and κ of the water-soluble fraction in determining the hygroscopicity of organic aerosol particles. Values of κ correlate positively (R = 0.89) with the fraction of m∕z 44 ion signal quantified using a mass spectrometric technique, demonstrating the importance of highly oxygenated organic compounds to the water uptake by Indonesian BB particles. These results provide an experimentally validated reference for hygroscopicity of organics-dominated particles, thus contributing to more accurate estimation of environmental and climatic impacts driven by Indonesian BB particles on both regional and global scales.
Publisher: American Chemical Society (ACS)
Date: 21-05-2013
DOI: 10.1021/ES400023N
Abstract: Real-time continuous chemical measurements of fine aerosol were made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer and fall 2011 in downtown Atlanta, Georgia. Organic mass spectra measured by the ACSM were analyzed by positive matrix factorization (PMF), yielding three conventional factors: hydrocarbon-like organic aerosol (HOA), semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA). An additional OOA factor that contributed to 33 ± 10% of the organic mass was resolved in summer. This factor had a mass spectrum that strongly correlated (r(2) = 0.74) to that obtained from laboratory-generated secondary organic aerosol (SOA) derived from synthetic isoprene epoxydiols (IEPOX). Time series of this additional factor is also well correlated (r(2) = 0.59) with IEPOX-derived SOA tracers from filters collected in Atlanta but less correlated (r(2) < 0.3) with a methacrylic acid epoxide (MAE)-derived SOA tracer, α-pinene SOA tracers, and a biomass burning tracer (i.e., levoglucosan), and primary emissions. Our analyses suggest IEPOX as the source of this additional factor, which has some correlation with aerosol acidity (r(2) = 0.3), measured as H(+) (nmol m(-3)), and sulfate mass loading (r(2) = 0.48), consistent with prior work showing that these two parameters promote heterogeneous chemistry of IEPOX to form SOA.
Publisher: Copernicus GmbH
Date: 14-09-2022
DOI: 10.5194/ACP-2022-603
Abstract: Abstract. Isoprene and monoterpenes emissions to the atmosphere are generally dominated by biogenic sources. The oxidation of these compounds can lead to the production of secondary organic aerosol, however the impact of this chemistry in polluted urban settings has been poorly studied. Isoprene and monoterpenes can form SOA heterogeneously via anthropogenic-biogenic interactions resulting in the formation of organosulfates (OS) and nitrooxy-organosulfates (NOS). Delhi, India is one of the most polluted cities in the world, but little is known about the emissions of biogenic VOCs or the sources of SOA. As part of the DELHI-FLUX project, gas phase mixing ratios of isoprene and speciated monoterpenes were measured during pre- and post-monsoon measurement c aigns in central Delhi. Nocturnal mixing ratios of the VOCs were substantially higher during the post-monsoon (isoprene: (0.65 ± 0.43) ppbv, limonene: (0.59 ± 0.11) ppbv, α-pinene: (0.13 ± 0.12) ppbv) than the pre-monsoon (isoprene: (0.13 ± 0.18) ppbv, limonene: 0.011 ± 0.025 (ppbv), α-pinene: 0.033 ± 0.009) period. At night, isoprene and monoterpene concentrations correlated strongly with CO across during the post-monsoon period. This is one of the first observations in Asia, suggesting monoterpene emissions are dominated by anthropogenic sources. Filter s les of particulate matter less than 2.5 microns in diameter (PM2.5) were collected and the OS and NOS content analysed using ultrahigh-performance liquid chromatography tandem mass spectrometry (UHPLC-MS2). Inorganic sulfate was shown to facilitate the formation of isoprene OS species across both c aigns. Sulfate contained within OS and NOS species were shown to contribute significantly to the sulfate signal measured via AMS. Strong nocturnal enhancements of NOS species were observed across both c aigns. The total concentration of OS/NOS species contributed an average of (2.0 ± 0.9) % and (1.8 ± 1.4) % to the total oxidised organic aerosol, and up to a maximum of 4.2 % and 6.6 % across the pre- and post-monsoon periods, respectively. Overall, this study provides the first molecular level measurements of SOA derived from isoprene and monoterpene in Delhi and demonstrates that both biogenic and anthropogenic sources of these compounds can be important in urban areas.
Publisher: Copernicus GmbH
Date: 10-03-2015
Publisher: American Chemical Society (ACS)
Date: 30-03-2017
Abstract: Light-absorbing brown carbon (BrC) constituents of organic aerosol (OA) have been shown to significantly absorb ultraviolet (UV) and visible light and thus impact radiative forcing. However, molecular identification of the BrC constituents is still limited. In this study, we characterize BrC constituents at the molecular level in (i) aerosols emitted by combustion of peat, fern/leaf, and charcoal from Indonesia and (ii) ambient aerosols collected in Singapore during the 2015 haze episode. Aerosols were analyzed using ultra performance liquid chromatography instrument interfaced to a diode array detector and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer operated in the negative ion mode. In the laboratory-generated aerosols, we identified 41 compounds that can potentially absorb near-UV and visible wavelengths, such as oxygenated-conjugated compounds, nitroaromatics, and S-containing compounds. The sum of BrC constituents in peat, fern/leaf, and charcoal burning aerosols are 16%, 35%, and 28% of the OA mass, respectively, giving an average contribution of 24%. On average, the BrC constituents account for 0.4% of the ambient OA mass however, large uncertainties in mass closure remain because of the lack of authentic standards. This study highlights the potential of light-absorbing BrC OA constituents from peat, fern/leaf, and charcoal burning and their importance in the atmosphere.
Publisher: Copernicus GmbH
Date: 03-01-2023
Abstract: Abstract. Isoprene and monoterpene emissions to the atmosphere are generally dominated by biogenic sources. The oxidation of these compounds can lead to the production of secondary organic aerosol however the impact of this chemistry in polluted urban settings has been poorly studied. Isoprene and monoterpenes can form secondary organic aerosol (SOA) heterogeneously via anthropogenic–biogenic interactions, resulting in the formation of organosulfate (OS) and nitrooxy-organosulfate (NOS) species. Delhi, India, is one of the most polluted cities in the world, but little is known about the emissions of biogenic volatile organic compounds (VOCs) or the sources of SOA. As part of the DELHI-FLUX project, gas-phase mixing ratios of isoprene and speciated monoterpenes were measured during pre- and post-monsoon measurement c aigns in central Delhi. Nocturnal mixing ratios of the VOCs were substantially higher during the post-monsoon (isoprene: (0.65±0.43) ppbv limonene: (0.59±0.11) ppbv α-pinene: (0.13±0.12) ppbv) than the pre-monsoon (isoprene: (0.13±0.18) ppbv limonene: 0.011±0.025 (ppbv) α-pinene: 0.033±0.009) period. At night, isoprene and monoterpene concentrations correlated strongly with CO during the post-monsoon period. Filter s les of particulate matter less than 2.5 µm in diameter (PM2.5) were collected and the OS and NOS content analysed using ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS2). Inorganic sulfate was shown to facilitate the formation of isoprene OS species across both c aigns. Sulfate contained within OS and NOS species was shown to contribute significantly to the sulfate signal measured via AMS. Strong nocturnal enhancements of NOS species were observed across both c aigns. The total concentration of OS and NOS species contributed an average of (2.0±0.9) % and (1.8±1.4) % to the total oxidized organic aerosol and up to a maximum of 4.2 % and 6.6 % across the pre- and post-monsoon periods, respectively. Overall, this study provides the first molecular-level measurements of SOA derived from isoprene and monoterpene in Delhi and demonstrates that both biogenic and anthropogenic sources of these compounds can be important in urban areas.
Publisher: American Geophysical Union (AGU)
Date: 11-09-2020
DOI: 10.1029/2020JD032706
Publisher: Copernicus GmbH
Date: 16-04-2015
DOI: 10.5194/ACPD-15-11223-2015
Abstract: Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O ( 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a "triangle plot" of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2 if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass resolution data is available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.
Publisher: American Chemical Society (ACS)
Date: 29-11-2021
Publisher: American Chemical Society (ACS)
Date: 21-01-2019
DOI: 10.26434/CHEMRXIV.7597397.V1
Abstract: Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), a key isoprene oxidation product, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. Herein, we reveal that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate ratio (IEPOX:Sulf inorg ), as determined by laboratory and field measurements. We further demonstrate that organosulfur greatly modifies critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights reveal that changes in SO 2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX:Sulf inorg will play a central role in understanding historical climate and determining future impacts of biogenic SOA on global climate and air quality.
Publisher: Elsevier BV
Date: 04-2016
Publisher: Copernicus GmbH
Date: 02-07-2014
Abstract: Abstract. Currently, there are a limited number of field studies that evaluate the long-term performance of the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011–2012. Intercomparison of two collocated ACSMs resulted in strong correlations (r2 0.8) for all chemical species, except chloride (r2 = 0.21) indicating that ACSM instruments are capable of stable and reproducible operation. In general, speciated ACSM mass concentrations correlate well (r2 0.7) with the filter-adjusted continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Correlations of the ACSM NR-PM1 (non-refractory particulate matter with aerodynamic diameter less than or equal to 1 μm) plus elemental carbon (EC) with tapered element oscillating microbalance (TEOM) PM2.5 and Federal Reference Method (FRM) PM1 mass are strong with r2 0.7 and r2 0.8, respectively. Discrepancies might be attributed to evaporative losses of semi-volatile species from the filter measurements used to adjust the collocated continuous measurements. This suggests that adjusting the ambient aerosol continuous measurements with results from filter analysis introduced additional bias to the measurements. We also recommend to calibrate the ambient aerosol monitoring instruments using aerosol standards rather than gas-phase standards. The fitting approach for ACSM relative ionization for sulfate was shown to improve the comparisons between ACSM and collocated measurements in the absence of calibrated values, suggesting the importance of adding sulfate calibration into the ACSM calibration routine.
Publisher: American Chemical Society (ACS)
Date: 03-06-2014
DOI: 10.1021/EZ5001353
Publisher: Copernicus GmbH
Date: 06-01-2017
Abstract: Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model–measurement gap. When taking into account deviations from ideality, including both inorganic (when RH SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.
Publisher: American Chemical Society (ACS)
Date: 13-06-2019
Abstract: Polarity distribution of water-soluble organic matter (WSOM) is an important factor in determining the hygroscopic and cloud nucleation abilities of organic aerosol particles. We applied a novel framework to quantitatively classify WSOM based on the 1-octanol-water partition coefficient (
Publisher: Copernicus GmbH
Date: 23-10-2018
Publisher: American Chemical Society (ACS)
Date: 28-10-2021
Location: United Kingdom of Great Britain and Northern Ireland
Location: United States of America
No related grants have been discovered for Sri Hapsari Budisulistiorini.