Organic Aerosol Concentrations Research Articles

Simulations of organic aerosol concentrations during springtime in the Guanzhong Basin, China

Abstract. The organic aerosol (OA) concentration is simulated in the Guanzhong Basin, China from 23 to 25 April 2013 utilizing the WRF-CHEM model. Two approaches are used to predict OA concentrations: (1) a traditional secondary organic aerosol (SOA) module; (2) a non-traditional SOA module including the volatility basis-set modeling method in which primary organic aerosol (POA) is assumed to be semivolatile and photochemically reactive. Generally, the spatial patterns and temporal variations of the calculated hourly near-surface ozone and fine particle matters agree well with the observations in Xi'an and surrounding areas. The model also yields reasonable distributions of daily PM2.5 and elemental carbon (EC) compared to the filter measurements at 29 sites in the basin. Filter-measured organic carbon (OC) and EC are used to evaluate OA, POA, and SOA using the OC ∕ EC ratio approach. Compared with the traditional SOA module, the non-traditional module significantly improves SOA simulations and explains about 88 % of the observed SOA concentration. Oxidation and partitioning of POA treated as semivolatile constitute the most important pathway for the SOA formation, contributing more than 75 % of the SOA concentrations in the basin. Residential emissions are the dominant anthropogenic OA source, constituting about 50 % of OA concentrations in urban and rural areas and 30 % in the background area. The OA contribution from transportation emissions decreases from 25 % in urban areas to 20 % in the background area, and the industry emission OA contribution is less than 6 %.

Sampling strategies and post-processing methods for increasing the time resolution of organic aerosol measurements requiring long sample-collection times

Abstract. The composition and properties of atmospheric organic aerosols (OAs) change on timescales of minutes to hours. However, some important OA characterization techniques typically require greater than a few hours of sample-collection time (e.g., Fourier transform infrared (FTIR) spectroscopy). In this study we have performed numerical modeling to investigate and compare sample-collection strategies and post-processing methods for increasing the time resolution of OA measurements requiring long sample-collection times. Specifically, we modeled the measurement of hydrocarbon-like OA (HOA) and oxygenated OA (OOA) concentrations at a polluted urban site in Mexico City, and investigated how to construct hourly resolved time series from samples collected for 4, 6, and 8 h. We modeled two sampling strategies – sequential and staggered sampling – and a range of post-processing methods including interpolation and deconvolution. The results indicated that relative to the more sophisticated and costly staggered sampling methods, linear interpolation between sequential measurements is a surprisingly effective method for increasing time resolution. Additional error can be added to a time series constructed in this manner if a suboptimal sequential sampling schedule is chosen. Staggering measurements is one way to avoid this effect. There is little to be gained from deconvolving staggered measurements, except at very low values of random measurement error (< 5 %). Assuming 20 % random measurement error, one can expect average recovery errors of 1.33–2.81 µg m−3 when using 4–8 h-long sequential and staggered samples to measure time series of concentration values ranging from 0.13–29.16 µg m−3. For 4 h samples, 19–47 % of this total error can be attributed to the process of increasing time resolution alone, depending on the method used, meaning that measurement precision would only be improved by 0.30–0.75 µg m−3 if samples could be collected over 1 h instead of 4 h. Devising a suitable sampling strategy and post-processing method is a good approach for increasing the time resolution of measurements requiring long sample-collection times.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Applications and limitations of constrained high-resolution peak fitting on low resolving power mass spectra from the ToF-ACSM

Abstract. The applicability, methods and limitations of constrained peak fitting on mass spectra of low mass resolving power (m∕Δm50 ∼ 500) recorded with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) are explored. Calibration measurements as well as ambient data are used to exemplify the methods that should be applied to maximise data quality and assess confidence in peak-fitting results. Sensitivity analyses and basic peak fit metrics such as normalised ion separation are employed to demonstrate which peak-fitting analyses commonly performed in high-resolution aerosol mass spectrometry are appropriate to perform on spectra of this resolving power. Information on aerosol sulfate, nitrate, sodium chloride, methanesulfonic acid as well as semi-volatile metal species retrieved from these methods is evaluated. The constants in a commonly used formula for the estimation of the mass concentration of hydrocarbon-like organic aerosol may be refined based on peak-fitting results. Finally, application of a recently published parameterisation for the estimation of carbon oxidation state to ToF-ACSM spectra is validated for a range of organic standards and its use demonstrated for ambient urban data.

Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

Abstract. In this work, the Aerodyne soot particle – aerosol mass spectrometer (SP-AMS) was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD) of China, for online characterization of the submicron aerosols (PM1). The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC) simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics). The average PM1 concentration was found to be 28.2 µg m−3, with organics (45 %) as the most abundant component, following by sulfate (19.3 %), nitrate (13.6 %), ammonium (11.1 %), rBC (9.7 %), and chloride (1.3 %). These PM1 species together can reconstruct ∼ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (< 100 nm vacuum aerodynamic diameter) were dominated by organics and rBC, while large particles had significant contributions from secondary inorganic species. Source apportionment of organic aerosols (OA) yielded four OA subcomponents, including hydrocarbon-like OA (HOA), cooking-related OA (COA), semi-volatile oxygenated OA (SV-OOA), and low-volatility oxygenated OA (LV-OOA). Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA) dominated the total OA mass (55.5 %), but primary organic aerosol (POA, equal to the sum of HOA and COA) can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand, in contrast to other species, sulfate, and LV-OOA concentrations increased in the afternoon, and showed no positive correlations with relative humidity (RH), likely indicating the contribution from photochemical oxidation is dominant over that of aqueous-phase processing for their formations. The bivariate polar plots show that the SV-OOA was formed locally, and the variations of hydrogen-to-carbon (H ∕ C) and oxygen-to-carbon (O ∕ C) ratios in the Van Krevelen space further suggests an evolution pathway of SV-OOA to LV-OOA. Our findings regarding springtime aerosol chemistry in Nanjing may have important implications for the air quality remediation in the densely populated regions.

The aerosol radiative effects of uncontrolled combustion of domestic waste

Abstract. Open, uncontrolled combustion of domestic waste is a potentially significant source of aerosol; however, this aerosol source is not generally included in many global emissions inventories. To provide a first estimate of the aerosol radiative impacts from domestic-waste combustion, we incorporate the Wiedinmyer et al. (2014) emissions inventory into GEOS-Chem-TOMAS, a global chemical-transport model with online aerosol microphysics. We find domestic-waste combustion increases global-mean black carbon and organic aerosol concentrations by 8 and 6 %, respectively, and by greater than 40 % in some regions. Due to uncertainties regarding aerosol optical properties, we estimate the globally averaged aerosol direct radiative effect to range from −5 to −20 mW m−2; however, this range increases from −40 to +4 mW m−2 when we consider uncertainties in emission mass and size distribution. In some regions with significant waste combustion, such as India and China, the aerosol direct radiative effect may exceed −0.4 W m−2. Similarly, we estimate a cloud-albedo aerosol indirect effect of −13 mW m−2, with a range of −4 to −49 mW m−2 due to emission uncertainties. In the regions with significant waste combustion, the cloud-albedo aerosol indirect effect may exceed −0.4 W m−2.

Quantifying the effect of organic aerosol aging and intermediate-volatility emissions on regional-scale aerosol pollution in China.

Secondary organic aerosol (SOA) is one of the least understood constituents of fine particles; current widely-used models cannot predict its loadings or oxidation state. Recent laboratory experiments demonstrated the importance of several new processes, including aging of SOA from traditional precursors, aging of primary organic aerosol (POA), and photo-oxidation of intermediate volatility organic compounds (IVOCs). However, evaluating the effect of these processes in the real atmosphere is challenging. Most models used in previous studies are over-simplified and some key reaction trajectories are not captured, and model parameters are usually phenomenological and lack experimental constraints. Here we comprehensively assess the effect of organic aerosol (OA) aging and intermediate-volatility emissions on regional-scale OA pollution with a state-of-the-art model framework and experimentally constrained parameters. We find that OA aging and intermediate-volatility emissions together increase OA and SOA concentrations in Eastern China by about 40% and a factor of 10, respectively, thereby improving model-measurement agreement significantly. POA and IVOCs both constitute over 40% of OA concentrations, and IVOCs constitute over half of SOA concentrations; this differs significantly from previous apportionment of SOA sources. This study facilitates an improved estimate of aerosol-induced climate and health impacts, and implies a shift from current fine-particle control policies.

Composition and Sources of Particulate Matter Measured near Houston, TX: Anthropogenic-Biogenic Interactions

Particulate matter was measured in Conroe, Texas (~60 km north of downtown Houston, Texas) during the September 2013 DISCOVER-AQ campaign to determine the sources of particulate matter in the region. The measurement site is influenced by high biogenic emission rates as well as transport of anthropogenic pollutants from the Houston metropolitan area and is therefore an ideal location to study anthropogenic-biogenic interactions. Data from an Aerosol Chemical Speciation Monitor (ACSM) suggest that on average 64 percent of non-refractory PM1 was organic material, including a high fraction (27%–41%) of organic nitrates. There was little diurnal variation in the concentrations of ammonium sulfate; however, concentrations of organic and organic nitrate aerosol were consistently higher at night than during the day. Potential explanations for the higher organic aerosol loadings at night include changing boundary layer height, increased partitioning to the particle phase at lower temperatures, and differences between daytime and nighttime chemical processes such as nitrate radical chemistry. Positive matrix factorization was applied to the organic aerosol mass spectra measured by the ACSM and three factors were resolved—two factors representing oxygenated organic aerosol and one factor representing hydrocarbon-like organic aerosol. The factors suggest that the measured aerosol was well mixed and highly processed, consistent with the distance from the site to major aerosol sources, as well as the high photochemical activity.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

Abstract. Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS instead treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/Ox) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using −log(NOx : NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 × . From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6–2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. The VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.

Simulating the formation of carbonaceous aerosol in a European Megacity (Paris) during the MEGAPOLI summer and winter campaigns

Abstract. We use a three-dimensional regional chemical transport model (PMCAMx) with high grid resolution and high-resolution emissions (4 × 4 km2) over the Paris greater area to simulate the formation of carbonaceous aerosol during a summer (July 2009) and a winter (January/February 2010) period as part of the MEGAPOLI (megacities: emissions, urban, regional, and global atmospheric pollution and climate effects, and Integrated tools for assessment and mitigation) campaigns. Model predictions of carbonaceous aerosol are compared against Aerodyne aerosol mass spectrometer and black carbon (BC) high time resolution measurements from three ground sites. PMCAMx predicts BC concentrations reasonably well reproducing the majority (70 %) of the hourly data within a factor of two during both periods. The agreement for the summertime secondary organic aerosol (OA) concentrations is also encouraging (mean bias = 0.1 µg m−3) during a photochemically intense period. The model tends to underpredict the summertime primary OA concentrations in the Paris greater area (by approximately 0.8 µg m−3) mainly due to missing primary OA emissions from cooking activities. The total cooking emissions are estimated to be approximately 80 mg d−1 per capita and have a distinct diurnal profile in which 50 % of the daily cooking OA is emitted during lunch time (12:00–14:00 LT) and 20 % during dinner time (20:00–22:00 LT). Results also show a large underestimation of secondary OA in the Paris greater area during wintertime (mean bias = −2.3 µg m−3) pointing towards a secondary OA formation process during low photochemical activity periods that is not simulated in the model.

Drying-Induced Evaporation of Secondary Organic Aerosol during Summer.

This study characterized the effect of drying on the concentration of atmospheric secondary organic aerosol (SOA). Simultaneous measurements of water-soluble organic carbon in the gas (WSOCg) and particle (WSOCp) phases were carried out in Baltimore, MD during the summertime. To investigate the effect of drying on SOA, the WSOCp measurement was alternated through an ambient channel (WSOCp) and a "dried" channel (WSOCp,dry) maintained at ∼35% relative humidity (RH). The average mass ratio between WSOCp,dry and WSOCp was 0.85, showing that significant evaporation of the organic aerosol occurred due to drying. The average amount of evaporated water-soluble organic matter (WSOM = WSOC × 1.95) was 0.6 μg m(-3); however, the maximum evaporated WSOM concentration exceeded 5 μg m(-3), demonstrating the importance of this phenomenon. The systematic difference between ambient and dry channels indicates a significant and persistent source of aqueous SOA formed through reversible uptake processes. The wide-ranging implications of the work are discussed, and include: new insight into atmospheric SOA formation; impacts on particle measurement techniques; a newly identified bias in PM2.5 measurements using the EPA's Federal Reference and Equivalent Methods (FRM and FEM); atmospheric model evaluations; and the challenge in relating ground-based measurements to remote sensing of aerosol properties.

Gas–particle partitioning and hydrolysis of organic nitrates formed from the oxidation of <i>α</i>-pinene in environmental chamber experiments

Abstract. Gas–particle partitioning and hydrolysis of organic nitrates (ON) influences their role as sinks and sources of NOx and their effects on the formation of tropospheric ozone and organic aerosol (OA). In this work, organic nitrates were formed from the photo-oxidation of α-pinene in environmental chamber experiments under different conditions. Particle-phase ON hydrolysis rates, consistent with observed ON decay, exhibited a nonlinear dependence on relative humidity (RH): an ON decay rate of 2 day−1 was observed when the RH ranged between 20 and 60 %, and no significant ON decay was observed at RH lower than 20 %. In experiments when the highest observed RH exceeded the deliquescence RH of the ammonium sulfate seed aerosol, the particle-phase ON decay rate was as high as 7 day−1 and more variable. The ON gas–particle partitioning was dependent on total OA concentration and temperature, consistent with absorptive partitioning theory. In a volatility basis set, the ON partitioning was consistent with mass fractions of [0 0.11 0.03 0.86] at saturation mass concentrations (C*) of [1 10 100 1000] µg m−3.

What do correlations tell us about anthropogenic–biogenic interactions and SOA formation in the Sacramento plume during CARES?

Abstract. During the Carbonaceous Aerosols and Radiative Effects Study (CARES) the US Department of Energy (DOE) G-1 aircraft was used to sample aerosol and gas phase compounds in the Sacramento, CA, plume and surrounding region. We present data from 66 plume transects obtained during 13 flights in which southwesterly winds transported the plume towards the foothills of the Sierra Nevada. Plume transport occurred partly over land with high isoprene emission rates. Our objective is to empirically determine whether organic aerosol (OA) can be attributed to anthropogenic or biogenic sources, and to determine whether there is a synergistic effect whereby OA concentrations are enhanced by the simultaneous presence of high concentrations of carbon monoxide (CO) and either isoprene, MVK + MACR (sum of methyl vinyl ketone and methacrolein), or methanol, which are taken as tracers of anthropogenic and biogenic emissions, respectively. Linear and bilinear correlations between OA, CO, and each of three biogenic tracers, “Bio”, for individual plume transects indicate that most of the variance in OA over short timescales and distance scales can be explained by CO. For each transect and species a plume perturbation, (i.e., ΔOA, defined as the difference between 90th and 10th percentiles) was defined and regressions done amongst Δ values in order to probe day-to-day and location-dependent variability. Species that predicted the largest fraction of the variance in ΔOA were ΔO3 and ΔCO. Background OA was highly correlated with background methanol and poorly correlated with other tracers. Because background OA was ∼ 60 % of peak OA in the urban plume, peak OA should be primarily biogenic and therefore non-fossil, even though the day-to-day and spatial variability of plume OA is best described by an anthropogenic tracer, CO. Transects were split into subsets according to the percentile rankings of ΔCO and ΔBio, similar to an approach used by Setyan et al. (2012) and Shilling et al. (2013) to determine if anthropogenic–biogenic (A–B) interactions enhance OA production. As found earlier, ΔOA in the data subset having high ΔCO and high ΔBio was several-fold greater than in other subsets. Part of this difference is consistent with a synergistic interaction between anthropogenic and biogenic precursors and part to an independent linear dependence of ΔOA on precursors. The highest values of ΔO3, along with high temperatures, clear skies, and poor ventilation, also occurred in the high ΔCO–high ΔBio data set. A complicated mix of A–B interactions can result. After taking into account linear effects as predicted from low concentration data, an A–B enhancement of OA by a factor of 1.2 to 1.5 is estimated.

Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

Abstract. The composition of PM1 (particulate matter with diameter less than 1 µm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two high-resolution time-of-flight aerosol mass spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the contribution from different sources is distinctly different between the two sites. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC; measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical processing as rBC in the atmosphere. Although the atomic O : C ratio of OOA is substantially larger than that of solid fuel OA and hydrocarbon-like OA, these three factors have similar volatility, which is inferred from the change in mass concentration after heating at 120 °C. Finally, we discuss the relationship between the mass fraction remaining (MFR) of OA after heating in the TD and atomic O : C of OA and find that particles with a wide range of O : C could have similar MFR after heating. This analysis emphasizes the importance of understanding the distribution of volatility and O : C in bulk OA.

Effects of emission reductions on organic aerosol in the southeastern United States

Abstract. Long-term (1999 to 2013) data from the Southeastern Aerosol Research and Characterization (SEARCH) network are used to show that anthropogenic emission reductions led to important decreases in fine-particle organic aerosol (OA) concentrations in the southeastern US On average, 45 % (range 25 to 63 %) of the 1999 to 2013 mean organic carbon (OC) concentrations are attributed to combustion processes, including fossil fuel use and biomass burning, through associations of measured OC with combustion products such as elemental carbon (EC), carbon monoxide (CO), and nitrogen oxides (NOx). The 2013 mean combustion-derived OC concentrations were 0.5 to 1.4 µg m−3 at the five sites operating in that year. Mean annual combustion-derived OC concentrations declined from 3.8 ± 0.2 µg m−3 (68 % of total OC) to 1.4 ± 0.1 µg m−3 (60 % of total OC) between 1999 and 2013 at the urban Atlanta, Georgia, site (JST) and from 2.9 ± 0.4 µg m−3 (39 % of total OC) to 0.7 ± 0.1 µg m−3 (30 % of total OC) between 2001 and 2013 at the urban Birmingham, Alabama (BHM), site. The urban OC declines coincide with reductions of motor vehicle emissions between 2006 and 2010, which may have decreased mean OC concentrations at the urban SEARCH sites by > 2 µg m−3. BHM additionally exhibits a decline in OC associated with SO2 from 0.4 ± 0.04 µg m−3 in 2001 to 0.2 ± 0.03 µg m−3 in 2013, interpreted as the result of reduced emissions from industrial sources within the city. Analyses using non-soil potassium as a biomass burning tracer indicate that biomass burning OC occurs throughout the year at all sites. All eight SEARCH sites show an association of OC with sulfate (SO4) ranging from 0.3 to 1.0 µg m−3 on average, representing ∼ 25 % of the 1999 to 2013 mean OC concentrations. Because the mass of OC identified with SO4 averages 20 to 30 % of the SO4 concentrations, the mean SO4-associated OC declined by ∼ 0.5 to 1 µg m−3 as SO4 concentrations decreased throughout the SEARCH region. The 2013 mean SO4 concentrations of 1.7 to 2.0 µg m−3 imply that future decreases in mean SO4-associated OC concentrations would not exceed ∼ 0.3 to 0.5 µg m−3. Seasonal OC concentrations, largely identified with ozone (O3), vary from 0.3 to 1.4 µg m−3 ( ∼ 20 % of the total OC concentrations).

Hygroscopicity of materials internally mixed with black carbon measured in Tokyo

AbstractBlack carbon (BC) aerosols become internally mixed with non‐BC compounds (BC coatings) during aging in the atmosphere. In this study, we measured the hygroscopicity parameter κ on a single‐particle basis for both BC‐coating materials (κBC‐coat) and BC‐free particles (κBC‐free) in the urban atmosphere of Tokyo, using a single‐particle soot photometer (SP2). In our measurement system, dry ambient particles were first mass selected by an aerosol particle mass analyzer, then humidified, and then passed to the SP2 for detection of their refractory BC mass content and optical diameter. A quadrupole aerosol mass spectrometer was also employed to interpret the hygroscopicity data. During the observation period, the measured κBC‐coat generally agreed with κBC‐free to within ±25% and was usually in typical range for inorganic and organic aerosols. These results indicate that BC‐coating materials and BC‐free particles in Tokyo usually had similar chemical compositions, internal mixtures of inorganic and organic compounds, even in a source region. However, occasionally κBC‐coat was much higher than κBC‐free values, when the mass concentrations of BC and organic aerosols were poorly correlated. This indicates external mixing of BC‐containing and BC‐free particles from different sources. These findings improve our understanding of the cloud condensation nuclei activity of BC‐containing particles, which strongly influences their wet removal, and optical properties in the ambient air.

Water uptake by organic aerosol and its influence on gas/particle partitioning of secondary organic aerosol in the United States

Abstract Organic aerosol (OA) is at least partly hygroscopic, i.e., water partitions into the organic phase to a degree determined by the relative humidity (RH), the organic chemical composition, and the particle size. This organic-phase water increases the aerosol mass and provides a larger absorbing matrix while decreasing its mean molecular weight, which can encourage additional condensation of semi-volatile organic compounds. Most regional and global atmospheric models account for water uptake by inorganic salts but do not explicitly account for organic-phase water and its subsequent impact on gas/particle partitioning of semi-volatile OA. In this work, we incorporated the organic-phase water model described by Pankow et al. (2015) into the UCD/CIT air quality model to simulate water uptake by OA and assessed its influence on total OA mass concentrations. The model was run for one summer month over two distinct regions: South Coast Air Basin (SoCAB) surrounding Los Angeles, California and the eastern United States (US). In SoCAB where the OA was dominated by non-hygroscopic primary OA (POA), there was very little organic-phase water uptake (0.1–0.2 μg m−3) and consequently very little enhancement (or growth) in total OA concentrations (OA + organic-phase water): a 3% increase in total OA mass was predicted for a 0.1 increase in relative humidity. In contrast, in the eastern US where secondary OA (SOA) from biogenic sources dominated the OA, substantial organic-phase water uptake and enhancement in total OA concentrations was predicted, even in urban locations. On average, the model predicted a 20% growth in total OA mass for a 0.1 increase in relative humidity; the growth was equivalent to a 250 nm particle with a hygroscopicity parameter (κ) of 0.15. Further, for the same relative humidity, the exact extent of organic-phase water uptake and total OA enhancement was found to be dependent on the particle mixing state. When the source-oriented mixing state of aerosols was considered, generally, less organic-phase water uptake was predicted than when simple internal mixing approximations were made. Overall, the results indicated that organic-phase water can significantly influence predicted total OA concentrations under certain conditions. Regional models applied in areas with high humidity and significant SOA formation should include calculations for organic-phase water in order to capture this effect.

Non-linear partitioning and organic volatility distributions of urban aerosols.

Gas-to-particle partitioning of organic aerosols (OA) is represented in most models by Raoult's law, and depends on the existing mass of particles into which organic gases can dissolve. This raises the possibility of non-linear response of particle-phase OA mass to the emissions of precursor volatile organic compounds (VOCs) that contribute to this partitioning mass. Implications for air quality management are evident: a strong non-linear dependence would suggest that reductions in VOC emission would have a more-than-proportionate benefit in lowering ambient OA concentrations. Chamber measurements on simple VOC mixtures generally confirm the non-linear scaling between OA and VOCs, usually stated as a mass-dependence of the measured OA yields. However, for realistic ambient conditions including urban settings, no single component dominates the composition of the organic particles, and deviations from linearity are presumed to be small. Here we re-examine the linearity question using volatility spectra from several sources: (1) chamber studies of selected aerosols, (2) volatility inferred for aerosols sampled in two megacities, Mexico City and Paris, and (3) an explicit chemistry model (GECKO-A). These few available volatility distributions suggest that urban OA may be only slightly super-linear, with most values of the normalized sensitivity exponent in the range 1.1-1.3, also substantially lower than seen in chambers for some specific aerosols. The rather low exponents suggest that OA concentrations in megacities are not an inevitable convergence of non-linear effects, but can be addressed (much like in smaller urban areas) by proportionate reductions in emissions.

The Simulation of Long-Range Transport of Biomass Burning Plume and Short-Range Transport of Anthropogenic Pollutants to a Mountain Observatory in East Asia during the 7-SEAS/2010 Dongsha Experiment

The Community Multi-scale Air Quality Model (CMAQ) is used to simulate the long-range transport of biomass burning (BB) pollutants from Southeast Asia (SEA) towards the Taiwan Central Mountain Range (CMR) in March and April 2010. The results show that a proportion of the BB plume was blocked and compressed at the windward side of CMR. High-altitude BB plume is shown to influence air quality on the ground via three mechanisms: (1) the subsidence in the anticyclone, (2) the downward motion in the cold surge, and (3) the vertical mixing of the boundary layer over land. Two case studies are further investigated to probe the chemical evolution of the air parcel approaching Mt. Lulin. The first case shows that the third mechanism also explained the increase in the concentrations of peroxyacyl nitrate (PAN), higher peroxyacyl nitrate (PANX), NH3, SO2, and volatile organic compounds in the BB plume when entering the land over western Taiwan. Meanwhile, the percentage of NO3– in the plume is also significantly increased. The second case reveals that valley wind transported air pollutants from the ground to the mountains. The air parcel, accompanied with considerable concentrations of PAN, PANX, SULF, and anthropogenic secondary organic aerosol, moved up Mt. Lulin. The pollutant concentrations, except for elemental carbon, in the air parcel decreased on approach to Mt. Lulin because the air parcel was mixed with a clean air.

Airmass aging metrics derived from particle and other measurements near Fort Worth

Abstract The composition, concentration, and size of submicron particulate matter (PM1) were measured at five-minute resolution by an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) at a semi-rural location northwest of the Dallas-Fort Worth, TX, area during June 2011. Because of increased organic aerosol (OA) levels, focus here is placed on the period from June 17–30. The total measured PM1 mass concentration ranged between 1.1 and 16.5 μg m−3, with a mean of 4.4 ± 2.6 (one s.d.) μg m−3. Significant variability is observed in the time series of total PM1 and of four individual HR-ToF-AMS species, particularly between June 21 and 25. The average PM1 mass composition was dominated by OA (55.0 ± 14.8%) and sulfate (30.7 ± 12.3%). Organic aerosol concentrations were correlated positively with carbon monoxide (CO) (R = 0.81). This study uses a variety of aging metrics and their relations to OA/ΔCO to characterize secondary organic aerosol. Photochemical age is estimated by using the toluene to benzene ratio. The average photochemical age was 26.7 ± 5.3 h. Other metrics of age used in this work include the ratio of sulfate to total sulfur and the ratio of nitrogen oxides to total reactive nitrogen. The correlations between the OA/ΔCO and nitrogen aging metrics indicate consistent aging, and a weak relationship is observed between OA/ΔCO and sulfur aging. However, the relationship between photochemical age and OA/ΔCO does not show a statistically significant correlation.