ALBERT

Description: Brown carbon (BrC) contributes significantly to aerosol light absorption and thus can affect the Earth's radiation balance and atmospheric photochemical processes. In this study, we examined the light absorption properties and molecular compositions of water-soluble (WS-BrC) and water-insoluble (WI-BrC) BrC in PM2.5 collected from a rural site in the Guanzhong Basin – a highly polluted region in northwest China. Both WS-BrC and WI-BrC showed elevated light absorption coefficients (Abs) in winter (4–7 times those in summer) mainly attributed to enhanced emissions from residential biomass burning (BB) for heating of homes. While the average mass absorption coefficients (MACs) at 365 nm (MAC365) of WS-BrC were similar between daytime and nighttime in summer (0.99±0.17 and 1.01±0.18 m2 g−1, respectively), the average MAC365 of WI-BrC was more than a factor of 2 higher during daytime (2.45±1.14 m2 g−1) than at night (1.18±0.36 m2 g−1). This difference was partly attributed to enhanced photochemical formation of WI-BrC species, such as oxygenated polycyclic aromatic hydrocarbons (OPAHs). In contrast, the MACs of WS-BrC and WI-BrC were generally similar in winter and both showed few diel differences. The Abs of wintertime WS-BrC correlated strongly with relative humidity, sulfate and NO2, suggesting that aqueous-phase reaction is an important pathway for secondary BrC formation during the winter season in northwest China. Nitrophenols on average contributed 2.44±1.78 % of the Abs of WS-BrC in winter but only 0.12±0.03 % in summer due to faster photodegradation reactions. WS-BrC and WI-BrC were estimated to account for 0.83±0.23 % and 0.53±0.33 %, respectively, of the total down-welling solar radiation in the ultraviolet (UV) range in summer, and 1.67±0.72 % and 2.07±1.24 %, respectively, in winter. The total absorption by BrC in the UV region was about 55 %–79 % relative to the elemental carbon (EC) absorption.

Description: Severe haze episodes have occurred frequently in the Seoul metropolitan area (SMA) and throughout East Asian countries, especially during winter and early spring. Although notable progress has been attained in understanding these issues, the causes of severe haze formation have not yet been fully investigated. SMA haze is especially difficult to understand, because the area is impacted by both local emissions from anthropogenic and biogenic activities and emissions transported from upwind sources. Here, we investigated the emission sources and formation processes of particulate matter (PM) during three haze episodes measured in early spring of 2019, from 22 February to 2 April, using a high-resolution aerosol mass spectrometer (HR-AMS). Overall, the average concentration of nonrefractory submicron aerosol (NR-PM1) + BC (black carbon) was 35.1 µg m−3, which was composed of 38 % organics, 12 % SO4, 30 % NO3, 13 % NH4, and 5 % BC. The organics had an average oxygen-to-carbon ratio (O∕C) of 0.52 and an average organic mass to organic carbon ratio (OM∕OC) of 1.86. Seven distinct sources of organic aerosols (OAs) were identified via positive matrix factorization (PMF) analysis of the HR-AMS data: vehicle-emitted hydrocarbon-like OA (HOA), cooking OA (COA), solid-fuel-burning emitted OA (SFOA), and four different types of oxidized secondary OA with varying oxidation degrees and temporal trends. Of the 40 d of the measurement period, 23 were identified as haze days (daily average: 〉35 µg m−3), during which three severe haze episodes were recorded. In particular, PM1 concentration exceeded 100 µg m−3 during the first episode when an alert was issued, and strict emission controls were implemented in the SMA. Our results showed that nitrate dominated during the three haze episodes and accounted for 39 %–43 % of the PM1 concentration on average (vs. 21 %–24 % during the low-loading period), for which there were indications of regional-transport influences. Two regional-transport-influenced oxidized organic aerosols (OOAs), i.e., less oxidized OOA2 (LO-OOA2) and more oxidized OOA2 (MO-OOA2), contributed substantially to the total PM1 during the haze period (12 %–14 % vs. 7 % during the low-loading period), as well. In contrast, HOA and COA only contributed little (4 %–8 % vs. 4 %–6 % during the low-loading period) to the PM1 concentration during the haze days, indicating that local emissions were likely not the main reason for the severe haze issues. Hence, from simultaneous downwind (SMA) and upwind (Beijing) measurements using HR-AMS and ACSM (aerosol chemical speciation monitor) over the same period, the temporal variations in PM1 and each chemical species showed peak values on the order of Beijing (upwind) to the SMA for approximately 2 d. Furthermore, lead (Pb) derived from HR-AMS measurements was observed to increase significantly during the haze period and showed good correlations with MO-OOA2 and LO-OOA2, which is consistent with regional sources. A multiple linear regression model indicated that the transported regionally processed air masses contributed significantly to Pb in the SMA (31 %), especially during the haze period, although local burning was also important by contributing 38 %. The above results suggest that regional transport of polluted air masses might have played an important role in the formation of the haze episodes in the SMA during early spring.

Description: The meltwater scavenging coefficient (MSC) of black carbon (BC) is a crucial parameter in snow and sea ice models, as it determines the BC enrichment in the surface layer of melting snow over sea ice and therefore modulates the BC–snow–albedo feedbacks. We present a new method for MSC estimation by sampling the melt–refreeze ice layer that is produced from refreezing of the meltwater within snowpack and its overlying snow and measuring their physical characteristics in Elson Lagoon northeast of Utqiaġvik (formerly Barrow), Alaska, during the melting season. The bias of estimated MSC ranges from −5.4 % to 7.3 %, which is not exactly dependent on the degree of ablation. The average MSC value calculated with this proposed method is slightly lower than that derived from the repeating sampling (RS) method in Elson Lagoon while still being within its best estimate range. Further estimation demonstrates that the MSC in the Canada Basin (23.6 %±2.1 %) is close to that in Greenland (23.0 %±12.5 %) and larger than that in the Chukchi Sea (17.9 %±5.0 %) in the northwest of Utqiaġvik. Elson Lagoon has the lowest MSC (14.5 %±2.6 %) in the study areas. The method suggested in this study provides a possible approach for large-scale measurements of MSC over the sea ice area in the Arctic. Of course, this method depends on the presence of a melt–refreeze ice layer in the observation area.

Description: Latitudinal and altitudinal gradients can be utilized to forecast the impacts of climate changes on forests. To improve the understanding of forest dynamics on these gradients, we tested two hypotheses: (1) the change in the tree growth-climate relationship is similar along both latitudinal and altitudinal gradients, and (2) the time periods during which climate affects growth the most occur later towards higher latitudes and altitudes. We used tree-ring data from a latitudinal gradient in Finland and two altitudinal gradients on the Tibetan Plateau. We analysed the latitudinal and altitudinal growth patterns in tree-rings and investigated the growth-climate relationships of trees by correlating ring-width index chronologies with climate variables calculated with flexible time-windows, using daily-resolution climate data. The high latitude and altitude plots showed higher correlations between the tree-ring chronologies and growing season temperature. However, the effects of winter temperature showed differing patterns for the gradients. The timing of highest correlation with summer temperatures in southern sites was approximately one month ahead of the northern sites in the latitudinal gradient. In one out of the two altitudinal gradients the timing of strongest negative correlation with summer temperatures at low altitude sites was ahead of the treeline sites, possibly due to differences in moisture limitation. Mean values and the standard deviation of tree-ring width was found to increase with increasing mean summer temperatures on both types of gradients. Our results showed similarities of tree growth responses to growing season temperature between latitudinal and altitudinal gradients. However, differences in climate-growth relationships were also found between the gradients, due to differences in other factors, such as moisture conditions. Changes in the timing of the most critical climate variables demonstrated the need to use daily resolution climate data in studies on environmental gradients.

Description: Understanding the properties and life cycle processes of aerosol particles in regional air masses is crucial for constraining the climate impacts of aerosols on a global scale. In this study, characteristics of aerosols in the boundary layer (BL) and free troposphere (FT) of a remote continental region in the western US were studied using a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) deployed at the Mount Bachelor Observatory (MBO; 2763 m a.s.l.) in central Oregon in summer 2013. In the absence of wildfire influence, the average (±1σ) concentration of non-refractory submicrometer particulate matter (NR-PM1) at MBO was 2.8 (±2.8) µg m−3 and 84 % of the mass was organic. The other NR-PM1 components were sulfate (11 %), ammonium (2.8 %), and nitrate (0.9 %). The organic aerosol (OA) at MBO from these clean periods showed clear diurnal variations driven by the boundary layer dynamics with significantly higher concentrations occurring during daytime, upslope conditions. NR-PM1 contained a higher mass fraction of sulfate and was frequently acidic when MBO resided in the FT. In addition, OA in the FT was found to be highly oxidized (average O∕C of 1.17) with low volatility while OA in BL-influenced air masses was moderately oxidized (average O∕C of 0.67) and semivolatile. There are indications that the BL-influenced OA observed at MBO was more enriched in organonitrates and organosulfur compounds (e.g., MSA) and appeared to be representative of biogenic secondary organic aerosol (SOA) originated in the BL. A summary of the chemical compositions of NR-PM1 measured at a number of other high-altitude locations in the world is presented and similar contrasts between FT and BL aerosols were observed. The significant compositional and physical differences observed between FT and BL aerosols may have important implications for understanding the climate effects of regional background aerosols.

Description: Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from −5.62 to −2.42 µg m−3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m−3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.

Description: Highly time-resolved chemical characterization of nonrefractory submicrometer particulate matter (NR-PM1) was conducted in Seoul, the capital and largest metropolis of Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The measurements were performed during winter, when elevated particulate matter (PM) pollution events are often observed. This is the first time that detailed real-time aerosol measurement results have been reported from Seoul, Korea, and they reveal valuable insights into the sources and atmospheric processes that contribute to PM pollution in this region. The average concentration of submicron aerosol (PM1 =  NR-PM1+ black carbon (BC)) was 27.5 µg m−3, and the total mass was dominated by organics (44 %), followed by nitrate (24 %) and sulfate (10 %). The average atomic ratios of oxygen to carbon (O / C), hydrogen to carbon (H / C), and nitrogen to carbon (N / C) of organic aerosols (OA) were 0.37, 1.79, and 0.018, respectively, which result in an average organic mass-to-carbon (OM / OC) ratio of 1.67. The concentrations (2.6–90.7 µg m−3) and composition of PM1 varied dynamically during the measurement period due to the influences of different meteorological conditions, emission sources, and air mass origins. Five distinct sources of OA were identified via positive matrix factorization (PMF) analysis of the HR-ToF-AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA, O / C  =  0.06), cooking activities represented by a cooking OA factor (COA, O / C  =  0.14), wood combustion represented by a biomass burning OA factor (BBOA, O / C  =  0.34), and secondary organic aerosol (SOA) represented by a semivolatile oxygenated OA factor (SV-OOA, O / C  = 0.56) and a low-volatility oxygenated OA factor (LV-OOA, O / C  =  0.68). On average, primary OA (POA = HOA + COA + BBOA) accounted for 59 % the OA mass, whereas SV-OOA and LV-OOA contributed 15 and 26 %, respectively. Our results indicate that air quality in Seoul during winter is influenced strongly by secondary aerosol formation, with sulfate, nitrate, ammonium, SV-OOA, and LV-OOA together accounting for 64 % of the PM1 mass during this study. However, aerosol sources and composition were found to be significantly different between clean and polluted periods. During stagnant periods with low wind speed (WS) and high relative humidity (RH), PM concentration was generally high (average ±1σ = 43.6 ± 12.4 µg m−3) with enhanced fractions of nitrate (27 %) and SV-OOA (8 %), which suggested a strong influence from local production of secondary aerosol. Low-PM loading periods (12.6 ± 7.1 µg m−3) tended to occur under higher-WS and lower-RH conditions and appeared to be more strongly influenced by regional air masses, as indicated by higher mass fractions of sulfate (12 %) and LV-OOA (20 %) in PM1. Overall, our results indicate that PM pollutants in urban Korea originate from complex emission sources and atmospheric processes and that their concentrations and composition are controlled by various factors, including meteorological conditions, local anthropogenic emissions, and upwind sources.

Description: Non-refractory submicrometer particulate matter (NR-PM1) was measured in the Seoul Metropolitan Area (SMA), Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) from 14 April to 15 June 2016, as a part of the Korea-US Air Quality Study (KORUS-AQ) campaign. This was the first highly time-resolved, real-time measurement study of springtime aerosol in SMA and the results reveal valuable insights into the sources and atmospheric processes that contribute to PM pollution in this region. The average concentration of submicrometer aerosol (PM1 =  NR-PM1 + black carbon (BC)) was 22.1 µg m−3, which was composed of 44 % organics, 20 % sulfate, 17 % nitrate, 12 % ammonium, and 7 % BC. Organics had an average atomic oxygen-to-carbon (O ∕ C) ratio of 0.49 and an average organic mass-to-carbon (OM/OC) ratio of 1.82. Four distinct sources of OA were identified via positive matrix factorization (PMF) analysis of the HR-ToF-AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA; O ∕ C  =  0.15; 17 % of OA mass), food cooking activities represented by a cooking-influenced OA factor (COA; O ∕ C  =  0.19; 22 % of OA mass), and secondary organic aerosol (SOA) represented by a semi-volatile oxygenated OA factor (SV-OOA; O ∕ C  =  0.44; 27 % of OA mass) and a low-volatility oxygenated OA factor (LV-OOA; O ∕ C  =  0.91; 34 % of OA mass). Our results indicate that air quality in SMA during KORUS-AQ was influenced strongly by secondary aerosol formation, with sulfate, nitrate, ammonium, SV-OOA, and LV-OOA together accounting for 76 % of the PM1 mass. In particular, the formation of LV-OOA and sulfate was mainly promoted by elevated ozone concentrations and photochemical reactions during daytime, whereas SV-OOA and nitrate formation was contributed by both nocturnal processing of VOC and nitrogen oxides, respectively, and daytime photochemical reactions. In addition, lower nighttime temperature promoted gas-to-particle partitioning of semivolatile species and formation of SV-OOA and nitrate. During a period of 4 days (from 20 to 23 May ), LV-OOA increased dramatically and accounted for up to 41 % of the PM1 mass. This intense LV-OOA formation event was associated with large enhancements of both anthropogenic and biogenic VOCs (e.g., isoprene and toluene), high concentration of Ox ( =  O3 + NO2), strong solar radiation, and stagnant conditions, suggesting that it was mainly driven by local photochemical formation. We have also investigated the formation and evolution mechanisms of severe haze episodes. Unlike the winter haze events which were mainly caused by intense local emissions coupled with stagnant meteorological conditions, the spring haze events appeared to be influenced by both regional and local factors. For example, there were episodes of long-range transport of plumes followed by calm meteorology conditions, which promoted the formation and accumulation of local secondary species, leading to high concentrations of PM. Overall, our results indicate that PM pollutants in urban Korea originate from complex emission sources and atmospheric processes and that the concentrations and composition of PM are controlled by various factors, including meteorological conditions, local anthropogenic emissions, and upwind sources.

Description: This study discusses an analysis of combined airborne and ground observations of particulate nitrate (NO3−(p)) concentrations made during the wintertime DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically resolved observations relevant to Air Quality) study at one of the most polluted cities in the United States – Fresno, CA – in the San Joaquin Valley (SJV) and focuses on developing an understanding of the various processes that impact surface nitrate concentrations during pollution events. The results provide an explicit case-study illustration of how nighttime chemistry can influence daytime surface-level NO3−(p) concentrations, complementing previous studies in the SJV. The observations exemplify the critical role that nocturnal chemical production of NO3−(p) aloft in the residual layer (RL) can play in determining daytime surface-level NO3−(p) concentrations. Further, they indicate that nocturnal production of NO3−(p) in the RL, along with daytime photochemical production, can contribute substantially to the buildup and sustaining of severe pollution episodes. The exceptionally shallow nocturnal boundary layer (NBL) heights characteristic of wintertime pollution events in the SJV intensify the importance of nocturnal production aloft in the residual layer to daytime surface concentrations. The observations also demonstrate that dynamics within the RL can influence the early-morning vertical distribution of NO3−(p), despite low wintertime wind speeds. This overnight reshaping of the vertical distribution above the city plays an important role in determining the net impact of nocturnal chemical production on local and regional surface-level NO3−(p) concentrations. Entrainment of clean free-tropospheric (FT) air into the boundary layer in the afternoon is identified as an important process that reduces surface-level NO3−(p) and limits buildup during pollution episodes. The influence of dry deposition of HNO3 gas to the surface on daytime particulate nitrate concentrations is important but limited by an excess of ammonia in the region, which leads to only a small fraction of nitrate existing in the gas phase even during the warmer daytime. However, in the late afternoon, when diminishing solar heating leads to a rapid fall in the mixed boundary layer height (BLH), the impact of surface deposition is temporarily enhanced and can lead to a substantial decline in surface-level particulate nitrate concentrations; this enhanced deposition is quickly arrested by a decrease in surface temperature, which drops the gas-phase fraction to near zero. The overall importance of enhanced late-afternoon gas-phase loss to the multiday buildup of pollution events is limited by the very shallow nocturnal boundary layer. The case study here demonstrates that mixing down of NO3−(p) from the RL can contribute a majority of the surface-level NO3−(p) in the morning (here,  ∼  80 %), and a strong influence can persist into the afternoon even when photochemical production is maximum. The particular day-to-day contribution of aloft nocturnal NO3−(p) production to surface concentrations will depend on prevailing chemical and meteorological conditions. Although specific to the SJV, the observations and conceptual framework further developed here provide general insights into the evolution of pollution episodes in wintertime environments.

Description: An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed along with other online instruments to study the highly time resolved chemistry and sources of submicron aerosols (PM1) at Waliguan (WLG) Baseline Observatory, a high-altitude (3816 m a.s.l.) background station located at the northeast edge of the Qinghai–Tibet Plateau (QTP), during 1–31 July 2017. The average PM1 mass concentration during this study was 9.1 µg m−3 (ranging from 0.3 to 28.1 µg m−3), which was distinctly higher than those (2.0–5.7 µg m−3) measured with the Aerodyne AMS at other high-elevation sites in the southern or central QTP. Sulfate showed a dominant contribution (38.1 %) to PM1 at WLG followed by organics (34.5 %), ammonium (15.2 %), nitrate (8.1 %), BC (3.0 %) and chloride (1.1 %). Accordingly, bulk aerosols appeared to be slightly acidic throughout this study, mainly related to the enhanced sulfate contribution. All chemical species peaked at the accumulation mode, indicating the well-mixed and highly aged aerosol particles at WLG from long-range transport. Positive matrix factorization (PMF) on the high-resolution organic mass spectra resolved four distinct organic aerosol (OA) components, including a traffic-related hydrocarbon-like OA (HOA), a relatively fresh biomass burning OA (BBOA), an aged biomass burning OA (agBBOA) and a more-oxidized oxygenated OA (OOA). On average, the two relatively oxidized OAs, OOA and agBBOA, contributed 34.4 % and 40.4 % of organics, respectively, while the rest were 18.4 % for BBOA and 6.8 % for HOA. Source analysis for air masses showed that higher mass concentrations of PM1 and enhanced contributions of sulfate and biomass-burning-related OA components (agBBOA + BBOA) were from the northeast of the WLG with shorter transport distance, whereas lower PM1 mass concentrations with enhanced OOA contribution were from the west after long-range transport, suggesting their distinct aerosol sources and significant impacts of regional transport on aerosol mass loadings and chemistry at WLG.