Oxygenated Organic Aerosol Research Articles

Anthropogenic and biogenic pollutants in a forested environment: SPRUCE-22 campaign overview

The SPRUCE-22 field campaign was conducted during July 2022 on a remote mountainous forested site in Greece to assess interactions of biogenic and anthropogenic pollutants in the Eastern Mediterranean. Particle chemical composition and size distributions along with concentrations of organic and inorganic gases were measured at high temporal resolution, while samples were collected and analyzed off-line. PM1 had a surprisingly high average concentration of 13 μg m−3 consisting primarily of organics (57%), followed by sulfate (30%), ammonium (9%), and black carbon (2%). Nitrates (both inorganic and organic) were less than 1% of the PM1 despite the relatively high NOx emissions in the Balkans. The PM2.5 concentrations at this remote site were similar and even higher than those in major cities across Greece including Athens, indicating the importance of regional transport for summertime pollution in the Eastern Mediterranean. The relatively constant average diurnal profiles of major anthropogenic pollutants are consistent with only minimal effects from local sources. Sulfates are not any more the dominant component of fine PM in Greece due to the reduction of SO2 emissions of coal-burning powerplants. The organic aerosol (OA) was quite oxidized with an average oxygen to carbon ratio (O:C) equal to 0.83. The average concentration of isoprene was 0.6 ppb, of monoterpenes 0.5 ppb, while the biogenic secondary organic aerosol factor (obtained through source apportionment analysis) was estimated to contribute 22% of the OA. Additional biogenic secondary organic aerosol (SOA) may be part of the two oxygenated OA (OOA) factors that were also identified. Radiocarbon analysis indicated that the non-fossil carbon was approximately equal to the sum of the biogenic and the more oxidized oxygenated OA, implying that the less oxidized OOA in this study was mostly associated to anthropogenic fossil fuel combustion. The biogenic SOA was quite aged (O:C equal to 0.63) and was also mostly transported to the site. Nearby new particle formation events occurred during 20 % of the days, with an average SO2 concentration of 0.3 ppb. The oxidative potential of the PM per unit of mass was quite high. The source attribution of the fine PM and the interactions among its anthropogenic and biogenic components are also discussed.

Study on performance and water deactivation mechanism of low-temperature denitrification catalyst in high-humidity flue gas

To address water poisoning issues of Selective Catalytic Reduction (SCR) denitrification catalysts in high-humidity flue gas, this study synthesized catalysts including Co–Mn/TiO2, Co–Mn–Ce/TiO2, Co–Mn–Ce/TiO2–Si, and Co–Mn–Ce/TiO2 (stearic acid). The activity of the catalysts at low temperatures and high humidity (140–180 °C, 0–35 vol%) was evaluated. Furthermore, the characterization of the most effective of these (the Co–Mn–Ce/TiO2 (stearic acid) catalyst) was performed. The results revealed distinct mechanisms of water poisoning under high- and low-humidity conditions. Under high humidity, the dissolution of water molecules affected the catalyst structure and thereby, resulted in reduced dispersibility of the active components. Conversely, at low humidity, the dissolution effect was relatively marginal, which resulted in a more stable catalyst structure. High-humidity flue gas reduced the catalyst acidity and thereby, hindered NH3 adsorption. Meanwhile, low-humidity flue gas had a lesser impact on the catalyst. High-humidity flue gas hinders the conversion of Co ions in Co–Mn–Ce/TiO2（stearic acid ) to higher oxidation states and reduced Ce4+ to Ce3+. This resulted in decreased Mn4+ on the catalyst surface and reduced chemisorbed oxygen (Oa). This, in turn, affected the adsorption and storage of oxygen by the catalyst.

Major source categories of PM2.5 oxidative potential in wintertime Beijing and surroundings based on online dithiothreitol-based field measurements

Fine particulate matter (PM2.5) causes millions of premature deaths each year worldwide. Oxidative potential (OP) has been proposed as a better metric for aerosol health effects than PM2.5 mass concentration alone. In this study, we report for the first time online measurements of PM2.5 OP in wintertime Beijing and surroundings based on a dithiothreitol (DTT) assay. These measurements were combined with co-located PM chemical composition measurements to identify the main source categories of aerosol OP. In addition, we highlight the influence of two distinct pollution events on aerosol OP (spring festival celebrations including fireworks and a severe regional dust storm). Source apportionment coupled with multilinear regression revealed that primary PM and oxygenated organic aerosol (OOA) were both important sources of OP, accounting for 41 ± 12 % and 39 ± 10 % of the OPvDTT (OP normalized by the sampled air volume), respectively. The small remainder was attributed to fireworks and dust, mainly resulting from the two distinct pollution events. During the 3.5-day spring festival period, OPvDTT spiked to 4.9 nmol min−1 m−3 with slightly more contribution from OOA (42 ± 11 %) and less from primary PM (31 ± 15 %). During the dust storm, hourly-averaged PM2.5 peaked at a very high value of 548 μg m−3 due to the dominant presence of dust-laden particles (88 % of total PM2.5). In contrast, only mildly elevated OPvDTT values (up to 1.5 nmol min−1 m−3) were observed during this dust event. This observation indicates that variations in OPvDTT cannot be fully explained using PM2.5 alone; one must also consider the chemical composition of PM2.5 when studying aerosol health effects. Our study highlights the need for continued pollution control strategies to reduce primary PM emissions, and more in-depth investigations into the source origins of OOA, to minimize the health risks associated with PM exposure in Beijing.

Characterization of size-resolved aerosol hygroscopicity and liquid water content in Nanjing of the Yangtze River Delta

Aerosol hygroscopicity and liquid water content (ALWC) have important influences on the environmental and climate effect of aerosols. In this study, we measured the hygroscopic growth factors (GF) of particles with dry diameters of 40, 80, 150, and 200 nm during the wintertime in Nanjing. Both the GF-derived hygroscopicity parameter (κgf) and ALWC increased with particle size, but displayed differing diurnal variations, with κgf peaking around the midday, while ALWC peaking in the early morning. Nitrate, ammonium and oxygenated organic aerosols (OOA) were found as the chemical components mostly strongly correlated with ALWC. A closure study suggests that during midday photo-oxidation and nighttime high ALWC periods, the κ of organic aerosols (κorg) was underestimated when using previous parameterizations. Accordingly, we re-constructed parameterizations for κorg and the oxidation level of organics for these periods, which indicates a higher hygroscopicity of photochemically formed OOA than the aqueous OOA, yet both being much higher than the generally assumed OOA hygroscopicity. Additionally, in a typical high ALWC episode, concurrently increased ALWC, nitrate, OOA as well as aerosol surface area and mass concentrations were observed under elevated ambient RH. This strongly indicates a coupled effect that the hygroscopic secondary aerosols, in particular nitrate with strong hygroscopicity, led to large increase in ALWC, which in turn synergistically boosted nitrate and OOA formation by heterogeneous/aqueous reactions. Such interaction may represent an important mechanism contributing to enhanced formation of secondary aerosols and rapid growth of fine particulate matter under relatively high RH conditions.

Variation in chemical composition and volatility of oxygenated organic aerosol in different rural, urban, and mountain environments

Abstract. The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC​​​​​​​) and lower oxygen-to-carbon (O : C) ratios at the urban sites (nC: 9.8 ± 0.7; O : C: 0.76 ± 0.03; average ±1 standard deviation) compared to the rural (nC: 8.8 ± 0.6; O : C: 0.80 ± 0.05) and mountain stations (nC: 8.1 ± 0.8; O : C: 0.91 ± 0.07), indicative of different emission sources and chemistry. Compounds containing only carbon, hydrogen, and oxygen atoms (CHO) contribute the most to the total OOA mass at the rural sites (79.9 ± 5.2 %), in accordance with their proximity to forested areas (66.2 ± 5.5 % at the mountain sites and 72.6 ± 4.3 % at the urban sites). The largest contribution of nitrogen-containing compounds (CHON) is found at the urban stations (27.1 ± 4.3 %), consistent with their higher NOx levels. Moreover, we parametrize OOA volatility (saturation mass concentrations, Csat) using molecular composition information and compare it with the bulk apparent volatility derived from thermal desorption of the OOA particles within the FIGAERO. We find differences in Csat values of up to ∼ 3 orders of magnitude and variation in thermal desorption profiles (thermograms) across different locations and systems. From our study, we draw the general conclusion that environmental conditions (e.g., ambient temperature) do not directly affect OOA apparent volatility but rather indirectly by influencing the sources and chemistry of the environment and thus the chemical composition. The comprehensive dataset provides results that show the complex thermodynamics and chemistry of OOA and their changes during its lifetime in the atmosphere. We conclude that generally the chemical description of OOA suffices to predict its apparent volatility, at least qualitatively. Our study thus provides new insights that will help guide choices of, e.g., descriptions of OOA volatility in different model frameworks such as air quality models and cloud parcel models.

Increasing Contributions of Temperature-Dependent Oxygenated Organic Aerosol to Summertime Particulate Matter in New York City.

As part of the summer 2022 NYC-METS (New York City metropolitan Measurements of Emissions and TransformationS) campaign and the ASCENT (Atmospheric Science and Chemistry mEasurement NeTwork) observational network, speciated particulate matter was measured in real time in Manhattan and Queens, NY, with additional gas-phase measurements. Largely due to observed reductions in inorganic sulfate aerosol components over the 21st century, summertime aerosol composition in NYC has become predominantly organic (80-83%). Organic aerosol source apportionment via positive matrix factorization showed that this is dominated by secondary production as oxygenated organic aerosol (OOA) source factors comprised 73-76% of OA. Primary factors, including cooking-related organic aerosol (COA) and hydrocarbon-like organic aerosol (HOA) comprised minor fractions of OA, only 13-15% and 10-11%, respectively. The two sites presented considerable spatiotemporal variations in OA source factor concentrations despite similar average PM2.5 concentrations. The less- and more-oxidized OOA factors exhibited clear temperature dependences at both sites with increased concentrations and greater degrees of oxidation at higher temperatures, including during a heatwave. With strong temperature sensitivity and minimal changes in summertime concentrations since 2001, secondary OA poses a particular challenge for air quality policy in NYC that will very likely be exacerbated by continued climate change and extreme heat events.

Oxidized and Unsaturated: Key Organic Aerosol Traits Associated with Cellular Reactive Oxygen Species Production in the Southeastern United States.

Exposure to ambient fine particulate matter (PM2.5) is associated with millions of premature deaths annually. Oxidative stress through overproduction of reactive oxygen species (ROS) is a possible mechanism for PM2.5-induced health effects. Organic aerosol (OA) is a dominant component of PM2.5 worldwide, yet its role in PM2.5 toxicity is poorly understood due to its chemical complexity. Here, through integrated cellular ROS measurements and detailed multi-instrument chemical characterization of PM in urban southeastern United States, we show that oxygenated OA (OOA), especially more-oxidized OOA, is the main OA type associated with cellular ROS production. We further reveal that highly unsaturated species containing carbon-oxygen double bonds and aromatic rings in OOA are major contributors to cellular ROS production. These results highlight the key chemical features of ambient OA driving its toxicity. As more-oxidized OOA is ubiquitous and abundant in the atmosphere, this emphasizes the need to understand its sources and chemical processing when formulating effective strategies to mitigate PM2.5 health impacts.

A 1-year aerosol chemical speciation monitor (ACSM) source analysis of organic aerosol particle contributions from anthropogenic sources after long-range transport at the TROPOS research station Melpitz

Abstract. Atmospheric aerosol particles are a complex combination of primary emitted sources (biogenic and anthropogenic) and secondary aerosol resulting from aging processes such as condensation, coagulation, and cloud processing. To better understand their sources, investigations have been focused on urban areas in the past, whereas rural-background stations are normally less impacted by surrounding anthropogenic sources. Therefore, they are predisposed for studying the impact of long-range transport of anthropogenic aerosols. Here, the chemical composition and organic aerosol (OA) sources of submicron aerosol particles measured by an aerosol chemical speciation monitor (ACSM) and a multi-angle absorption photometer (MAAP) were investigated at Melpitz from September 2016 to August 2017. The location of the station at the frontier between western and eastern Europe makes it the ideal place to investigate the impact of long-range transport over Europe. Indeed, the station is under the influence of less polluted air masses from westerly directions and more polluted continental air masses from eastern Europe. The OA dominated the submicron particle mass concentration and showed strong seasonal variability ranging from 39 % (in winter) to 58 % (in summer). It was followed by sulfate (15 % and 20 %) and nitrate (24 % and 11 %). The OA source identification was performed using the rolling positive matrix factorization (PMF) approach to account for the potential temporal changes in the source profile. It was possible to split OA into five factors with a distinct temporal variability and mass spectral signature. Three were associated with anthropogenic primary OA (POA) sources: hydrocarbon-like OA (HOA; 5.2 % of OA mass in winter and 6.8 % in summer), biomass burning OA (BBOA; 10.6 % and 6.1 %) and coal combustion OA (CCOA; 23 % and 8.7 %). Another two are secondary and processed oxygenated OA (OOA) sources: less oxidized OOA (LO-OOA; 28.4 % and 36.7 %) and more oxidized OOA (MO-OOA; 32.8 % and 41.8 %). Since equivalent black carbon (eBC) was clearly associated with the identified POA factors (sum of HOA, BBOA, and CCOA; R2= 0. 87), eBC's contribution to each of the POA factors was achieved using a multilinear regression model. Consequently, CCOA represented the main anthropogenic sources of carbonaceous aerosol (sum of OA and eBC) not only during winter (56 % of POA in winter) but also in summer (13 % of POA in summer), followed by BBOA (29 % and 69 % of POA in winter and summer, respectively) and HOA (15 % and 18 % of POA in winter and summer, respectively). A seasonal air mass cluster analysis was used to understand the geographical origins of the different aerosol types and showed that during both winter and summer time, PM1 (PM with an aerodynamic diameter smaller than 1 µm) air masses with eastern influence were always associated with the highest mass concentration and the highest coal combustion fraction. Since during wintertime CCOA is a combination of domestic heating and power plant emissions, the summer contribution of CCOA emphasizes the critical importance of coal power plant emissions to rural-background aerosols and its impact on air quality, through long-range transportation.

Formation pathways of organic aerosols over a tropical coastal atmosphere

The characteristics of non-refractory submicron aerosols (NR-PM1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O3+NO2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (кorganics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere.

Emissions from ships’ activities in the anchorage zone: A potential source of sub-micron aerosols in port areas

Busan Port is among the world’s top ten most air-polluted ports, but the role of the anchorage zone as a significant contributor to pollution has not been studied. To assess the emission characteristics of sub-micron aerosols, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in Busan, South Korea from September 10 to October 6, 2020. The concentration of all AMS-identified species and black carbon were highest when the winds came from the anchorage zone (11.9 µg·m−3) and lowest with winds from the open ocean (6.64 µg·m−3). The positive matrix factorization model identified one hydrocarbon-like organic aerosol (HOA) and two oxygenated organic aerosol (OOA) sources. HOAs were highest with winds from Busan Port, while oxidized OOAs were predominant with winds from the anchorage zone (less oxidized) and the open ocean (more oxidized). We calculated the emissions from the anchorage zone using ship activity data and compared them to the total emissions from Busan Port. Our results suggest that emissions from ship activities in the anchorage zone should be considered a significant source of pollution in the Busan Port area, especially given the substantial contributions of gaseous emissions (NOx: 8.78%; volatile organic compounds: 7.52%) and their oxidized moieties as secondary aerosols.

Investigation of four-year chemical composition and organic aerosol sources of submicron particles at the ATOLL site in northern France

This study presents the first long-term online measurements of submicron (PM1) particles at the ATOLL (ATmospheric Observations in liLLe) platform, in northern France. The ongoing measurements using an Aerosol Chemical Speciation Monitor (ACSM) started at the end of 2016 and the analysis presented here spans through December 2020. At this site, the mean PM1 concentration is 10.6 μg m−3, dominated by organic aerosols (OA, 42.3%) and followed by nitrate (28.9%), ammonium (12.3%), sulfate (8.6%), and black carbon (BC, 8.0%). Large seasonal variations of PM1 concentrations are observed, with high concentrations during cold seasons, associated with pollution episodes (e.g. over 100 μg m−3 in January 2017). To study OA origins over this multiannual dataset we performed source apportionment analysis using rolling positive matrix factorization (PMF), yielding two primary OA factors, a traffic-related hydrocarbon-like OA (HOA) and biomass-burning OA (BBOA), and two oxygenated OA (OOA) factors. HOA showed a homogeneous contribution to OA throughout the seasons (11.8%), while BBOA varied from 8.1% (summer) to 18.5% (winter), the latter associated with residential wood combustion. The OOA factors were distinguished between their less and more oxidized fractions (LO-OOA and MO-OOA, on average contributing 32% and 42%, respectively). During winter, LO-OOA is identified as aged biomass burning, so at least half of OA is associated with wood combustion during this season. Furthermore, ammonium nitrate is also a predominant aerosol component during cold-weather pollution episodes – associated with fertilizer usage and traffic emissions. This study provides a comprehensive analysis of submicron aerosol sources at the recently established ATOLL site in northern France from multiannual observations, depicting a complex interaction between anthropogenic and natural sources, leading to different mechanisms of air quality degradation in the region across different seasons.

Characterization of volatile organic compounds and submicron organic aerosol in a traffic environment

Abstract. Urban air consists of a complex mixture of gaseous and particulate species from anthropogenic and biogenic sources that are further processed in the atmosphere. This study investigated the characteristics and sources of volatile organic compounds (VOCs) and submicron organic aerosol (OA) in a traffic environment in Helsinki, Finland, in late summer. The anthropogenic VOCs (aVOCs; aromatic hydrocarbons) and biogenic VOCs (bVOCs; terpenoids) relevant for secondary-organic-aerosol formation were analyzed with an online gas chromatograph mass spectrometer, whereas the composition and size distribution of submicron particles was measured with a soot particle aerosol mass spectrometer. This study showed that aVOC concentrations were significantly higher than bVOC concentrations in the traffic environment. The largest aVOC concentrations were measured for toluene (campaign average of 1630 ng m−3) and p/m xylene (campaign average of 1070 ng m−3), while the dominating bVOC was α-pinene (campaign average of 200 ng m−3). For particle-phase organics, the campaign-average OA concentration was 2.4 µg m−3. The source apportionment analysis extracted six factors for OA. Three OA factors were related to primary OA sources – traffic (24 % of OA, two OA types) and a coffee roastery (7 % of OA) – whereas the largest fraction of OA (69 %) consisted of oxygenated OA (OOA). OOA was divided into less oxidized semi-volatile OA (SV-OOA; 40 % of OA) and two types of low-volatility OA (LV-OOA; 30 %). The focus of this research was also on the oxidation potential of the measured VOCs and the association between VOCs and OA in ambient air. Production rates of the oxidized compounds (OxPR) from the VOC reactions revealed that the main local sources of the oxidation products were O3 oxidation of bVOCs (66 % of total OxPR) and OH radical oxidation of aVOCs and bVOCs (25 % of total OxPR). Overall, aVOCs produced a much smaller portion of the oxidation products (18 %) than bVOCs (82 %). In terms of OA factors, SV-OOA was likely to originate from biogenic sources since it correlated with an oxidation product of monoterpene, nopinone. LV-OOA consisted of highly oxygenated long-range or regionally transported OA that had no correlation with local oxidant concentrations as it had already spent several days in the atmosphere before reaching the measurement site. In general, the main sources were different for VOCs and OA in the traffic environment. Vehicle emissions impacted both VOC and OA concentrations. Due to the specific VOCs attributed to biogenic emissions, the influence of biogenic emissions was more clearly detected in the VOC concentrations than in OA. In contrast, the emissions from the local coffee roastery had a distinctive mass spectrum for OA, but they could not be seen in the VOC measurements due to the measurement limitations for the large VOC compounds. Long-range transport increased the OA concentration and oxidation state considerably, while its effect was observed less clearly in the VOC measurements due to the oxidation of most VOC in the atmosphere during the transport. Overall, this study revealed that in order to properly characterize the impact of different emission sources on air quality, health, and climate, it is of importance to describe both gaseous and particulate emissions and understand how they interact as well as their phase transfers in the atmosphere during the aging process.

Characteristics and Oxidative Potential of Ambient PM2.5 in the Yangtze River Delta Region: Pollution Level and Source Apportionment

Fine particulate matter (PM2.5) is a major contributor to the degree of air pollution, and it is associated with a range of adverse health impacts. Moreover, the oxidative potential (OP, as a tracer of oxidative stress) of PM2.5 has been thought to be a possible determinant of its health impact. In this study, the OP of 136 fine aerosol filter samples collected in Changzhou in two seasons (spring and summer) were determined using a dithiothreitol (DTT) assay. Source apportionments of the PM2.5 and DTT activity were further performed. Our results showed that the daily average ± standard deviation of the DTTv (volume-normalized DTT activity) in the PM2.5 was 1.16 ± 0.58 nmol/min/m3 and 0.85 ± 0.16 nmol/min/m3 in the spring and summer, respectively, and the DTTm (mass-normalized DTT activity) was 13.56 ± 5.45 pmol/min/μg and 19.97 ± 6.54 pmol/min/μg in the spring and summer, respectively. The DTTv was higher in the spring compared to the summer while the opposite was true for the DTTm. Most of the detected components (including the organic component, element component, NH4+, Mn, Cu, Zn, etc.) exhibited a moderately positive correlation with the DTTv, but the opposite was found with the DTTm. An aerodyne high-resolution aerosol mass spectrometer (HP-AMS) was deployed to probe the chemical properties of the water-soluble organic matter (WSOA). Positive matrix factorization (PMF) coupled with multiple linear regression was used to obtain the relative source contributions to the DTT activity for the WSOA in the PM2.5. The results showed that the sensitivity sequences of the DTTv to the WSOA sources were oxygenated organic aerosol (OOA) &gt; biomass burning OA (BBOA) &gt; hydrocarbon-like OA (HOA) in the spring and HOA &gt; nitrogen-enriched OA (NOA) &gt; OOA in the summer. The PMF suggested the highest contribution from traffic emissions to the DTTv of the PM2.5 in both seasons. Our findings point to the importance of both organic components from secondary formation and transition metals to adverse health effects in this region. This study can provide an important reference for adopting appropriate public health policies regarding the detrimental outcomes of exposure to PM2.5.

Measurement report: Intensive biomass burning emissions and rapid nitrate formation drive severe haze formation in the Sichuan Basin, China – insights from aerosol mass spectrometry

Abstract. Haze pollution is a severe environmental problem, caused by elevation of fine particles (aerodynamic diameter &lt;2.5 µm, PM2.5), which is related to secondary aerosol formation, unfavourable synoptic conditions and regional transport, etc. The regional haze formation in basin areas, along with intensive emission of precursors, high relative humidity and poor dispersion conditions, is still limitedly understood. In this study, a field campaign was conducted to investigate the factors resulting in haze formation in the Sichuan Basin (SCB) during winter in 2021. The fine aerosol chemical composition was characterised using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM), which also provided detailed information on the sources for organic aerosols (OAs). The average concentration of non-refractory fine particles (NR-PM2.5) was 98.5±38.7 µg m−3, and organics aerosols, nitrate, sulfate, ammonium and chloride took up 40.3 %, 28.8 %, 10.6 %, 15.3 % and 5.1 % of PM2.5. Three factors, including a hydrocarbon-like OA (HOA), a biomass burning OA (BBOA) and an oxygenated OA (OOA), were identified by applying the positive matrix factorisation (PMF) analysis, and they constituted 24.2 %, 24.2 % and 51.6 % of OA on average, respectively. Nitrate formation was promoted by gas-phase and aqueous-phase oxidation, while sulfate was mainly formed through aqueous-phase process. OOA showed strong dependence on Ox, demonstrating the contribution of photooxidation to OOA formation. OOA concentration increased as aerosol liquid water content (ALWC) increased within 200 µg m−3 and kept relatively constant when ALWC &gt;200 µg m−3, suggesting the insignificant effect of aqueous-phase reactions on OOA formation. Among the three haze episodes identified during the whole campaign, the driving factors were different: the first haze episode (H1) was driven by nitrate formation through photochemical and aqueous-phase reactions, and the second haze episode (H2) was mainly driven by the intense emission of primary organic aerosols from biomass burning and vehicle exhaust, while the third haze episode (H3) was mainly driven by reactions involving nitrate formation and biomass burning emission. HOA and BBOA were scavenged, while OOA, nitrate and sulfate formation was enhanced by aqueous-phase reactions during fog periods, which resulted in the increase of O:C from pre-fog to post-fog periods. This study revealed the factors driving severe haze formation in the SCB and implied the benefit of controlling nitrate as well as intense biomass burning and vehicle exhaust emission for the mitigation of heavy aerosol pollution in this region.

Impact of aging on the sources, volatility, and viscosity of organic aerosols in Chinese outflows

Abstract. To investigate the impact of aging on the sources, volatility, and viscosity of organic aerosol (OA) in Chinese outflows, a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) coupled with a thermodenuder (TD) was deployed in the spring of 2018 in Dongying, which is a regional receptor site of metropolitan emissions in the North China Plain (NCP). The average mass concentration of PM1 is 31.5±22.7 µg m−3, which is mainly composed of nitrate (33 %) and OA (25 %). The source apportionment results show that the OA is mainly contributed by oxygenated OA (OOA) from secondary sources, including background-OOA (33 %) representing a background concentration of OA (2.6 µg m−3) in the NCP area, and transported-OOA (33 %) oxidized from urban emissions. The other two factors include aged hydrocarbon-liked OA (aged-HOA, 28 %) from transported vehicle emissions and biomass burning OA (BBOA, 5 %) from local open burning. The volatility of total OA (average C*=3.2×10-4 µg m−3) in this study is generally lower than that reported in previous field studies, which is mainly due to the high OA oxidation level resulting from aging processes during transport. The volatilities of OA factors follow the order of background-OOA (average C*=2.7×10-5 µg m−3) &lt; transported-OOA (3.7×10-4µgm-3)&lt; aged-HOA (8.1×10-4µgm-3)&lt; BBOA (0.012 µg m−3). Extremely low volatilities in ambient air indicate that oligomers may exist in aged plumes. The viscosity estimation suggests that the majority of ambient OA in this study behaves as semisolid (60 %), liquifies at higher relative humidity (RH) (21 %), and solidifies (19 %) during noon when the RH is low and the oxidation level is high. Finally, the estimated mixing time of molecules in 200 nm OA varies dramatically from minutes at night to years in the afternoon, emphasizing the need to consider its dynamic kinetic limits when modeling OA. In general, the overall results of this study improve our understanding of the impact of aging on OA volatility and viscosity.

Relationships of the Hygroscopicity of HULIS With Their Degrees of Oxygenation and Sources in the Urban Atmosphere

AbstractHumic‐like substances (HULIS) are unresolved compounds isolated from organic matter in atmospheric aerosols. Understanding the chemical structures and sources that control the hygroscopicity of HULIS is important for predicting its environmental impacts and possibly useful for parameterization of the hygroscopicity of organic aerosol (OA). Here, the hygroscopic growth of HULIS from total suspended particles samples in Beijing was analyzed using a hygroscopicity tandem differential mobility analyzer. The hygroscopicity parameter of HULIS (κHULIS) was determined to be 0.06 ± 0.03, and was found to correlate positively with O:C and f44 from offline aerosol mass spectrometry. Additionally, κHULIS was correlated positively with oxygenated organic aerosol (OOA) and correlated negatively with cooking OA and biomass burning OA, for which the source‐related OA types were from mass‐spectral‐based positive matrix factorization analyses. Further analysis resolved substantial κ values of 0.09 and 0.22, respectively, for less‐oxidized and more‐oxidized OOA, in contrast to the low κ values for cooking OA and biomass burning OA. Extensions of O:C‐ and source‐based parameterizations reasonably estimated the hygroscopicity of total OA with a moderate contribution from HULIS. This result and the fact that the obtained OOA contributions to κ of OA were similar to those from different environments suggest the applicability of parameterizing the hygroscopicity for a wide range of OA in particular based on source‐related structural characteristics.

Staggered-peak production is a mixed blessing in the control of particulate matter pollution.

Staggered-peak production (SP)-a measure to halt industrial production in the heating season-has been implemented in North China Plain to alleviate air pollution. We compared the variations of PM1 composition in Beijing during the SP period in the 2016 heating season (SPhs) with those in the normal production (NP) periods during the 2015 heating season (NPhs) and 2016 non-heating season (NPnhs) to investigate the effectiveness of SP. The PM1 mass concentration decreased from 70.0 ± 54.4 μg m-3 in NPhs to 53.0 ± 56.4 μg m-3 in SPhs, with prominent reductions in primary emissions. However, the fraction of nitrate during SPhs (20.2%) was roughly twice that during NPhs (12.7%) despite a large decrease of NOx, suggesting an efficient transformation of NOx to nitrate during the SP period. This is consistent with the increase of oxygenated organic aerosol (OOA), which almost doubled from NPhs (22.5%) to SPhs (43.0%) in the total organic aerosol (OA) fraction, highlighting efficient secondary formation during SP. The PM1 loading was similar between SPhs (53.0 ± 56.4 μg m-3) and NPnhs (50.7 ± 49.4 μg m-3), indicating a smaller difference in PM pollution between heating and non-heating seasons after the implementation of the SP measure. In addition, a machine learning technique was used to decouple the impact of meteorology on air pollutants. The deweathered results were comparable with the observed results, indicating that meteorological conditions did not have a large impact on the comparison results. Our study indicates that the SP policy is effective in reducing primary emissions but promotes the formation of secondary species.

Submicron Aerosol Composition and Source Contribution across the Kathmandu Valley, Nepal, in Winter.

The Kathmandu valley experiences an average wintertime PM1 concentration of ∼100 μg m-3 and daily peaks over 200 μg m-3. We present ambient nonrefractory PM1 chemical composition, and concentration measured by a mini aerosol mass spectrometer (mAMS) sequentially at Dhulikhel (on the valley exterior), then urban Ratnapark, and finally suburban Lalitpur in winter 2018. At all sites, organic aerosol (OA) was the largest contributor to combined PM1 (C-PM1) (49%) and black carbon (BC) was the second largest contributor (21%). The average background C-PM1 at Dhulikhel was 48 μg m-3; the urban enhancement was 120% (58 μg m-3). BC had an average of 6.1 μg m-3 at Dhulikhel, an urban enhancement of 17.4 μg m-3. Sulfate (SO4) was 3.6 μg m-3 at Dhulikhel, then 7.5 μg m-3 at Ratnapark, and 12.0 μg m-3 at Lalitpur in the brick kiln region. Chloride (Chl) increased by 330 and 250% from Dhulikhel to Ratnapark and Lalitpur on average. Positive matrix factorization (PMF) identified seven OA sources, four primary OA sources, hydrocarbon-like (HOA), biomass burning (BBOA), trash burning (TBOA), a sulfate-containing local OA source (sLOA), and three secondary oxygenated organic aerosols (OOA). OOA was the largest fraction of OA, over 50% outside the valley and 36% within. HOA (traffic) was the most prominent primary source, contributing 21% of all OA and 44% of BC. Brick kilns were the second largest contributor to C-PM1, 12% of OA, 33% of BC, and a primary emitter of aerosol sulfate. These results, though successive, indicate the importance of multisite measurements to understand ambient particulate matter concentration heterogeneity across urban regions.

Contributions of primary sources to submicron organic aerosols in Delhi, India

Abstract. Delhi, India, experiences extremely high concentrations of primary organic aerosol (POA). Few prior source apportionment studies on Delhi have captured the influence of biomass burning organic aerosol (BBOA) and cooking organic aerosol (COA) on POA. In a companion paper, we develop a new method to conduct source apportionment resolved by time of day using the underlying approach of positive matrix factorization (PMF). We call this approach “time-of-day PMF” and statistically demonstrate the improvements of this approach over traditional PMF. Here, we quantify the contributions of BBOA, COA, and hydrocarbon-like organic aerosol (HOA) by applying positive matrix factorization (PMF) resolved by time of day on two seasons (winter and monsoon seasons of 2017) using organic aerosol measurements from an aerosol chemical speciation monitor (ACSM). We deploy the EPA PMF tool with the underlying Multilinear Engine (ME-2) as the PMF solver. We also conduct detailed uncertainty analysis for statistical validation of our results. HOA is a major constituent of POA in both winter and the monsoon. In addition to HOA, COA is found to be a major constituent of POA in the monsoon, and BBOA is found to be a major constituent of POA in the winter. Neither COA nor the different types of BBOA were resolved in the seasonal (not time-resolved) analysis. The COA mass spectra (MS) profiles are consistent with mass spectral profiles from Delhi and around the world, particularly resembling MS of heated cooking oils with a high m/z 41. The BBOA MS have a very prominent m/z 29 in addition to the characteristic peak at m/z 60, consistent with previous MS observed in Delhi and from wood burning sources. In addition to separating the POA, our technique also captures changes in MS profiles with the time of day, a unique feature among source apportionment approaches available. In addition to the primary factors, we separate two to three oxygenated organic aerosol (OOA) components. When all factors are recombined to total POA and OOA, our results are consistent with seasonal PMF analysis conducted using EPA PMF. Results from this work can be used to better design policies that target relevant primary sources of organic aerosols in Delhi.

Tracing the Formation of Secondary Aerosols Influenced by Solar Radiation and Relative Humidity in Suburban Environment

AbstractSecondary particulate matter exerts adverse effects on air quality and human health. The production or reaction rate of secondary aerosols in polluted environments remains uncertain and is complicated by diverse emissions and meteorological conditions. By concurrently measuring the mass spectra of compounds in both particulate (using an aerosol mass spectrometer) and gas phases (using proton‐transfer‐reaction mass spectrometry) in suburban Beijing, we linked the secondary organic aerosol (OA) and volatile organic compounds (VOCs) to photochemical age (tage) and obtained their reaction or production rates. Factorization analysis of the mass spectra of OA and the 108 VOC species resolved three oxygenated OAs (OOA) and three secondary VOC factors at different oxidation levels. Primary organic aerosols and VOCs from traffic sources were determined to be important sources for secondary aerosol formation. At high pollution levels under the conditions of weaker solar radiation and higher relative humidity, moderately oxygenated OA (O/C = 0.61) and secondary inorganics were coproduced in combination with rapid consumption of all VOCs. At lower pollution levels, the intense solar radiation caused substantial and rapid production of OOA (O/C = 0.81) and intermediate VOCs (both in a high oxidation state) at a rate of 15.0% h−1 and 14.0% h−1, respectively. These results highlight the feedback effects between radiation and moisture in terms of altering the formation mechanism of secondary aerosols. In particular, highly oxygenated secondary airborne products under strong radiation should be considered in regard to their environmental impact.