Multilinear Engine Research Articles

Development of an integrated framework for dissecting source-oriented ecological and health risks of heavy metals in soils

Heavy metals (HMs) in soils pose significant risks on ecosystem and human health. To design targeted regulatory measures for mitigating and controlling the risk, it is necessary to accurately identify the pollution sources and environmental risks of soil HMs, as well as to reveal the linkages between them. To date, yet systematic investigation aimed at deciphering the links between source apportionment of soil HMs and their associated environmental risks is still lacking. To fill the gap, an integrated framework has been developed in this study and applied for dissecting the source-sink relationship and source-oriented ecological and health risks of soil HMs in Shanxi, a province with rich coal resource, in which long-term coal mining activities in history has resulted in soil HMs pollution and unavoidably posed environmental risks. Two advanced receptor models, multivariate curve resolution alternating least squares based on maximum likelihood principal component analysis (MCR-ALS/MLPCA) and multilinear engine 2 (ME2), have been employed for apportioning the potential sources, and their apportionment results are jointly incorporated into a modified ecological risk index and a probabilistic health risk assessment model for identifying the source-oriented ecological and health risks posed by soil metals. The results show that the soils in study area have been polluted by HMs (i.e., Cd, Cr, Hg and As) to varying degrees. Industrial activities (35%–35.8%), agricultural activities (11.1%–20.5%), atmospheric deposition (10.5%–13%) and mix source (31.5%–42.6%) are apportioned as the main contributors of soil HMs in the area. The source-oriented ecological risk assessment suggests Hg has presented significant ecological risk and largely contributed by the sources from atmospheric deposition and industrial activities. The source-oriented health risk assessment shows the non-carcinogenic hazard level and carcinogenic risk posed by soil HMs in the study area are acceptable. Relatively, industrial activities and mix source have contributed more on the health risks.

Long-term source apportionment of PM2.5 across the contiguous United States (2000-2019) using a multilinear engine model

Identifying PM2.5 sources is crucial for effective air quality management and public health. This research used the Multilinear Engine (ME-2) model to analyze PM2.5 from 515 EPA Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE) sites across the U.S. from 2000 to 2019. The U.S. was divided into nine regions for detailed analysis. A total of seven source types (tracers) were resolved across the country: (1) Soil/Dust (Si, Al, Ca and Fe); (2) Vehicle emissions (EC, OC, Cu and Zn); (3) Biomass/wood burning (K); (4) Heavy oil/coal combustion (Ni, V, Cl and As); (5) Secondary sulfate (SO42-); (6) Secondary nitrate (NO3-) and (7) Sea salt (Mg, Na, Cl and SO42-). Furthermore, we extracted and calculated secondary organic aerosols (SOA) based on the secondary sulfate and nitrate factors. Notably, significant reductions in secondary sulfate, nitrate, and heavy oil/coal combustion emissions reflect recent cuts in fossil-fueled power sector emissions. A decline in SOA suggests effective mitigation of their formation conditions or precursors. Despite these improvements, vehicle emissions and biomass burning show no significant decrease, highlighting the need for focused control on these persistent pollution sources for future air quality management.

Quantifying the Chemical Composition and Real-Time Mass Loading of Nanoplastic Particles in the Atmosphere Using Aerosol Mass Spectrometry.

Plastic debris, including nanoplastic particles (NPPs), has emerged as an important global environmental issue due to its detrimental effects on human health, ecosystems, and climate. Atmospheric processes play an important role in the transportation and fate of plastic particles in the environment. In this study, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was employed to establish the first online approach for identification and quantification of airborne submicrometer polystyrene (PS) NPPs from laboratory-generated and ambient aerosols. The fragmentation ion C8H8+ is identified as the major tracer ion for PS nanoplastic particles, achieving an 1-h detection limit of 4.96 ng/m3. Ambient PS NPPs measured at an urban location in Texas are quantified to be 30 ± 20 ng/m3 by applying the AMS data with a constrained positive matrix factorization (PMF) method using the multilinear engine (ME-2). Careful analysis of ambient data reveals that atmospheric PS NPPs were enhanced as air mass passed through a waste incinerator plant, suggesting that incineration of waste may serve as a source of ambient NPPs. The online quantification of NPPs achieved through this study can significantly improve our understanding of the source, transport, fate, and climate effects of atmospheric NPPs to mitigate this emerging global environmental issue.

Insights into PM2.5 pollution of four small and medium-sized cities in Chinese representative regions: Chemical compositions, sources and health risks

Fine particles (PM2.5) pollution is still a severe issue in some cities in China, where the chemical characteristics of PM2.5 remain unclear due to limited studies there. Herein, we focused on PM2.5 pollution in small and medium-sized cities in key urban agglomerations and conducted a comprehensive study on the PM2.5 chemical characteristics, sources, and health risks. In the autumn and winter of 2019–2020, PM2.5 samples were collected simultaneously in four small and medium-sized cities in four key regions: Dingzhou (Beijing-Tianjin-Hebei region), Weinan (Fenwei Plain region), Fukang (Northern Slope of the Tianshan Mountain region), and Bozhou (Yangtze River Delta region). The results showed that secondary inorganic ions (43.1 %–67.0 %) and organic matter (OM, 8.6 %–36.4 %) were the main components of PM2.5 in all the cities. Specifically, Fukang with the most severe PM2.5 pollution had the highest proportion of SO42− (31.2 %), while the dominant components in other cities were NO3− and OM. The Multilinear Engine 2 (ME2) analysis identified five sources of PM2.5 in these cities. Coal combustion contributed most to PM2.5 in Fukang, but secondary sources in other cities. Combined with chemical characteristics and ME2 analysis, it was preliminarily determined that the primary emission of coal combustion had an important contribution to high SO42− in Fukang. Potential source contribution function (PSCF) analysis results showed that regional transport played an important role in PM2.5 in Dingzhou, Weinan and Bozhou, while PM2.5 in Fukang was mainly affected by short-range transport from surrounding areas. Finally, the health risk assessment indicated Mn was the dominant contributor to the total non-carcinogenic risks and Cr had higher carcinogenic risks in all cities. The findings provide a scientific basis for formulating more effective abatement strategies for PM2.5 pollution.

The application of positive matrix factorization with diagnostics to BIG DATA

Over the past decade, Positive Matrix Factorization (PMF) has become the most commonly used tool for source apportionment of air pollutants with a large fraction of those studies using the implementation developed by the U.S. Environmental Protection Agency (EPA-PMF) and its very useful diagnostic tools. During the same period, more studies are utilizing monitoring tools that provide hourly or even higher time resolution data leading to large data sets (millions of data points). Because of the nature of the graphic user interface in EPA-PMF, it cannot handle data sets more than approximately half a million data points. Thus, alternative approaches are needed to permit these larger data sets to be analyzed and still be able to provide the diagnostic outputs that permit better interpretations of the results. We have developed a protocol to use the multilinear engine (ME-2) that is the solver used in EPA-PMF to make such analyses. Here we report how to use this approach and present results for a representative data set of particle size distributions obtained in Rochester, New York between 2008 and 2019.

Real-time measurements of non-methane volatile organic compounds in the central Indo-Gangetic basin, Lucknow, India: source characterisation and their role in O3 and secondary organic aerosol formation

Abstract. Lucknow is the capital of India's largest state, Uttar Pradesh, one of South Asia's most polluted urban cities. Tropospheric photochemistry relies on non-methane volatile organic compounds (NMVOCs), which are ozone and secondary organic aerosol precursors. Using the proton-transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an urban background site in Lucknow, the chemical characterisation of NMVOCs was performed in real time from December 2020 to May 2021. About ∼ 173 NMVOCs from m/z 31.018 to 197.216 were measured during the study period, including aromatics, non-aromatics, oxygenates, and nitrogen-containing compounds. The campaign daily mean concentrations of the NMVOCs were 125.5 ± 37.5 ppbv. The NMVOC daily average concentrations were about ∼ 30 % higher during the winter months (December–February) than in summer (March–May). The oxygenated volatile organic compounds and aromatics were the dominant VOC families, accounting for ∼ 57 %–80 % of the total NMVOC concentrations. Acetaldehyde, acetone, and acetic acid were the major NMVOC species, 5–15 times higher than the other species. An advanced multi-linear engine (ME-2) model was used to perform the NMVOC source apportionment using positive matrix factorisation (PMF). It resolves the five main sources contributing to these organic compounds in the atmosphere. They include traffic (23.5 %), two solid fuel combustion factors, SFC 1 (28.1 %) and SFC 2 (13.2 %), secondary volatile organic compounds (SVOCs) (18.6 %), and volatile chemical products (VCPs) (16.6 %). Aged and fresh emissions from solid fuel combustion (SFCs 1 and 2) were the dominant contributors to the total NMVOCs, and compounds related to these factors had a high secondary organic aerosol (SOA) formation potential. Interestingly, the traffic factor was the second-highest contributor to the total NMVOCs, and compounds related to this factor had a high ozone formation potential. Significant differences in the composition of the two solid fuel combustions indicate the influence of local emissions and transport of regional pollution to the city. The high temperature during summer leads to more volatilisation of oxygenated VOCs, related to the VCP factor. The study is the first attempt to highlight the sources of NMVOCs and their contribution to secondary pollutant (SOA and O3) formation in the city of Lucknow during winter and summer. The insights from the study would help various stakeholders to manage primary and secondary pollutants within the city.

Molecular tracers, mass spectral tracers and oxidation of organic aerosols emitted from cooking and fossil fuel burning sources

Secondary organic aerosol (SOA) composes a substantial fraction of atmospheric particles, yet the formation and aging mechanism of SOA remains unclear. Here we investigate the initial oxidation of primary organic aerosol (POA) and further aging of SOA in winter Beijing by using aerosol mass spectrometer (AMS) measurements along with offline molecular tracer analysis. Multilinear engine (ME-2) source apportionment was conducted to capture the characteristic of source-related SOA, and connect them with specific POA. Our results show that urban cooking and fossil fuel burning sources contribute significantly (17 % and 20 %) to total organic aerosol (OA) in winter Beijing. Molecular tracer analysis by two-dimensional gas chromatography-time-of-flight mass spectrometer (GC × GC-ToF-MS) reveals that cooking SOA (CSOA) is produced through both photooxidation and aqueous-phase processing, while less oxidized SOA (LO-SOA) is the photooxidation product of fossil fuel burning OA (FFOA) and may experience aqueous-phase aging to form more-oxidized oxygenated OA (MO-OOA). Furthermore, CHOm/z 69 and CHOm/z 85 are mass spectral tracers indicating the initial photooxidation, while CHO2+ and C2H2O2+ imply further aqueous-phase aging of OA. Tracer analysis indicates that the formation of diketones is involved in the initial photooxidation of POA, while the formation of glyoxal and diacids is involved in the further aqueous-phase aging of SOA.

Secondary organic aerosol formation in China from urban-lifestyle sources: Vehicle exhaust and cooking emission.

An increasing number of people tend to live in cities, where they suffer from serious air pollution from anthropogenic sources. Vehicle exhaust and cooking emission are closely related to daily life of urban residents, and could be defined as "urban-lifestyle sources". The primary emissions of urban-lifestyle sources tend to form abundant secondary organic aerosols (SOA) through complicated atmospheric chemistry processes. The newly formed SOA is a kind of complex mixture and causes considerable health effects with high uncertainty. Most studies focus on formation pathway, mass growth potential and chemical feature of urban-lifestyle SOA under simple laboratory conditions. Few studies have measured the urban-lifestyle SOA in ambient air, let alone verified laboratory findings under complicated atmospheric conditions. In this work, we established a new method that combined laboratory simulation and field observation, which quantified the urban-lifestyle SOA with high time resolution under the real atmospheric condition. The complex SOA was measured and resolved by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The multilinear engine model (ME-2) and multilinear correction methods were used to apply laboratory results into ambient SOA apportionment. It was found that the vehicle source dominated the SOA formation during the diurnal photochemical process, and the SOA:POA ratio of vehicle source was about 1.4 times larger than that of cooking source. The vehicle emission may undergo an alcohol/peroxide & carboxylic acid oxidation pathway and form higher oxidized SOA, while the cooking emission may undergo an alcohol/peroxide oxidation pathway and form relatively lower oxidized SOA. The vehicle SOA and cooking SOA contributed 45.6 % and 24.8 % of OA during a local episode in 2021 winter of downtown Beijing. Our findings could not only provide a new way to quantify urban SOA but also demonstrate some laboratory hypotheses, conducing to understand its ambient contributions, chemical features, and environmental effects.

Source apportionment resolved by time of day for improved deconvolution of primary source contributions to air pollution

Abstract. Present methodologies for source apportionment assume fixed source profiles. Since meteorology and human activity patterns change seasonally and diurnally, application of source apportionment techniques to shorter rather than longer time periods generates more representative mass spectra. Here, we present 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 in this approach over traditional PMF. We report on source apportionment conducted on four example time periods in 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. Compared to the traditional seasonal PMF approach, we extract a larger number of factors as well as PMF factors that represent the expected sources of primary organic aerosol using time-of-day PMF. By capturing diurnal time series patterns of sources at a low computational cost, time-of-day PMF can utilize large datasets collected using long-term monitoring and improve the characterization of sources of organic aerosol compared to traditional PMF approaches that do not resolve by time of day.

Sources and processes of organic aerosol in non-refractory PM1 and PM2.5 during foggy and haze episodes in an urban environment of the Yangtze River Delta, China

Organic aerosol (OA) generally accounts for a large fraction of fine particulate matter (PM2.5) in the urban atmosphere. Despite significant advances in the understanding their emission sources, transformation processes and optical properties in the submicron aerosol fraction (PM1), larger size fractions - e.g., PM2.5 - still deserve complementary investigations. In this study, we conducted a comprehensive analysis on sources, formation process and optical properties of OA in PM1 and PM2.5 under haze and foggy environments in the Yangtze River Delta (eastern China), using two aerosol chemical speciation monitors, as well as a photoacoustic extinctiometer at 870 nm. Positive matrix factorization analysis - using multilinear engine (ME2) algorithm - was conducted on PM1 and PM2.5 organic mass spectra. Four OA factors were identified, including three primary OA (POA) factors, i.e., hydrocarbon-like OA (HOA), cooking OA (COA), and biomass burning OA (BBOA), and a secondary OA (SOA) factor, i.e., oxidized oxygenated OA (OOA). An enhanced PM1-2.5 COA concentration was clearly observed during cooking peak hours, suggesting important contribution of fresh cooking emissions on large-sized particles (i.e., PM1-2.5). The oxidation state and concentration of PM2.5 HOA were higher than that in PM1, suggesting that large-sized HOA particles might be linked to oxidized POA. High contribution (44%) of large-sized OOA to non-refractory PM2.5 mass was observed during haze episodes. During foggy episodes, PM1 and PM2.5 OOA concentrations increased as a positive relationship over time, along with an exponential increase in the PM2.5-OOA to PM1-OOA ratio. Meanwhile, OOA loadings increased with the aerosol liquid water content (ALWC) during foggy episodes. Random forest cross-validation analysis also supported the important influence of ALWC on OOA variations, supporting substantial impact of aqueous process on SOA formation during haze and/or foggy episodes. Obtained results also indicated high OOA contributions (21%–36%) and low POA contributions (6%–14%) to the PM2.5 scattering coefficient during haze and foggy episodes, respectively. Finally, we could illustrate that atmospheric vertical diffusion and horizontal transport have important but different effects on the concentrations of different primary and secondary OA factors in different particle size fractions.

Response of aerosol composition to the clean air actions in Baoji city of Fen-Wei River Basin

The implementation of air pollution control measures could alter the compositions of submicron aerosols. Identifying the changes can evaluate the atmospheric responses of the implemented control measures and provide more scientific basis for the formulation of new measures. The Fen-Wei River Basin is the most air polluted region in China, and thereby is a key area for the reduction of emissions. Only limited studies determine the changes in the chemical compositions of submicron aerosols. In this study, Baoji was selected as a representative city in the Fen-Wei River Basin. The compositions of submicron aerosols were determined between 2014 and 2019. Organic fractions were determined through an online instrument (Quadrupole Aerosol Chemical Speciation Monitor, Q-ACSM) and source recognition was performed by the Multilinear Engine (ME-2). The Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) was also employed to evaluate the contributions of emissions reduction and meteorological conditions to the changes of submicron aerosol compositions. The results indicate that the mass concentrations of submicron aerosols have been substantially decreased after implementation of air pollution control measures. This was mainly attributed to the emission reductions of sulfur dioxide (SO2) and primary organic aerosol (POA). In addition, the main components that drove the pollution episodes swapped from POA, sulfate, nitrate and less-oxidized organic (LO-OOA) in 2014 to nitrate and more-oxidized OOA (MO-OOA) in 2019. Due to the changes of chemical compositions of both precursors and secondary pollutants, the pollution control measures should be modernized to focus on the emissions of ammonia (NH3), nitrogen oxides (NOx) and volatile organic compounds (VOCs) in this region.

Large contribution from worship activities to the atmospheric soot particles in northwest China

Worship activities like burning joss paper during the Chinese Hanyi festival is a common, traditional custom in northwest China. However, the pollutants of e.g., soot particles, released from joss paper burning and the corresponding impacts on urban air quality were poorly investigated, which can be a particular concern since these activities are conducted in an uncontrolled manner. In this study, a long time-of-flight (LToF) soot particle aerosol mass spectrometry (SP-AMS) was deployed to characterize the refractory black carbon (rBC) emitted from the joss paper burning, as well as crop residue, coal combustion, and traffic during the Hanyi Festival in mid-November 2020 in the northwestern city of Xi'an in China. Large difference (from <5% to >100%) in the fragmentation patterns (Cn+) for the measured rBC from different source emissions were found when compared to the reference Regal Black. Using the receptor model of positive matrix factorization (PMF) with the multilinear engine (ME-2) algorithm, the obtained rBC mass spectra were used as the anchoring profiles to evaluate the emission strengths of different source types to the atmospheric rBC. Our results show that the burning of joss paper accounted for up to 42% of the atmospheric rBC mass, higher than traffic (14–17%), crop residue (10–17%), coal (18–20%) during the Hanyi festival in northwest China. Moreover, we show that the overall air quality can be worsened due to the practice of uncontrolled burning of joss paper during the festival, which is not just confined to the people who do the burning. Although worship activities occur mainly during festival periods, the pollution events contributed by joss paper burning may pose an acute exposure risk for public health. This is particularly important since burning joss paper during worship activities is common in China and most Asian countries with similar traditions.

An integrated multidisciplinary-based framework for characterizing environmental risks of heavy metals and their effects on antibiotic resistomes in agricultural soils

In this study, a new integrated multidisciplinary-based framework has been proposed to better understand the environmental risks of heavy metals (HMs) in agricultural soils. The source apportionment results revealed by a multilinear engine model were incorporated into the geochemical indexes and the probabilistic health risk assessment models for identifying the source-oriented risks of HMs in the environment. High-throughput sequencing-based metagenomic assembly analysis was used for characterizing the prevalence and dissemination risk of antibiotic resistomes and their associations with the geochemical enrichment of HMs in the soils. Results showed agricultural and industrial activities were the main sources of HMs in the environment. Although the soils were contaminated moderately by HMs and the health risks posed by soil metals were negligible for both adult and children, source-oriented risk evaluation suggested agricultural activities contributed relatively higher contamination and health risks than the other sources. Notably, abundant and diverse antibiotic resistant genes, mobile gene elements, virulence factors, and antibiotic-resistant bacterial pathogens were identified in the agricultural soils, as well as their co-occurrences on the same contigs, implying a non-negligible resistome risk. Further, statistical and network analyses showed the geochemical enrichment of HMs exerted significant effects on the antibiotic resistomes in the environment.

On the use of reference mass spectra for reducing uncertainty in source apportionment of solid-fuel burning in ambient organic aerosol

Abstract. Reference mass spectra are routinely used to facilitate source apportionment of ambient organic aerosol (OA) measured by aerosol mass spectrometers. However, source apportionment of solid-fuel-burning emissions can be complicated by the use of different fuels, stoves, and burning conditions. In this study, the organic aerosol mass spectra produced from burning a range of solid fuels in several heating stoves have been compared using an aerosol chemical speciation monitor (ACSM). The same samples of biomass briquettes and smokeless coal were burnt in a conventional stove and Ecodesign stove (Ecodesign refers to a stove conforming to EU Directive 2009/125/EC), while different batches of wood, peat, and smoky coal were also burnt in the conventional stove, and the OA mass spectra were compared to those previously obtained using a boiler stove. The results show that although certain ions (e.g., m/z 60) remain important markers for solid-fuel burning, the peak intensities obtained at specific m/z values in the normalized mass spectra were not constant with variations ranging from &lt; 5 % to &gt; 100 %. Using the OA mass spectra of peat, wood, and coal as anchoring profiles and the variation of individual m/z values for the upper/lower limits (the limits approach) in the positive matrix factorization (PMF) analysis with the Multilinear Engine algorithm (ME-2), the respective contributions of these fuels to ambient submicron aerosols during a winter period in Dublin, Ireland, were evaluated and compared with the conventional a-value approach. The ME-2 solution was stable for the limits approach with uncertainties in the range of 2 %–7 %, while relatively large uncertainties (8 %–29 %) were found for the a-value approach. Nevertheless, both approaches showed good agreement overall, with the burning of peat (39 % vs. 41 %) and wood (14 % vs. 11 %) accounting for the majority of ambient organic aerosol during polluted evenings, despite their small uses compared to electricity and gas. This study, thus, accounts for the source variability in ME-2 modelling and provides better constraints on the primary factor contributions to the ambient organic aerosol estimations. The finding from this study has significant implications for public health and policymakers considering that it is often the case that different batches of solid fuels are often burnt in different stoves in real-world applications.

Mass spectral characterization of secondary organic aerosol from urban cooking and vehicular sources

Abstract. In the present work, we conducted experiments of secondary organic aerosol (SOA) formation from urban cooking and vehicular sources to characterize the mass spectral features of primary organic aerosol (POA) and SOA using an high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Our results showed that the cooking styles have a greater impact on aged COA (cooking organic aerosol) mass spectra than oxidation conditions. However, the oxidation conditions affect the aged HOA (hydrocarbon-like OA) spectra more significantly than vehicle operating conditions. In our study, we use mass spectra similarity analysis and positive matrix factorization (PMF) analysis to establish the POA and SOA mass spectra of these two sources. These mass spectra are used as source constraints in a multilinear engine (ME-2) model to apportion the OA (organic aerosol) sources in the atmosphere. Compared with the traditional ambient PMF results, the improved ME-2 model can better quantify the contribution of POA and SOA from cooking and vehicular sources. Our work, for the first time, establishes the vehicle and cooking SOA source profiles, and can be further used in the OA source apportionment in the ambient atmosphere.

Time-dependent source apportionment of submicron organic aerosol for a rural site in an alpine valley using a rolling positive matrix factorisation (PMF) window

Abstract. We collected 1 year of aerosol chemical speciation monitor (ACSM) data in Magadino, a village located in the south of the Swiss Alpine region, one of Switzerland's most polluted areas. We analysed the mass spectra of organic aerosol (OA) by positive matrix factorisation (PMF) using Source Finder Professional (SoFi Pro) to retrieve the origins of OA. Therein, we deployed a rolling algorithm, which is closer to the measurement, to account for the temporal changes in the source profiles. As the first-ever application of rolling PMF with multilinear engine (ME-2) analysis on a yearlong dataset that was collected from a rural site, we resolved two primary OA factors (traffic-related hydrocarbon-like OA (HOA) and biomass burning OA (BBOA)), one mass-to-charge ratio (m/z) 58-related OA (58-OA) factor, a less oxidised oxygenated OA (LO-OOA) factor, and a more oxidised oxygenated OA (MO-OOA) factor. HOA showed stable contributions to the total OA through the whole year ranging from 8.1 % to 10.1 %, while the contribution of BBOA showed an apparent seasonal variation with a range of 8.3 %–27.4 % (highest during winter, lowest during summer) and a yearly average of 17.1 %. OOA (sum of LO-OOA and MO-OOA) contributed 71.6 % of the OA mass, varying from 62.5 % (in winter) to 78 % (in spring and summer). The 58-OA factor mainly contained nitrogen-related variables which appeared to be pronounced only after the filament switched. However, since the contribution of this factor was insignificant (2.1 %), we did not attempt to interpolate its potential source in this work. The uncertainties (σ) for the modelled OA factors (i.e. rotational uncertainty and statistical variability in the sources) varied from ±4 % (58-OA) to a maximum of ±40 % (LO-OOA). Considering that BBOA and LO-OOA (showing influences of biomass burning in winter) had significant contributions to the total OA mass, we suggest reducing and controlling biomass-burning-related residential heating as a mitigation strategy for better air quality and lower PM levels in this region or similar locations. In Appendix A, we conduct a head-to-head comparison between the conventional seasonal PMF analysis and the rolling mechanism. We find similar or slightly improved results in terms of mass concentrations, correlations with external tracers, and factor profiles of the constrained POA factors. The rolling results show smaller scaled residuals and enhanced correlations between OOA factors and corresponding inorganic salts compared to those of the seasonal solutions, which was most likely because the rolling PMF analysis can capture the temporal variations in the oxidation processes for OOA components. Specifically, the time-dependent factor profiles of MO-OOA and LO-OOA can well explain the temporal viabilities of two main ions for OOA factors, m/z 44 (CO2+) and m/z 43 (mostly C2H3O+). Therefore, this rolling PMF analysis provides a more realistic source apportionment (SA) solution with time-dependent OA sources. The rolling results also show good agreement with offline Aerodyne aerosol mass spectrometer (AMS) SA results from filter samples, except for in winter. The latter discrepancy is likely because the online measurement can capture the fast oxidation processes of biomass burning sources, in contrast to the 24 h filter samples. This study demonstrates the strengths of the rolling mechanism, provides a comprehensive criterion list for ACSM users to obtain reproducible SA results, and is a role model for similar analyses of such worldwide available data.

PM2.5 composition and sources in the San Joaquin Valley of California: A long-term study using ToF-ACSM with the capture vaporizer

The San Joaquin Valley (SJV) of California has suffered persistent particulate matter (PM) pollution despite many years of control efforts. To further understand the chemical drivers of this problem and to support the development of State Implementation Plan for PM, a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) outfitted with a PM2.5 lens and a capture vaporizer has been deployed at the Fresno-Garland air monitoring site of the California Air Resource Board (CARB) since Oct. 2018. The instrument measured non-refractory species in PM2.5 continuously at 10-min resolution. In this study, the data acquired from Oct. 2018 to May 2019 were analyzed to investigate the chemical characteristics, sources and atmospheric processes of PM2.5 in the SJV. Comparisons of the ToF-ACSM measurement with various co-located aerosol instruments show good agreements. The inter-comparisons indicated that PM2.5 in Fresno was dominated by submicron particles during the winter whereas refractory species accounted for a major fraction of PM2.5 mass during the autumn associated with elevated PM10 loadings. A rolling window positive matrix factorization analysis was applied to the organic aerosol (OA) mass spectra using the Multilinear Engine (ME-2) algorithm. Three distinct OA sources were identified, including vehicle emissions, local and regional biomass burning, and formation of oxygenated species. There were significant seasonal variations in PM2.5 composition and sources. During the winter, residential wood burning and oxidation of nitrogen oxides were major contributors to the occurrence of haze episodes with PM2.5 dominated by biomass burning OA and nitrate. In autumn, agricultural activities and wildfires were found to be the main cause of PM pollution. PM2.5 concentrations decreased significantly after spring and were dominated by oxygenated OA during March to May. Our results highlight the importance of using seasonally dependent control strategies to mitigate PM pollution in the SJV.

Real-time quantification and source apportionment of fine particulate matter including organics and elements in Delhi during summertime

Delhi is one of the most polluted cities globally, with frequent severe air pollution episodes and haze events occurring in recent years, thereby compelling us to understand the sources to develop effective mitigation plans. Complete chemical characterization of fine particulate matter (PM2.5) components (non-refractory, refractory and elements) with high time resolution has been done during the summer season (June–July 2019). The total PM equivalent (PM2.5(eq)) was 28.7 ± 13.2 μg m−3 of which elements dominated the PM2.5(eq) with 34% contribution followed by organics (28%), black carbon (BC) (17%), SO42− (10%), Cl− (5%) NH4+ (3.5%) and NO3− (2.5%). The contributions from organic aerosols (OA) and SO42− were observed to be more than Cl− and NO3−. The total elemental mass concentration (PMEl) was mostly contributed (~96%) by Si, S, Cl, Ca, K, Fe and Al with Si and S alone contributing around 50% of PMEl. Crustal elements (Al, Fe, Ca and Si) were highly enhanced in summer than elements emitted from anthropogenic emissions (Cl, S, K, Pb and Zn). Source apportionment (SA) of PM was performed using positive matrix factorization (PMF) together with ME-2 (multilinear engine) for OA and elements, separately. PMF on both datasets helped resolve sources such as combustion, industrial, dust-related, incineration and traffic. OA PMF identified three factors related to primary emissions: hydrocarbon-like OA (HOA, 12.3%), solid fuel combustion (SFC, 16.2%) and cooking OA (COA, 7.3%) and two oxygenated OA (OOA): semi-volatile OOA (SVOOA, 15.2%) and low-volatile OOA (LVOOA, 49.1%). The elemental PMF resolved 8 factors: dust (52.5%), S-rich (16.2%), Cl-rich (10.7%), 2 SFC factors (10.5%), non-exhaust (7.2%), Cu-rich (1.5%) and industrial (1.4%). The contribution of BC to total PM mass is shown to increase in the summer compared to previous studies reported for the winter season. The secondary oxidized sources dominated both the OA and elements SA during the summer with 64.3% and 27% (dust not considered) contribution, respectively. The domination of secondary sources implies that it is crucial to control the secondary aerosols' precursors in Delhi for developing pollution control strategies. The ME-2 resolved factors, coupled with concentration weighted trajectory (CWT) showed the probable major elemental source regions of local origin (Delhi- National Capital Region (Delhi-NCR)) as well as regional (from Punjab, Haryana, Uttar Pradesh and Pakistan). The local sources included Cu-rich (Haryana) and SFC-II (Delhi and Uttar Pradesh), while the regional sources were dust (south-west (SW)), industrial, Cl-rich (north-west (NW)), SFC-I (east and south-east (SE)) and S-rich (SE).

Seasonal variations in the highly time-resolved aerosol composition, sources and chemical processes of background submicron particles in the North China Plain

Abstract. For the first time in the North China Plain (NCP) region, we investigated the seasonal variations in submicron particles (NR-PM1) and their chemical composition at a background mountainous site of Xinglong using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer. The average concentration of NR-PM1 was highest in autumn (15.1 µg m−3) and lowest in summer (12.4 µg m−3), with a greater abundance of nitrate in spring (34 %), winter (31 %) and autumn (34 %) and elevated organics (40 %) and sulfate (38 %) in summer. PM1 in Xinglong showed higher acidity in summer and moderate acidity in spring, autumn and winter, with average pH values of 2.7±0.6, 4.2±0.7, 3.5±0.5 and 3.7±0.6, respectively, which is higher than those estimated in the United States and Europe. The size distribution of all PM1 species showed a consistent accumulation mode peaking at approximately 600–800 nm (dva), indicating a highly aged and internally mixed nature of the background aerosols, which was further supported by the source appointment results using positive matrix factorization and multilinear engine analysis. Significant contributions of aged secondary organic aerosol (SOA) in organic aerosol (OA) were resolved in all seasons (&gt;77 %), especially in summer. The oxidation state and the process of evolution of OAs in the four seasons were further investigated, and an enhanced carbon oxidation state (−0.45–0.10) and O/C (0.54–0.75) and OM/OC (1.86–2.13) ratios – compared with urban studies – were observed, with the highest oxidation state appearing in summer, likely because of the relatively stronger photochemical processing that dominated the formation processes of both less oxidized OA (LO-OOA) and more oxidized OA (MO-OOA). Aqueous-phase processing also contributed to the SOA formation and prevailed in winter, with the share to MO-OOA being more important than that to LO-OOA. In addition, regional transport also played an important role in the variations in SOA. Especially in summer, continuous increases in SOA concentration as a function of odd oxygen (Ox=O3+NO2) were found to be associated with the increases in wind speed. Furthermore, backward trajectory analysis showed that higher concentrations of submicron particles were associated with air masses transported short distances from the southern regions in all four seasons, while long-range transport from Inner Mongolia (western and northern regions) also contributed to summertime particulate pollution in the background areas of the NCP. Our results illustrate that the background particles in the NCP are influenced significantly by aging processes and regional transport, and the increased contribution of aerosol nitrate highlights how regional reductions in nitrogen oxide emissions are critical for remedying occurrence of nitrate-dominated haze events over the NCP.

Source apportionment and impact of long-range transport on carbonaceous aerosol particles in central Germany during HCCT-2010

Abstract. The identification of different sources of the carbonaceous aerosol (organics and black carbon) was investigated at a mountain forest site located in central Germany from September to October 2010 to characterize incoming air masses during the Hill Cap Cloud Thuringia 2010 (HCCT-2010) experiment. The near-PM1 chemical composition, as measured by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), was dominated by organic aerosol (OA; 41 %) followed by sulfate (19 %) and nitrate (18 %). Source apportionment of the OA fraction was performed using the multilinear engine (ME-2) approach, resulting in the identification of the following five factors: hydrocarbon-like OA (HOA; 3 % of OA mass), biomass burning OA (BBOA; 13 %), semi-volatile-like OA (SV-OOA; 19 %), and two oxygenated OA (OOA) factors. The more oxidized OOA (MO-OOA, 28 %) was interpreted as being influenced by aged, polluted continental air masses, whereas the less oxidized OOA (LO-OOA, 37 %) was found to be more linked to aged biogenic sources. Equivalent black carbon (eBC), measured by a multi-angle absorption photometer (MAAP) represented 10 % of the total particulate matter (PM). The eBC was clearly associated with HOA, BBOA, and MO-OOA factors (all together R2=0.83). Therefore, eBC's contribution to each factor was achieved using a multi-linear regression model. More than half of the eBC (52 %) was associated with long-range transport (i.e., MO-OOA), whereas liquid fuel eBC (35 %) and biomass burning eBC (13 %) were associated with local emissions, leading to a complete apportionment of the carbonaceous aerosol. The separation between local and transported eBC was well supported by the mass size distribution of elemental carbon (EC) from Berner impactor samples. Air masses with the strongest marine influence, based on back trajectory analysis, corresponded with a low particle mass concentration (6.4–7.5 µg m−3) and organic fraction (≈30 %). However, they also had the largest contribution of primary OA (HOA ≈ 4 % and BBOA 15 %–20 %), which was associated with local emissions. Continental air masses had the highest mass concentration (11.4–12.6 µg m−3), and a larger fraction of oxygenated OA (≈45 %) indicated highly processed OA. The present results emphasize the key role played by long-range transport processes not only in the OA fraction but also in the eBC mass concentration and the importance of improving our knowledge on the identification of eBC sources.