ABSTRACT
Cities in Northeast China, e.g., Harbin, were brought to the forefront of air pollution control by a national-level policy promulgated in 2021, i.e., the Circular on Further Promoting the Pollution Prevention and Control Battle (the FP3CB Circular) which aimed at eliminating heavy or severe air pollution events. In this study, we explored the response of Harbin aerosol to the FP3CB Circular, based on observational results from two campaigns conducted during 2020-2021 and 2021-2022. A clear decreasing trend was identified for the impact of domestic biomass burning between the two winters, presumably driven by the clean heating actions. The 2021-2022 winter was also characterized by reduced formation of secondary organic aerosol but enhanced production of nitrate, which could be attributed to the less humid conditions but higher temperatures, respectively, compared to the 2020-2021 winter. The overall effect of these changes was a decrease in the contribution of organic species to wintertime aerosol in Harbin. In addition, the number of heavy or severe pollution days rebounded in the 2021-2022 winter compared to 2020-2021 (5 vs. 3), indicating that the emissions of primary particles and gaseous precursors must be further reduced to achieve the ambitious goals of the FP3CB Circular.
ABSTRACT
Biomass burning (BB) is a very important emission source that significantly adversely impacts regional air quality. BB produces a large number of primary organic aerosol (POA) and black carbon (BC). Besides, BB also provides many precursors for secondary organic aerosol (SOA) generation. In this work, the ratio of levoglucosan (LG) to organic carbon (OC) and the fire hotspots map was used to identify the open biomass burning (OBB) events, which occurred in two representative episodes, October 13 to November 30, 2020, and April 1 to April 30, 2021. The ratio of organic aerosol (OA) to reconstructed PM2.5 concentration (PM2.5*) increased with the increase of LG/OC. When LG/OC ratio is higher than 0.03, the highest OA/PM2.5* ratio can reach 80%, which means the contribution of OBB to OA is crucial. According to the ratio of LG to K+, LG to mannosan (MN) and the regional characteristics of Longfengshan, it can be determined that the crop residuals are the main fuel. The occurrence of OBB coincides with farmers' preferred choices, i.e., burning biomass in "bright weather". The "bright weather" refers to the meteorological conditions with high temperature, low humidity, and without rain. Meteorological factors indirectly affect regional biomass combustion pollution by influencing farmers' active choices.
Subject(s)
Air Pollutants , Particulate Matter , Particulate Matter/analysis , Air Pollutants/analysis , Biomass , Seasons , Environmental Monitoring , China , Carbon/analysis , Meteorological Concepts , Aerosols/analysisABSTRACT
Black Carbon (BC), the second-largest contributor to global warming, has detrimental effects on human health and the environment. However, the accurate quantification of BC poses a significant challenge, impeding the comprehensive assessment of its impacts. Therefore, this paper aims to critically review three quantitative methods for measuring BC: Thermal Optical Analysis (TOA), the Optical Method, and Laser-Induced Incandescence (LII). The determination principles, available commercial instruments, sources of deviation, and correction approaches associated with these techniques are systematically discussed. By synthesizing and comparing the quantitative results reported in previous studies, this paper aims to elucidate the underlying relationships and fundamental disparities among Elemental Carbon (EC), Equivalent Black Carbon (eBC), and Refractory Black Carbon (rBC). Finally, based on the current advancements in BC quantification, recommendations are proposed to guide future research directions.
ABSTRACT
Fine particulate matter (PM2.5) in Northeast China was targeted by national-level clean air policy for the first time in 2022, with the release of Action Plan to eliminate heavy air pollution events. In this study, we investigated sources of PM2.5 during three successive winters in Harbin, a megacity in Northeast China, based on observational results from several recent campaigns in 2018-2021. During the 2020-2021 campaign, daytime and nighttime samples were collected in specific months in addition to 24-h integrated measurements, and the two sets of samples were combined in different ways to run a positive matrix factorization model. The source apportionment results suggested that the resolved secondary organic carbon (SOCPMF) had an uncertainty of â¼12%. Secondary aerosols were found to show the following features for the typical winters without agricultural fires. First, SOCPMF could be properly constrained by results from another widely-used approach for SOC estimation, the elemental carbon-tracer method. Second, secondary PM2.5 calculated using SOCPMF and secondary inorganic ions were generally in line with the independent estimations based on air quality data. Third, secondary components accounted for more than 50% of PM2.5 on average and contributed even more significantly during severe haze episodes, which were the focus of the latest Action Plan. This study also found that the wintertime PM2.5 decreased more slowly during 2017-2021 compared to 2013-2017, by â¼1 and 10 µg/m3 per year, respectively, for the metropolitan area where Harbin is located at. Our results highlighted the importance of secondary aerosols for further improving air quality in Northeast China, and for avoiding heavy pollution as required by the latest Action Plan.
Subject(s)
Air Pollutants , Air Pollution , Air Pollutants/analysis , Environmental Monitoring/methods , Particulate Matter/analysis , Air Pollution/analysis , China , Seasons , Aerosols/analysis , Carbon/analysisABSTRACT
Brown carbon (BrC) represents not only a major component of haze pollution but also a non-negligible contributor to positive radiative forcing, making it a key species for coordinating air quality and climate policies. In China, field observations on BrC remain limited given the highly variable emission sources and meteorological conditions across different regions. Here we focused on the optical properties of BrC in a distinct but rarely studied megacity in Northeast China, which is within a major agricultural region and experiences extremely cold winter. Agricultural fires were evident in April of 2021 and the fall of 2020, although open burning was strictly prohibited. Such emissions enhanced BrC's mass absorption efficiency at 365 nm (MAE365), more efficiently by the fall fires which were inferred to have relatively high combustion efficiencies (CE). After taking CE into consideration, the relationships between MAE365 and the levoglucosan to organic carbon ratio (a measure of the significance of agricultural fire influence) roughly converged for the fire episodes in different seasons, including those identified in February and March of 2019 by a previous campaign. Agricultural fires also influenced the determination of absorption Ångström exponent (AAE), by resulting in non-linearity for BrC's absorption spectra shown on ln-ln scale. Based on three indicators developed by this study, the non-linearity was inferred to be caused by similar chromophores although the fires were characterized by various CE levels in different seasons. In addition, for the samples without significant influence of open burning, coal combustion emissions were identified as the dominant influencing factor for MAE365, whereas none solid link was found between the solution-based AAE and aerosol source.
ABSTRACT
Monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth and thus influence climate feedback. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H2O2 concentration, which is a proxy for HO2 concentration. The high O/C ratios observed in the α-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NOx photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, nonlinear dependence on the input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.
Subject(s)
Air Pollutants , Volatile Organic Compounds , Aerosols/chemistry , Air Pollutants/analysis , Hydrogen Peroxide , Monoterpenes/chemistry , Oxidants , Oxidation-ReductionABSTRACT
Oxidation of the monoterpene Δ3-carene (C10H16) is a potentially important and understudied source of atmospheric secondary organic aerosol (SOA). We present chamber-based measurements of speciated gas and particle phases during photochemical oxidation of Δ3-carene. We find evidence of highly oxidized organic molecules (HOMs) in the gas phase and relatively low-volatility SOA dominated by C7-C10 species. We then use computational methods to develop the first stages of a Δ3-carene photochemical oxidation mechanism and explain some of our measured compositions. We find that alkoxy bond scission of the cyclohexyl ring likely leads to efficient HOM formation, in line with previous studies. We also find a surprising role for the abstraction of primary hydrogens from methyl groups, which has been calculated to be rapid in the α-pinene system, and suggest more research is required to determine if this is more general to other systems and a feature of autoxidation. This work develops a more comprehensive view of Δ3-carene photochemical oxidation products via measurements and lays out a suggested mechanism of oxidation via computationally derived rate coefficients.
Subject(s)
Monoterpenes , Aerosols/chemistry , Bicyclic Monoterpenes , Monoterpenes/chemistry , Oxidation-ReductionABSTRACT
COVID-19 rebounded in China in January 2021, with Heilongjiang as one of the worst-affected provinces. This resulted in a new round of lockdown in Harbin, the capital city of Heilongjiang, from 20 January to 22 February of 2021. A field campaign was conducted to explore the responses of haze pollution in Harbin to the lockdown. Levoglucosan was used to reflect biomass burning emissions, while the molar ratio of sulfur (the sum of sulfur dioxide and sulfate) to nitrogen (the sum of nitrogen dioxide and nitrate), i.e., RS/N, was used as an indicator for the relative importance of coal combustion and vehicle emissions. Based on a synthesis of the levoglucosan and RS/N results, reference period was selected with minimal influences of non-lockdown-related emission variations. As indicated by the almost unchanged sulfur dioxide concentrations, coal combustion emissions were relatively stable throughout the lockdown and reference periods, presumably because the associated activities, e.g., heating supply, power generation, etc., were usually uninterruptible. On the other hand, as suggested by the increase of RS/N, vehicle emissions were considerably reduced during lockdown, likely due to the stay-at-home orders. Compared to results from the reference samples, the lockdown period exhibited higher levels of ozone and various indicators for secondary aerosol formation, pointing to an enhancement of secondary pollution. In addition, photochemistry-related reactions in aqueous phase appeared to be present during the lockdown period, which have not been reported in the frigid atmosphere over Northeast China.
Subject(s)
Air Pollutants , Air Pollution , COVID-19 , Aerosols/analysis , Air Pollutants/analysis , Air Pollution/analysis , China , Communicable Disease Control , Environmental Monitoring , Humans , Particulate Matter/analysis , SARS-CoV-2ABSTRACT
Gas/particle (G/P) partitioning is an important behavior for the atmospheric transport of polycyclic aromatic hydrocarbons (PAHs). In this study, paired daytime and nighttime air samples were collected for one year in order to study the diurnal and nocturnal variations of concentration and G/P partitioning of PAHs. Higher PAHs concentrations in total phase were observed in nighttime. The geomean (GM) concentrations of Σ15PAHs in total phase were 69.6 and 52.8 ng/m3 in nighttime and daytime, respectively. More obviously diurnal and nocturnal variations were observed in non-heating season, with the GM ratios of Σ15PAHs in nighttime to daytime of 1.65 and 1.06 in non-heating season and heating season, respectively. The results could be attributed to emission sources and meteorological conditions. The values of particulate phase fraction (ÏP) and G/P partitioning quotient (log KP) were used to quantify the phase distribution of PAHs. For most high molecular weight PAHs, the values of ÏP and log KP in nighttime were higher than those in daytime, which could be mainly attributed to the lower temperature in nighttime. However, for the three light molecular weight PAHs (Acy, Ace and Flu), higher values of ÏP and log KP were observed in daytime. The regression of log KP against log KOA for the three PAHs in daytime differed from those in nighttime. The chemical losses of PAHs in different phases might be responsible for the result. These findings suggested that the chemical loss of PAHs in gas phase should be considered for the G/P partitioning process.
Subject(s)
Air Pollutants , Polycyclic Aromatic Hydrocarbons , Air Pollutants/analysis , Environmental Monitoring/methods , Particulate Matter/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Seasons , TemperatureABSTRACT
To gain a comprehensive understanding of sources, health risks, and regional transport of PM2.5-bound metals in Beijing, one-year continuous measurement (K, Fe, Ca, Zn, Pb, Mn, Ba, Cu, As, Se, Cr, and Ni) was conducted from December 2016 to November 2017 and Positive Matrix Factorization analysis (PMF) was applied for source apportionment. It was found that the seasonal variation of sources could vary significantly among metals. Sources of Ca, Ba, As, Se, and Cr did not show much seasonal variations, with the contribution of its predominant source higher than 35% in each season. However, the major sources of K, Fe, Zn, Pb, Mn, Cu, and Ni exhibited obvious seasonal variations. In addition, the characteristics of metals in haze episodes were comprehensively investigated. Haze episodes in Beijing were characterized by higher metal concentrations and health risks, which were about 2- 6 times higher than non-haze periods. Moreover, the types of haze episode were different in winter and spring. Haze episodes in winter were mostly influenced by coal combustion, the contribution of which increased greatly and accounted for about 30% of PM2.5. The metals such as K, Zn, Pb, As, and Se significantly increased, which were mainly transported from south of Beijing. During haze episodes in spring, dust was an important source, which contributed to higher concentrations of crustal metals that transported from northwest of Beijing. To quickly and effectively identify source regions of metals in Beijing during haze episodes, a new diagnostic ratio method using Ca as a reference was developed. The ratios of some anthropogenic metals to Ca significantly increased when air mass was mainly from south of Beijing during haze episodes while the ratios remained constantly low in non-haze periods, when local emissions dominated. This method could be useful for rapid identification and control of metal pollution in Beijing.
Subject(s)
Air Pollutants , Particulate Matter , Air Pollutants/analysis , Beijing , China , Environmental Monitoring , Particulate Matter/analysis , Seasons , Vehicle Emissions/analysisABSTRACT
The massive agricultural sector in the Northeast Plain, which is of great importance for the food security in China, results in a huge amount of crop residues and thus substantial concern on haze pollution due to biomass burning (BB). To seek for effective control measures on BB emissions, a dramatic transition of open burning policy occurred in Heilongjiang Province, from the "legitimate burning" policy released in 2018 to the "strict prohibition" policy implemented in 2019 and beyond. Here we explored the BB aerosols during 2020-2021 in Harbin, the capital city of Heilongjiang. Although open burning was strictly prohibited by mandatory bans, agricultural fires were not actually eliminated, as indicated by the levoglucosan levels and fire count results. In general, the BB aerosols in Harbin were attributed to the overlaying of household burning and agricultural fire emissions. The former factor laid the foundation of biomass burning impacts, with BB contributions to organic carbon and elemental carbon (fBBOC and fBBEC) of 35 and 47%, respectively. The latter further enhanced the BB impacts during specific episodes breaking out in the spring of 2021 as well as the fall of 2020, when fBBOC and fBBEC increased to 64 and 57%, respectively. In addition, comparing to the fires of 2018-2019 which occurred in winter (in response to the "legitimate burning" policy), the agricultural fires were shifted to spring and fall in the 2020-2021 campaign, accompanied with an increase of combustion efficiency. This study illustrated how the agricultural fire emissions were influenced by the transition of open burning policy.
Subject(s)
Air Pollutants , Fires , Aerosols/analysis , Air Pollutants/analysis , Biomass , China , Environmental Monitoring , Particulate Matter/analysis , Policy , SeasonsABSTRACT
Severe haze hovered over Harbin during the heating season of 2019-2020, making it one of the ten most polluted Chinese cities in January of 2020. Here we focused on the optical properties and sources of brown carbon (BrC) during the extreme atmospheric pollution periods. Enhanced formation of secondary BrC (BrCsec) was evident as relative humidity (RH) became higher, accompanied with a decrease of ozone but concurrent increases of aerosol water content and secondary inorganic aerosols. These features were generally similar to the characteristics of haze chemistry observed during winter haze events in the North China Plain, and indicated that heterogeneous reactions involving aerosol water might be at play in the formation of BrCsec, despite the low temperatures in Harbin. Although BrCsec accounted for a substantial fraction of brown carbon mass, its contribution to BrC absorption was much smaller (6 vs. 28%), pointing to a lower mass absorption efficiency (MAE) of BrCsec compared to primary BrC. In addition, emissions of biomass burning BrC (BrCBB) were inferred to increase with increasing RH, coinciding with a large drop of temperature. Since both the less absorbing BrCsec and the more absorbing BrCBB increased as RH became higher, the MAE of total BrC were largely unchanged throughout the measurement period. This study unfolded the contrast in the source apportionment results of BrC mass and absorption, and could have implications for the simulation of radiative forcing by brown carbon.
Subject(s)
Air Pollutants , Carbon , Aerosols/analysis , Air Pollutants/analysis , Biomass , Carbon/analysis , Environmental Monitoring , SeasonsABSTRACT
Sustainable use of crop residues remains a challenge in main agricultural regions of China such as the Northeast Plain. Here we investigated the impacts of biomass burning on fine particle (PM2.5) during a six-month long heating season in the Harbin-Changchun (HC) metropolitan area, China's only national-level city cluster located in the severe cold climate region. Temporal variation of PM2.5 was found to coincide with that of levoglucosan. This was attributed to the strong contribution of biomass burning to organic aerosol (the dominant component in PM2.5), as supported by the source apportionment results and high levoglucosan-to-organic carbon (OC) ratios. Furthermore, the variation of biomass burning contribution was inferred to be driven mainly by agricultural fires with relatively low combustion efficiencies, based on a synthesis of the relationship between OC and elemental carbon (EC), the dependence of EC on carbon monoxide, and the relative abundances of different tracers for biomass burning. Nitrate formation was enhanced during biomass burning episodes whereas no evidence was observed to indicate enhanced sulfate formation or net increase of OC mass due to secondary formation. This study demonstrates the importance of open burning as a source of haze pollution in the HC region.
ABSTRACT
Complex air pollutant sources and distinct meteorological conditions resulted in unique wintertime haze pollution in the Harbin-Changchun (HC) metropolitan area, China's only national-level city cluster located in the severe cold climate region. In this study, field observation and air quality modeling were combined to investigate fine particulate matter (PM2.5) pollution during a six-month long heating season in HC's central city (Harbin). The model significantly underpredicted PM2.5 and organic carbon (by up to â¼230 µg/m3 and 110 µgC/m3, respectively, in terms of daily average) when levoglucosan concentrations were above 0.5 µg/m3. Based on a synthesis of levoglucosan concentrations and fire counts, the large gaps were attributed to underestimation of open burning emissions by the model. However, the model tended to overpredict elemental carbon (more significantly at higher NO2), likely pointing to an overestimation of vehicle emissions. With increasing levoglucosan, the difference between observed and simulated nitrate (nitrateobs â nitratemod, i.e., Δnitrate) showed a transition from negative to positive values. The positive Δnitrate were attributed to underprediction of the open-burning related nitrate, whereas the negative Δnitrate were likely caused by overprediction of nitrate from other sources (presumably vehicle emissions). The dependence of Δnitrate on levoglucosan indicated that with stronger impact of open burning, the overprediction effect was gradually offset and finally overwhelmed. Influence of open burning on sulfate formation was evident as well, but less apparent compared to nitrate. This study illustrates how the uncertainties in open burning emissions will influence PM2.5 simulation, on not only primary components but also secondary species.
Subject(s)
Air Pollutants , Air Pollution , Aerosols/analysis , Air Pollutants/analysis , Biomass , China , Cities , Environmental Monitoring , Particulate Matter/analysis , SeasonsABSTRACT
Agriculture-oriented cities in Northeastern China have experienced frequent atmospheric pollution events. Deeper understandings of the pollution characteristics, haze causes and effects of management on local air quality are crucial for conducting integrated management approaches for the sustainable development of agriculture-oriented cities. Taking a typical agriculture-dominant city (i.e., Suihua) in Northeast China, we analyzed in detail the characteristics and causes of atmospheric pollution and evaluated the straw-burning prohibition using multisource data. The results showed a clear temporal pattern of air quality index (AQI) on an annual scale (i.e., 2015-April 2019), with two typical pollution periods occurring in late autumn and early spring. The large areas of concentrated straw burning at local and regional scales accounted for the first period (i.e., October and November), while dust emissions and farming disturbances comprised the second period. The interannual variation in pollution periods among these years was large, showing similar trends from 2015 to 2017 and the postponed late-autumn pollution period in 2018. Our evaluation has shown that the prohibition effect of straw burning significantly improved air quality in 2018, with a reduction of 59% ± 88% in the PM2.5 concentrations in October and November compared to 2015-2017. However, From October to April of the following year, the improvement effect was not significant due to postponement of straw burning to February or March. Our analysis also highlighted the roles of meteorological conditions, Therefore, combined with the promotion of straw utilization, scientifically prescribed burning considering the burning amount and location, meteorological conditions and regional transportation should be implemented.
Subject(s)
Air Pollutants/analysis , Air Pollution/analysis , Agriculture , China , Cities , Environmental Monitoring , Particulate Matter/analysis , SeasonsABSTRACT
The characteristics of secondary inorganic aerosol including sulfate, nitrate and ammonium (SNA) were investigated during a six-month long heating season in the Harbin-Changchun metropolitan area, i.e., China's only national-level city cluster located in the severe cold climate region. The contribution of SNA to fine particulate matter (PM2.5) tended to decrease with increasing PM2.5 concentration, opposite to the trend repeatedly observed during winter in Beijing. Heterogeneous sulfate formation was still evident when the daily average temperature was as low as below -10 °C, with the preconditions of high relative humidity (RH; above â¼80%) and high nitrogen dioxide (above â¼60 µg/m3). Both the sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were enhanced at high RH, reaching â¼0.3. However, the high RH conditions were not commonly seen during the heating season, which should be responsible for the overall lack of linkage between the SNA contribution and PM2.5 temporal variation.
Subject(s)
Air Pollutants/analysis , Cold Climate , Environmental Monitoring , Aerosols/analysis , Beijing , China , Cities , Heating , Humidity , Nitrates/analysis , Nitrogen Dioxide , Nitrogen Oxides/analysis , Particulate Matter/analysis , Seasons , Sulfates/analysisABSTRACT
Organic aerosol (OA) constitutes a significant fraction of atmospheric fine particle mass. However, the precursors and chemical processes responsible for a majority of OA are rarely conclusively identified. We use online observations of hundreds of simultaneously measured molecular components obtained from 15 laboratory OA formation experiments with constraints on their effective saturation vapor concentrations to attribute the VOC precursors and subsequent chemical pathways giving rise to the vast majority of OA mass measured in two forested regions. We find that precursors and chemical pathways regulating OA composition and volatility are dynamic over hours to days, with their variations driven by coupled interactions between multiple oxidants. The extent of physical and photochemical aging, and its modulation by NOx, were key to a uniquely comprehensive combined composition-volatility description of OA. Our findings thus provide some of the most complete mechanistic-level guidance to the development of OA descriptions in air quality and Earth system models.
ABSTRACT
Fine particulate matter (PM2.5) pollution in Beijing was investigated based on field observation and air quality modeling. Measurement results showed that when using elemental carbon (EC) as the reference component, concurrent increases were observed in the relative abundances of sulfate, nitrate, organic carbon (OC) and water-soluble organic carbon (WSOC) when RH exceeded â¼65% during winter. The observed increases could not be explained by variations of primary biomass burning emissions, instead they likely pointed to heterogeneous chemistry and presumably indicated that formation of secondary inorganic and organic aerosols might be related during winter haze events in Beijing. Large gaps were found in winter when comparing the observational and modeling results. In summer, RH exhibited little influence on the observed sulfate/EC, OC/EC or WSOC/EC, and the observed and modeled results were in general comparable for the concentrations of sulfate, EC and OC. This study suggests that distinct yet poorly-understood atmospheric chemistry may be at play in China's winter haze events, and it could be a substantial challenge to properly incorporate the related mechanisms into air quality models.
Subject(s)
Aerosols/analysis , Air Pollutants/analysis , Air Pollution/analysis , Seasons , Beijing , Biomass , Carbon/analysis , China , Environmental Monitoring/methods , Particulate Matter/analysisABSTRACT
Atmospheric oxidation of natural and anthropogenic volatile organic compounds (VOCs) leads to secondary organic aerosol (SOA), which constitutes a major and often dominant component of atmospheric fine particulate matter (PM2.5). Recent work demonstrates that rapid autoxidation of organic peroxy radicals (RO2) formed during VOC oxidation results in highly oxygenated organic molecules (HOM) that efficiently form SOA. As NOx emissions decrease, the chemical regime of the atmosphere changes to one in which RO2 autoxidation becomes increasingly important, potentially increasing PM2.5, while oxidant availability driving RO2 formation rates simultaneously declines, possibly slowing regional PM2.5 formation. Using a suite of in situ aircraft observations and laboratory studies of HOM, together with a detailed molecular mechanism, we show that although autoxidation in an archetypal biogenic VOC system becomes more competitive as NOx decreases, absolute HOM production rates decrease due to oxidant reductions, leading to an overall positive coupling between anthropogenic NOx and localized biogenic SOA from autoxidation. This effect is observed in the Atlanta, Georgia, urban plume where HOM is enhanced in the presence of elevated NO, and predictions for Guangzhou, China, where increasing HOM-RO2 production coincides with increases in NO from 1990 to 2010. These results suggest added benefits to PM2.5 abatement strategies come with NOx emission reductions and have implications for aerosol-climate interactions due to changes in global SOA resulting from NOx interactions since the preindustrial era.
ABSTRACT
Black carbon (BC) is important due to its complex influences on the environment and on climate in particular. However, reported BC data are largely dependent on measurement techniques due to the multitude of measurement principles. Here we focused on thermal-optical method which has been widely used to determine BC mass (as elemental carbon, EC). Several factors influencing EC measurement were investigated. Results from source samples representing vehicle engine emissions pointed to a continuum of EC components in thermal stability and provided direct observational evidence for the premature evolution of EC in inert atmosphere. It was also found that EC masses may be substantially underestimated for the vehicle exhaust samples if the adopted protocol requires an oxidizing atmosphere to define the split point between organic carbon (OC) and EC. Results from a field campaign conducted during winter in Beijing showed that the optical attenuation (ATN; i.e., the filter transmittance signal, I) was largely saturated for the samples with relatively high loadings, indicating their EC results were unreliable. Improved measurement of EC was achieved by extracting these heavily loaded filters using methanol, given that ATN was considerably reduced by the extraction and, moreover, saturation of ATN (or I) became not evident for the extracted samples. The methanol extraction also significantly reduced the transformation of OC to char-OC, by removing the majority (i.e., ~85%) of the deposited organic aerosols. Higher EC were measured for the extracted samples compared with the untreated ones, indicating that EC tends to be underestimated due to the charring-induced uncertainties. In addition, the methanol extraction largely reduced the inter-protocol discrepancy in the EC measurement results. Similar effects of methanol extraction have been observed during summer in Beijing, despite the seasonal variations of aerosol sources and compositions. This study indicates the potential benefits of methanol extraction for EC measurement.