Response of Harbin aerosol to latest clean air actions in China.

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.

Considerable contribution of secondary aerosol to wintertime haze pollution in new target of the latest clean air actions in China.

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 ∼12%. 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 ∼1 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.

Agricultural fire impacts on brown carbon during different seasons in Northeast China.

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.

Exploring chemical changes of the haze pollution during a recent round of COVID-19 lockdown in a megacity in Northeast China.

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.

Non-equilibrium influence on G/P partitioning of PAHs: Evidence from the diurnal and nocturnal variation.

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 (ϕP) 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 ϕP 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 ϕP 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.

New open burning policy reshaped the aerosol characteristics of agricultural fire episodes in Northeast China.

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.

Primary nature of brown carbon absorption in a frigid atmosphere with strong haze chemistry.

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.

Strong biomass burning contribution to ambient aerosol during heating season in a megacity in Northeast China: Effectiveness of agricultural fire bans?

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.

Model vs. observation discrepancy in aerosol characteristics during a half-year long campaign in Northeast China: The role of biomass burning.

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 ∼230 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 ‒ 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.

Secondary inorganic aerosol during heating season in a megacity in Northeast China: Evidence for heterogeneous chemistry in severe cold climate region.

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 ∼80%) and high nitrogen dioxide (above ∼60 µg/m3). Both the sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were enhanced at high RH, reaching ∼0.3. 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.

Integration of field observation and air quality modeling to characterize Beijing aerosol in different seasons.

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 ∼65% 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.

Uncertainties in thermal-optical measurements of black carbon: Insights from source and ambient samples.

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.

The characteristics of carbonaceous aerosol in Beijing during a season of transition.

Carbonaceous aerosol was measured during fall of 2010 in Beijing. Daily variation of organic carbon (OC) was found to coincide with that of relative humidity (RH), and the OC to elemental carbon (EC) ratios were more than doubled during the more humid periods (RH above 0.75) compared to other conditions. This large increase in OC/EC could not be explained by the variations of primary biomass burning emissions but was accompanied by a five-fold increase in the sulfate to EC ratio. It was then inferred that secondary organic aerosol (SOA) formation was enhanced under the more humid conditions, presumably through aqueous-phase processes. This enhanced SOA formation might be partially associated with particles externally mixed with black carbon, as indicated by the RH-dependent relationships between aerosol optical attenuation and EC loading. In addition, organic aerosols exhibited different properties between the more humid and the other periods, such that they were less volatile and charred more significantly during thermal-optical analysis in the former case. These differences coincided with the evidence of enhanced SOA formation under the more humid conditions. This study highlights the necessity of incorporating aqueous-phase chemistry into air quality models for SOA.

Brown and black carbon in Beijing aerosol: Implications for the effects of brown coating on light absorption by black carbon.

Brown carbon (BrC) is increasingly included in climate models as an emerging category of particulate organic compounds that can absorb solar radiation efficiently at specific wavelengths. Water-soluble organic carbon (WSOC) has been commonly used as a surrogate for BrC; however, it only represents a limited fraction of total organic carbon (OC) mass, which could be as low as about 20% in urban atmosphere. Using methanol as the extraction solvent, up to approximately 90% of the OC in Beijing aerosol was isolated and measured for absorption spectra over the ultraviolet-to-visible wavelength range. Compared to methanol-soluble OC (MSOC), WSOC underestimated BrC absorption by about 50% at 365nm. The mass absorption efficiencies measured for BrC in Beijing aerosol were converted to the imaginary refractive indices of BrC and subsequently used to compute BrC coating-induced enhancement of light absorption (Eabs) by black carbon. Eabs attributed to lensing was reduced in the case of BrC coating relative to that caused by purely-scattering coating. However, this reduction was overwhelmed by the effect of BrC shell absorption, indicating that the overall effect of BrC coating was an increase in Eabs. Methanol extraction significantly reduced charring of OC during thermal-optical analysis, leading to a large increase in the measured elemental carbon (EC) mass and an apparent improvement in the consistency of EC measurements by different thermal-optical methods.

The characteristics of Beijing aerosol during two distinct episodes: impacts of biomass burning and fireworks.

The chemical composition of Beijing aerosol was measured during summer and winter. Two distinct episodes were identified. Water-soluble potassium (K(+)) increased significantly during the firework episode in winter with an episode to non-episode ratio of 4.97, whereas the biomass burning (BB) episode in summer was characterized by high episode to non-episode ratios of levoglucosan (6.38) and K(+) (6.90). The BB and firework episodes had only a minor influence on the water-soluble OC (organic carbon) to OC ratio. Based on separate investigations of episode and non-episode periods, it was found that: (i) sulfate correlated strongly with both relative humidity and nitrate during the typical winter period presumably indicating the importance of the aqueous-phase oxidation of sulfur dioxide by nitrogen dioxide, (ii) oxalate and WSOC during both winter and summer in Beijing were mainly due to secondary formation, and (iii) high humidity can significantly enhance the formation potential of WSOC in winter.

[Improvement and application of the method for determination of OCEC split].

Aerosol samples were collected in Beijing (BD) and Atlanta (GT) from July to August in 2011 using a Micro-Orifice Uniform Deposit Impactor (MOUDI) (0.18-18 microm, eight-stage) for organic carbon (OC) and elemental carbon (EC) measurement (Sunset Laboratory Inc, USA). The laser intensity of blank filters decreased with temperature in the process of OC & EC analysis because the structure of quartz filters was changed when burned which largely affected the determination of low concentration samples' splits. It would increase the accuracy of OC & EC split to determine it manually after the change of blank filter's laser intensity was recouped. The concentrations and size distributions of OC & EC using the improved method were different from taking the moment when oxygen was introduced as the split. The split may appear before oxygen addition, when the sample was rich in metal or substances that can be decomposed after heated. The concentrations of carbonaceous components were higher at BD than those at GT. The size distributions of OC showed a bimodal pattern with peaks appeared in the particles with size of (0.56-1.0) microm and (3.2-5.6) microm. The peak concentrations of OC were (2.82 +/- 1.59) microg x m(-3) and (1.95 +/- 0.76) microg x m(-3) at BD, and (1.28 +/- 0.41) microg x m(-3) and (0.64 +/- 0.19) microg x m(-3) at GT. EC showed a bimodal pattern at BD with peaks in particles with size of (0.56-1.0) microm and (3.2-5.6) microm, while showed a trimodal pattern at GT. The peak concentrations at BD were (0.32 +/- 0.24) microg x m(-3) and (0.26 +/- 0.19) microg x m(-3). EC at GT was preferably enriched in particles with size of (0.18-0.56) microm, the mass concentrations of EC in this size accounted for 44.6%. The OC and EC were more concentrated in accumulation mode at GT than those at BD, the reason may be that the main pollution source of GT is motor vehicle emission, while there are more industrial gas emissions at BD.

[Size distribution of particles collected by passive sampler].

Airborn particulate matters were sampled by two duplicate glass slides coated with thin layer of vaseline laid at the bottom of sampling cylinder of passive sampler for collecting both gaseous and particulate phase semi-volatile organic pollutant. Their size distribution was analyzed and found to be influenced by wind speed and coverage of the fine-screen-mesh (300 mesh) wrapping around the outside of sampling cylinder. In a windless (indoor) and semi-static windy conditions (sealed courtyard), diffusion of coarse particles (> 50 microm) was reduced effectively by covering sampling cylinder with the fine-screen-mesh, and accumulated size distribution curve of PM10 was similar with those collected by an active size-fractionated sampler (cascade impactor). In windy conditions (outdoor), coarse particles entered the sampling cylinder randomly, which is independent with wind speed, while the percentage of fine particulate with size of 3-5 microm decreased and those with size of 6-9 microm increased significantly.