[Effect of Biomass Burning on Carbonaceous Aerosol Composition and Light Absorption in Guangxi Regional Background Site].

Carbonaceous aerosols are an important component of fine particulate matter (PM2.5) in the atmosphere, having great impacts on air quality, human health, and the climate. In this study, PM2.5 samples were collected from November 2017 to October 2018 in a background site of Guangxi Province to investigate the potential impacts of biomass burning, an essential source of carbonaceous aerosols, on carbonaceous aerosols. Further, the composition of carbonaceous aerosols, sugar compounds, and the light absorption coefficient (babs) of water-soluble brown carbon (BrC) were also conducted. Considering the effect of the degradation of atmospheric levoglucosan (LG), the concentration of the corrected LG was quantified using the aging of air masses (AAM) index. Then, the contribution of biomass burning (BB) to organic carbon (OC) [BB-OC] was quantified using the corrected LG-derived molecular tracer method combined with the Bayesian mixing model. Here, we further explored the potential sources of water-soluble BrC using correlation analysis. In this research, the mean AAM index was 0.40±0.28 during the study period, indicating that the atmospheric LG had undergone a photochemical degradation process. The characteristic ratio combined with the Bayesian mixing model indicated that the crop straw (i.e., corn, rice, and sugarcane straw) was the dominant biomass fuel type in the Guangxi Region, contributing 22%, 23%, and 18% of OC without the correction of LG and 16%, 21%, and 17% with the corrected LG concentration, respectively. The neglection of LG degradation led to the underestimation of BB-OC, in which the BB-OC values with and without correction were 49.0% and 21.1%, respectively. Here, the annual mean babs of water-soluble BrC was (8.7±10.7) Mm-1, and its main sources were BB, fossil fuel combustion, and vegetation emission.

Application of cellulose to chromatographic media: Cellulose dissolution, and media fabrication and derivatization.

As the cornerstone of chromatographic technology, the development of high-performance chromatographic media is a crucial means to enhance the purification efficiency of biological macromolecules. Cellulose is a popular biological separation medium due to its abundant hydroxyl group on the surface, easy modification and, weak non-specific adsorption. In this paper, the development of cellulosic solvent systems, typical preparation methods of cellulosic chromatographic media, and the enhancement of chromatographic properties of cellulosic chromatographic media by polymeric ligand grafting strategies and their mechanism of action are reviewed. Ultimately, based on the current research status, a promising outlook for the preparation of high-performance cellulose-based chromatographic media was presented.

Increasing Nonfossil Fuel Contributions to Atmospheric Nitrate in Urban China from Observation to Prediction.

China's nitrogen oxide (NOx) emissions have undergone significant changes over the past few decades. However, nonfossil fuel NOx emissions are not yet well constrained in urban environments, resulting in a substantial underestimation of their importance relative to the known fossil fuel NOx emissions. We developed an approach using machine learning that is accurate enough to generate a long time series of the nitrogen isotopic composition (δ15N) of atmospheric nitrate using high-level accuracies of air pollutants and meteorology data. Air temperature was found to be the critical driver of the variation of nitrate δ15N at daily resolution based on this approach, while significant reductions of aerosol and its precursor emissions played a key role in the change of nitrate δ15N on the yearly scale. Predictions from this model found a significant decrease in nitrate δ15N in Chinese megacities (Beijing and Guangzhou as representative cities in the north and south, respectively) since 2013, implying an enhanced contribution of nonfossil fuel NOx emissions to nitrate aerosols (up to 22%-26% in 2021 from 18%-22% in 2013 quantified by an isotope mixing model), as confirmed by the Weather Research and Forecasting model coupled with online chemistry (WRF-Chem) simulation. Meanwhile, the declining contribution in coal combustion (34%-39% in 2013 to 31%-34% in 2021) and increasing contribution of natural gas combustion (11%-14% in 2013 to 14%-17% in 2021) demonstrated the transformation of China's energy structure from coal to natural gas. This approach provides missing records for exploring long-term variability in the nitrogen isotope system and may contribute to the study of the global reactive nitrogen biogeochemical cycle.

Important Role of NO3 Radical to Nitrate Formation Aloft in Urban Beijing: Insights from Triple Oxygen Isotopes Measured at the Tower.

Until now, there has been a lack of knowledge regarding the vertical profiles of nitrate formation in the urban boundary layer (BL) based on triple oxygen isotopes. Here, we conducted vertical measurements of the oxygen anomaly of nitrate (Δ17O-NO3-) on a 325 m meteorological tower in urban Beijing during the winter and summer. The simultaneous vertical measurements suggested different formation mechanisms of nitrate aerosols at ground level and 120 and 260 m in the winter due to the less efficient vertical mixing under stable atmospheric conditions. Particularly, different chemical processes of nitrate aerosols at the three heights were found between clean days and polluted days in the winter. On clean days, nocturnal chemistry (NO3 + HC and N2O5 uptake) contributed to nitrate production equally with OH/H2O + NO2 at ground level, while it dominated aloft (contributing 80% of nitrate production at 260 m), due to the higher aerosol liquid water content and O3 concentration there. On polluted days, nocturnal reactions dominated the formation of nitrate at the three heights. Particularly, the contribution of the OH/H2O + NO2 pathway to nitrate production increased from the ground level to 120 m might be attributed to the hydrolysis of NO2 to HONO and then further photolysis to OH radicals in the day. In contrast, the proportion of N2O5 + H2O decreased at 260 m, likely due to the low relative humidity aloft that inhibited the N2O5 hydrolysis reactions in the residual layer. Our results highlighted that the differences between meteorology and gaseous precursors could largely affect particulate nitrate formation at different heights within the polluted urban BL.

Impacts of chemical degradation of levoglucosan on quantifying biomass burning contribution to carbonaceous aerosols: A case study in Northeast China.

Biomass burning (BB) is an important source of carbonaceous aerosols in Northeast China (NEC). Quantifying the original contribution of BB to organic carbon (OC) [BB-OC] can provide an essential scientific information for the policy-makers to formulate the control measures to improve the air quality in the NEC region. Daily PM2.5 samples were collected in the rural area of Changchun city over the NEC region from May 2017 to May 2018. In addition to carbon contents, BB tracers (e.g., levoglucosan and K+BB, defined as potassium from BB) were also determined, in order to investigate the relative contribution of BB-OC. The results showed that OC was the dominant (28%) components of PM2.5 during the sampling period. Higher concentrations of OC, levoglucosan, and K+BB were observed in the autumn followed by the winter, spring, and summer, indicating that the higher BB activities during autumn and winter in Changchun. By using the Bayesian mixing model, it was found that burning of crop residues were the dominant source (65-79%) of the BB aerosols in Changchun. During the sampling period, the aging in air mass (AAM) ratio was 0.14, indicating that ~86% of levoglucosan in Changchun was degraded. Without considering the degradation of levoglucosan in the atmosphere, the BB-OC ratios were 23%, 28%, 7%, and 4% in the autumn, winter, spring, and summer, respectively, which were 1.4-4.8 time lower than those (14-42%) with consideration of levoglucosan degradation. This illustrated that the relative contribution of BB to OC would be underestimated (~59%) without considering degradation effects of levoglucosan. Although some uncertainty was existed in our estimation, our results did highlight that the control of straw burning was an efficient way to decrease the airborne PM2.5, improving the air quality in the NEC plain.

Light absorption and source apportionment of water soluble humic-like substances (HULIS) in PM2.5 at Nanjing, China.

Humic-like substances (HULIS), as important components of brown carbon (BrC), play an important role in climate change. In this study, one-year PM2.5 samples from 2017 to 2018 were collected at Nanjing, China and the water soluble HULIS and other chemical species were analyzed to investigate the seasonal variations, optical properties and possible sources. The HULIS concentrations exhibited highest in winter and lowest in summer. The annual averaged HULIS concentration was 2.61 ± 1.79 µg m-3, accounting for 45 ± 13% of water-soluble organic carbon (WSOC). The HULIS light absorption coefficient at 365 nm (Abs365, HULIS) averagely accounted for 71 ± 19% of that of WSOC, suggesting that HULIS are the main light-absorbing components in WSOC. The annual averaged Ångström absorption exponent and mass absorption efficiency of HULIS at 365 nm were 5.22 ± 0.77 and 1.71 ± 0.70 m2 g-1. Good correlations between HULIS with levoglucosan and K+ suggested biomass burning (BB) influence on HULIS. High concentrations of HULIS and secondary species (e.g., NO3-, SO42-, NH4+, C2O42-) were found in present of high relative humidity, indicating strong aqueous phase secondary HULIS formation. Secondary HULIS produced from anthropogenic and biogenic precursors were quantified based on the positive matrix factorization (PMF) model and the results showed that both fossil (55%) and biogenic (45%) emission sources made great contributions to HULIS. Fossil fuel combustion significantly contributed to HULIS formation throughout the whole year, which were enriched with more secondary HULIS (30%) than primary HULIS (25%). Strongest BB contribution (39%) was found in winter and biogenic SOA contribution (32%) was found in summer. A multiple linear regression (MLR) method was further applied to obtain specific source contributions to Abs365, HULIS and the results showed that strong light-absorbing chromophores were produced from anthropogenic precursors. Our results highlight the anthropogenic SOA and fossil fuels combustion contributions to HULIS in addition to the biggest contributor, BB, in urban area in China.

[High-frequency Evolution of Urban Atmospheric Ammonia and Ammonium and Its Gas-to-Particle Conversion Mechanism in Nanjing City].

In this study, hourly mass concentrations of atmospheric gases (mainly NH3) and secondary inorganic aerosols (mainly NH4+, NO3-, and SO42-) in Nanjing City were continuously measured during the fall of 2018 by an online gas and aerosol chemical component monitor. The dataset was used to investigate the variation characteristics of ambient NH3 and NH4+ during polluted and non-polluted periods, and to explore the potential chemical mechanism during gas-to-particle conversion between NH3 and NH4+. The results show that throughout the sampling period, the mean values (±1σ) of the mass concentrations of NH3 and NH4+ were (15.3±6.7) µg·m-3 and (11.3±7.8) µg·m-3, respectively, and that their diurnal profiles were distinct between pollution and non-pollution periods. Analysis of the potential contribution sources indicated that local contributions exceeded long-range transport as the dominant source of measured NH3 and NH4+, suggesting that urban areas can be hotspots of NH3 emissions. Further in-depth analysis revealed that the process of gas-to-particle conversion was the main driving force with respect to controlling diurnal variations in NH3 and NH4+. Specifically, pollution episodes were characterized by low temperature (7.5-12.5℃) and high humidity (50%-90%) meteorological conditions. These conditions tended to accelerate the reaction rate of gas-to-particle conversion and facilitate the formation of aerosol ammonium, leading to pronounced (NH4)2SO4 and NH4NO3 increases during pollution events. These findings clarify the sources of NH3 in the urban atmosphere and its potential contribution to the formation of particulate matter.