Insights into anthropogenic impact on atmospheric inorganic aerosols in the largest city of the Tibetan Plateau through multidimensional isotope analysis.

Particulate inorganic nitrogen aerosols (PIN) significantly influence air pollution and pose health risks worldwide. Despite extensive observations on ammonium (pNH4+) and nitrate (pNO3-) aerosols in various regions, their key sources and mechanisms in the Tibetan Plateau remain poorly understood. To bridge this gap, this study conducted a sampling campaign in Lhasa, the Tibetan Plateau's largest city, with a focus on analyzing the multiple isotopic signatures (δ15N, ∆17O). These isotopes were integrated into a Bayesian mixing model to quantify the source contributions and oxidation pathways for pNH4+ and pNO3-. Our results showed that traffic was the largest contributor to pNH4+ (31.8 %), followed by livestock (25.4 %), waste (21.8 %), and fertilizer (21.0 %), underscoring the impact of vehicular emissions on urban NH3 levels in Lhasa. For pNO3-, coal combustion emerged as the largest contributor (27.3 %), succeeded by biomass burning (26.3 %), traffic emission (25.3 %), and soil emission (21.1 %). In addition, the ∆17O-based model indicated a dominant role of NO2 + OH (52.9 %) in pNO3- production in Lhasa, which was similar to previous observations. However, it should be noted that the NO3 + volatile organic component (VOC) contributed up to 18.5 % to pNO3- production, which was four times higher than the Tibetan Plateau's background regions. Taken together, the multidimensional isotope analysis performed in this study elucidates the pronounced influence of anthropogenic activities on PIN in the atmospheric environment of Lhasa.

[Analysis of Formation Processes and Sources of PM2.5 Ammonium During Winter and Summer in Suburban Area of the Yangtze River Delta].

As the main pollutants of secondary inorganic aerosols(SIAs) in fine particulate matter(PM2.5), aerosol ammonium(p-NH4+) plays a significant role in the formation of haze. However, the contribution ratio of each potential source of atmospheric NHx(p-NH4+ and NH3) still remains controversial. In this study, 3 h high-frequency PM2.5 samples were collected in Dongshan, Suzhou during winter and summer in 2015, respectively. Meanwhile, we determined concentrations and δ15N isotope ratios of total nitrogen(TN) and p-NH4+ and quantitatively analyzed formation processes and sources of p-NH4+ based on the Bayesian mixing model(SIAR). SO42-, NO3-, and NH4+ were the main water-soluble ions(WSIs) both in winter and summer, accounting for more than 70% in general. The concentration change trends of PM2.5, TN, and p-NH4+ were consistent, and the concentrations in winter were 2-3 times those in summer. The δ15N-NH4+ value was in direct proportion to the p-NH4+ concentration both in winter and summer. However, δ15N-NH4+ values in winter(-1.7‰±4.3‰) were lower than those in summer(7.8‰±5.9‰). This indicated that the differences in δ15N-NH4+ were caused by different contribution rates of each potential source within each season, whereas it was mainly led by nitrogen isotope fractionation during ammonium-ammonia gas particle distribution in different seasons. The SIAR model calculated that non-agricultural sources were the dominant source of p-NH4+ in Dongshan, with the contribution rate of 59% in winter and 69% in summer, which indicated that NH3 emitted by fossil fuel combustion more easily formed particle aerosol ammonium than that volatilized from agricultural sources.

Effects of contrasting tillage managements on the vertical distribution of plant- and microbial-derived carbon in rice paddy.

Soil microbial necromass is considered a persistent component of soil organic carbon (SOC), constituting the final product of the microbial carbon pump (MCP). However, the mechanisms involved in the effects of tillage and rice residue managements on the vertical distribution of microbial necromass and plant residues in rice paddy soils remain unclear, limiting knowledge of SOC sequestration mechanisms. Therefore, we estimated microbial- and plant-derived C by biomarker amino sugars (AS) and lignin phenols (VSC) at the 0-30 cm soil depth, as well as their relationships with SOC contents and mineralization in a rice paddy soil under contrasting tillage practices, namely no-tillage (NT), reduced tillage (RT), and conventional tillage (CT). The results showed that the SOC contents in the rice paddy soil were positively correlated with soil AS and VSC contents. The NT resulted in significantly higher (P < 0.05) AS (expressed as per kilogram soil) at the 0-10 cm and 10-30 cm soil depths by 45-48 % than RT and CT. However, microbial-derived C contents and SOC mineralization were not significantly changed by NT. In contrast, the plant-derived C contents in the total SOC decreased significantly under the NT scenario, suggesting the consumption of plant-derived C even with more rice residue inputs (at the 0-10 cm soil depth). In summary, 5-year short-term NT management with more rice residue mulch on the soil surface in rice paddy maintained a low plant-derived C content (at a sampling date before rice transplanting), suggesting a different mode of C sequestration, except for the protection of plant-derived C under anaerobic conditions.

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.

Vertical measurements of stable nitrogen and oxygen isotope composition of fine particulate nitrate aerosol in Guangzhou city: Source apportionment and oxidation pathway.

Nowadays, the emission source and formation mechanism of fine particulate nitrate (pNO3-) in China are mired in controversy. In this study, the stable nitrogen isotope (δ15N-NO3-) and triple oxygen isotope (Δ17O-NO3-) were determined for the pNO3- samples collected at three heights under different atmospheric oxidation capacity (AOC) (Ox = O3 + NO2: 107 ± 29 µg m-3 at ground, 102 ± 28 µg m-3 at 118 m, 122 ± 23 µg m-3 at 488 m) conditions during the sampling period based on the Canton Tower, Guangzhou, China. The Bayesian mixing model showed that coal combustion was the largest contributor to pNO3- in this city, followed by biomass burning, vehicle exhaust, and soil emission. Interestingly, we found that vertical NOx and pNO3- concentrations displayed an opposite pattern owing to the different formation mechanisms among heights. The average contributions of oxidation pathways for (NO2 + OH, P1), (NO3 + DMS/HC, P2), and (N2O5 + H2O, P3) were 61 %, 12 %, and 27 % at the ground, respectively, and these values would vary greatly among heights. These results implied that both AOC and NOx loading played an important role in pNO3- production. The pNO3- displayed a positive correlation with NOx (r = 0.95) with an enhanced contribution of the P1 pathway under the relatively high AOC condition. However, pNO3- has a negative correlation with NOx (r = -0.99) with a rise of heterogeneous reaction (P2 and P3) under the relatively low AOC condition. Therefore, the current emission control strategy for air pollution in China needs to consider the AOC conditions among regions to effectively mitigate particulate air pollution.

Seasonal variations of low molecular alkyl amines in PM2.5 in a North China Plain industrial city: Importance of secondary formation and combustion emissions.

Atmospheric amines have unique acid-neutralizing capacity and play an important role in atmospheric chemical reactions. An integrated observation of PM2.5 samples (from Dec 2015 to Nov 15, 2016) was conducted in a typical industrial city (Xuzhou), China. Concentrations of total measured amines (∑amines, including methylamine (MA), ethylamine (EA), dimethylamine (DMA), propanamine (PA) and trimethylamine (TMA) + diethylamine (DEA)) were 172.0 ± 98.2 ng m-3, accounting 1.5 ± 0.6 ‰ of PM2.5 mass. ∑amines were higher in winter (249.0 ± 112.3 ng m-3) and spring (192.4 ± 75.9 ng m-3) than in summer (114.7 ± 33.3 ng m-3) and autumn (103.7 ± 34.3 ng m-3). Concentrations of MA and EA (the dominant amines) were highest in winter, while DMA, PA and TMA + DEA showed opposite seasonality. EA/MA ratios ranged from 0.04 to 8.7 with a median value of 0.3, and the averaged EA/MA ratio was 2.0 in winter, indicating large contribution of EA. Environmental factors including temperature (T), relative humidity (RH) and atmospheric oxidizing capacity (O3 and Ox represented) were found to influence concentrations of amines in PM2.5. The Positive Matrix Factorization (PMF) model identified secondary products (41.6 %), combustion emissions (39.8 %), soil and waste incineration emissions (13.2 %) and biological emissions and aging products (5.4 %) as the 4 sources of amines in PM2.5. MA was mainly secondary products (82.5 %) and had high contribution of local secondary formation, while EA was mainly derived from combustion emissions (83.7 %) and influenced by regional transportation. In winter, combustion emissions (including coal combustion, biomass burning and traffic emissions, contributed 57.7 %) surpassed secondary products (31.6 %) as the predominant sources of amines, especially under the influence of regional transportation (75.7 %).

Isotopic imprints of aerosol ammonium over the north China plain.

Atmospheric PM2.5 poses a variety of health and environmental risks to urban environments. Ammonium is one of the main components of PM2.5, and its role in PM2.5 pollution will likely increase in the coming years as NH3 emissions are still unregulated and rising in many cities worldwide. However, partitioning urban NH4+ sources remains challenging. Although the 15N natural abundance (δ15N) analysis is a promising approach for this purpose, it has seldom been applied across multiple cities within a given region. This limits our understanding of the regional patterns and controls of NH4+ sources in urban environments. Here, we collected PM2.5 samples using an active sampling technique during winter at six cities in the North China Plain to characterize the concentrations, δ15N and sources of NH4+ in PM2.5. We found substantial variations in both the concentrations and δ15N of NH4+ among the sites. The mean NH4+ concentrations across the six cities ranged from 3.6 to 12.1 µg m-3 on polluted days and from 0.9 to 10.6 µg m-3 on non-polluted days. The δ15N ranged from 6.5‰ to 13.9‰ on polluted days and from 8.7‰ to 13.5‰ on non-polluted days. The δ15N decreased with increasing NH4+ concentrations at all six sites. We found that non-agricultural sources (vehicle exhaust, ammonia slip and urban wastes) contributed 72%-94% and 56%-86% of the NH4+ on polluted and non-polluted days, respectively, and that during polluted days, combustion-related emissions (vehicle exhaust and ammonia slip) were positively associated with the proportion of urban area, population density and number of vehicles, highlighting the importance of local sources of particulate pollution. This study suggests that the analysis of 15N in aerosol NH4+ is a promising approach for apportioning atmospheric NH3 sources over a large region, and this approach has potential for mapping rapidly and precisely the sources of NH3 emissions.

[Changes in Carbonaceous Aerosol in the Northern Suburbs of Nanjing from 2015 to 2019].

Carbonaceous aerosol is an important component of atmospheric fine particles that has an important impact on air quality, human health, and climate change. In order to explore the long-term changes in carbonaceous aerosol under the background of emission reduction, this study measured the mass concentrations of organic carbon (OC) and elemental carbon (EC) of PM2.5, which collected in the northern suburbs of Nanjing for five years (December 17, 2014 to January 5, 2020). The results showed that the five-year average ρ(OC) and ρ(EC) were (10.2±5.3) µg·m-3 and (1.6±1.1) µg·m-3, accounting for 31.1% and 5.2% of PM2.5, respectively. OC and EC concentrations were both high in winter and low in summer. According to the nonparametric Mann-Kendall test and Sen's slope, the mass concentrations of OC and PM2.5 decreased significantly[OC:P<0.0001, -0.79 µg·(m3·a)-1, -0.29%·a-1; PM2.5:P<0.0001, -4.59 µg·(m3·a)-1, -1.58%·a-1]. Although EC had an upward trend, the significance and range of change were not obvious[P=0.02, 0.05 µg·(m3·a)-1, 0.02%·a-1]. OC and EC decreased significantly during winter from 2014 to 2019[OC:P<0.0001, -2.05 µg·(m3·a)-1, -0.74%·a-1; EC:P=0.001, -0.15 µg·(m3·a)-1, -0.05%·a-1], and the decline was more obvious than the whole. The correlation between OC and EC showed that the sources in winter and summer were more complex than those in spring and autumn. According to the characteristic ratio of OC and EC, the contribution of coal combustion and biomass burning decreased from 2015 to 2019, whereas the impact of industrial sources and vehicle emissions became more significant. Corresponding to this was the obvious decline in OC and the slight recovery of EC. The OC/EC ratio was over 2.0, indicating that there was secondary pollution in the study area. Further calculation revealed that the variation in SOC was consistent with that in OC, showing a significant decrease[P<0.0001, -0.47 µg·(m3·a)-1, -0.17%·a-1]. The average mass concentration of SOC was (5.0±3.5) µg·m-3, accounting for 49.2% of OC. These changes indicate clear effects of the prevention and control of air pollution in Nanjing in recent years. Furthermore, future control can focus on the emissions of VOCs to reduce secondary pollution.

[Analysis on the Characteristics of Oxidation Potential and Influence Sources of PM2.5 in Baoding City in Winter].

In order to explore the characteristics of PM2.5 oxidation potential and its impact sources in the suburbs of Baoding City in the winter of 2018, the dithiothreitol (DTT) method was used to determine the reactive oxygen species in PM2.5. Pearson correlation was used to analyze the relationship between the chemical components in PM2.5 and the oxidation potential. PMF was used to analyze the pollution source of DTTv. Firstly, the results showed that the average value of ρ(PM2.5) in Baoding in winter was (140.96±70.67) µg·m-3 higher than the concentration of PM2.5 in Beijing during the same period. Secondly, both the DTTv and DTTm values of the oxidation potential were higher during the day than those at night[DTTv was (2.37±0.76) nmol·(min·m3)-1 during the day and (2.14±1.17) nmol·(min·m3)-1 at night; DTTm was (0.96±0.60) pmol·(min·µg)-1 during the day and (0.76±0.41) pmol·(min·µg)-1 at night]. This showed that the atmospheric environment during the day was more conducive to the generation and survival of active oxygen. In addition, through the analysis of the correlation between DTTv and carbohydrates, inorganic salt ions, OC, EC, and water-soluble metals, it was found that metal Fe, oxalate, and NH4+ had a high correlation with DTTv both day and night (during the day:r=0.790, P<0.01, at night:r=0.960, P<0.01; during the day:r=0.609, P<0.01, at night:r=0.577, P<0.01; during the day:r=0.627, P<0.01, at night:r=0.586, P<0.01), and OC, levoglucan, mannan, and galactan were only highly correlated with DTTv in the daytime (r=0.675, P<0.01; r=0.701, P<0.01; r=0.662, P<0.01; r=0.671, P<0.01). Finally, according to the PMF source analysis, there were five main pollution sources that affected DTTv:secondary sources (29.9%), biomass combustion (29.2%), dust (11.2%), mineral dust and industrial sources (8.6%), and traffic sources (21.1%). The influence of secondary sources and biomass combustion on DTTv was dominant.

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.

Formation Mechanisms and Source Apportionments of Airborne Nitrate Aerosols at a Himalayan-Tibetan Plateau Site: Insights from Nitrogen and Oxygen Isotopic Compositions.

Formation pathways and sources of atmosphere nitrate (NO3-) have attracted much attention as NO3- had detrimental effects on Earth's ecosystem and climate change. Here, we measured nitrogen (δ15N-NO3-) and oxygen (δ18O-NO3- and Δ17O-NO3-) isotope compositions in nitrate aerosols at the Qomolangma station (QOMS) over the Himalayan-Tibetan Plateau (HTP) to quantify the formation mechanisms and emission sources of nitrate at the background site. At QOMS, the enhanced NO3- concentrations were observed in the springtime. The average δ15N-NO3-, δ18O-NO3-, and Δ17O-NO3- values were 0.4 ± 4.9, 64.7 ± 11.5 and 27.6 ± 6.9‰, respectively. Seasonal variations of isotope ratios at QOMS can be explained by the different emissions and formation pathways to nitrate. The average fractions of NO2 + OH and N2O5 + H2O to nitrate production were estimated to be 43 and 52%, respectively, when the NO3 + hydrocarbon (HC)/dimethyl sulfide (DMS) (NO3 + HC/DMS) pathway was assumed to be 5%. Using stable isotope analysis in the R (SIAR) model, the relative contributions of biomass burning (BB), biogenic soil emission, traffic, and coal combustion to nitrate were estimated to be 28, 25, 24, and 23%, respectively, on yearly basis. By FLEXible PARTicle (FLEXPART) dispersion model, we highlighted that NOx from BB emission over South Asia that had undergone N2O5 + H2O processes enhanced the nitrate concentrations in the springtime over the HTP region.

Substantial decreases of light absorption, concentrations and relative contributions of fossil fuel to light-absorbing carbonaceous aerosols attributed to the COVID-19 lockdown in east China.

To prevent spreads of Coronavirus disease-2019 (COVID-19), China adopted the lockdown measures in late January 2020, providing a platform to study the response of air quality and atmospheric chemical and physical properties to strict reduced emissions. In this study, the continuous measurements of aerosol light absorption were conducted in Nanjing, east China, from January 3 to March 31, 2020. Our results showed that the contribution of black carbon (BC) to light absorption at the different wavelengths was more than 75% and the rest light absorption was contributed by brown carbon (BrC), which was mainly originated from primary emissions. Secondary BrC absorption, which was mainly produced by photochemical oxidation, constituted a minor fraction (2-7%) of the total absorption. Compared with the sampling in the pre-lockdown, the significant decreases of BC (43%) and secondary BrC absorption (31%) were found during the lockdown period, resulting in a substantial decrease of solar energy absorbance by 36% on a local scale. The control measures also changed the diurnal variations of light absorption. Due to the reduced emissions, the relative fraction of fossil fuel to BC also dropped from 78% in the pre-lockdown to 71% in the lockdown. The concentrations of BC, PM2.5 and NO2 decreased 1.1 µg m-3, 33 µg m-3 and 9.1 ppb whereas O3 concentration increased 9.0 ppb during the COVID-19 lockdown period. The decreased concentrations of BC, PM2.5 and NO2 were mainly contributed by both emission reduction (51-64%) and meteorological conditions (36-49%). Our results highlighted that the balance of control measures in alleviation of particulate matter (PM) and O3 pollution, and meteorology should be seriously considered for improvement of air quality in this urban city of China.

Source apportionments of atmospheric volatile organic compounds in Nanjing, China during high ozone pollution season.

Atmospheric volatile organic compounds (VOCs) are not only harmful to human health, but also lead to ozone (O3) formation. From July 3 to August 1 of 2018, online measurements of atmospheric VOCs were conducted in Nanjing City, in order to investigate the source apportionments to VOCs since the Empirical Kinetic Modelling Approach (EKMA) suggested that O3 formation was VOC-limited at the receptor site. Using positive matrix factorization (PMF) model, we quantified eight sources of VOCs, including vehicle exhausts (23%), industrial source (18%), fuel evaporation (17%), petrochemical industry (12%), solvent usage (12%), biogenic emission (8%) and liquefied petroleum gas (7%) along with gasoline additive (3%). The diurnal distributions showed that the contributions of traffic-related sources maximized during the traffic rush hours. In contrast, biogenic sources had the highest contribution at noontime. Backward trajectory results showed that local traffic emissions were the main sources of VOC in Nanjing. Our results revealed that strict control of VOC emissions from local vehicle exhaust might be an important way to decrease high VOC pollution in Nanjing.

Development of a Monitoring System for Semicontinuous Measurements of Stable Carbon Isotope Ratios in Atmospheric Carbonaceous Aerosols: Optimized Methods and Application to Field Measurements.

Carbon content constitutes a major fraction of atmospheric particulate matter (PM) and directly influences the earth's climate and human health. The stable carbon isotope ratios (δ13C) can be used to track potential sources and atmospheric processes of carbonaceous aerosols. Previously, determination of δ13C was always conducted in offline carbonaceous aerosol samples. The poor time-resolution results cannot provide information regarding the temporal evolution of δ13C at a short-time scale. In this study, we developed a new system for online measurements of δ13C in atmospheric carbonaceous aerosols by combining a semicontinuous organic carbon/elemental carbon (OC/EC) analyzer and online cavity ring-down spectroscopy (CRDS) (OC/EC analyzer-CRDS). To provide better stability in the determination of δ13C, a carrier gas with CO2 (∼200 ppm) in "balance gas" was used, and Keeling analysis was employed to separate the δ13C signal of the sample from background CO2 gas. Our results showed that the accuracy and absolute precision of the δ13C measurements by the OC/EC analyzer-CRDS system were better than 0.1‰ and 0.5‰, respectively, for the samples containing carbon content more than 5 µg. Furthermore, we employed this system to monitor δ13C (δ13C-TC) in particulate total carbon (TC) with a time resolution of 2-4 h over Beijing in late summer and early autumn, 2019. During the sampling period, the TC concentrations varied from 0.1 to 12.0 µg m-3 with a mean value of 6.0 ± 2.4 µg m-3. The δ13C-TC ranged from -28.2 to -24.2‰ (mean value was -25.9 ± 0.9‰) without significant diurnal variations, suggesting similar contributing sources to TC. Comparing the δ13C signatures of different emissions, we found that liquid fuels and primary and secondary C3 plants were likely the dominant sources of particulate TC. Finally, we found that atmospheric heavy precipitation washed out the aged aerosols from the polluted air, resulting in significant depletion (∼2.4‰) of δ13C-TC in the atmosphere. This paper described a novel system for conducting online measurements of δ13C in atmospheric carbonaceous aerosols and provided us information to better understand the temporal evolution of emission sources and atmospheric processes of carbonaceous aerosols.

[Chemical Characteristics and Source Apportionment of Water-Soluble Ions in Atmosphere Aerosols over the East China Sea Island During Winter and Summer].

A total of 70 total suspended particulate (TSP) samples were collected from December 2017 to February 2018 and June to August 2018 in Shengsi Islet, East China Sea. In this study, the mass concentrations of water-soluble ions in the TSP (including Na+, K+, NH4+, Mg2+, Ca2+, Cl-, SO42-, NO3-, and MSA) samplers were determined by ion chromatography. The chemical characteristics, seasonal differences, and main sources of water-soluble ions in this background aerosol site were investigated by a multiple-technique analysis combining a HYSPLIT model, correlation analysis of water-soluble ions, and primary component analysis. The results showed that the average mass concentrations of TSP and the main water-soluble inorganic ions (WSIIs) were both high in winter and low in summer; the average mass concentration of total WSIIs in winter was (26.5±16.3) µg·m-3, and in summer was (8.8±3.8) µg·m-3. Secondary inorganic ions (NO3-, SO42-, and NH4+) are the most important ionic components in TSP, which accounted for 86.2% and 74.9% of TWSIIs in winter and summer, respectively. Meanwhile, the study site was affected by seasonal temperature change, long-distance transmission, and summer biogenic sulfates. The mass concentration of nitrate was highest in winter, and the mass concentration of sulfate was highest in summer. Anthropogenic sources were the main source of nss-SO42- in atmospheric aerosols. The analysis of sulfate sources showed that contributions of biogenic sulfates to nss-SO42- were 28.1% and 5.9% in summer and winter, respectively. The results of principal component analysis indicated that the main sources of aerosol chemical composition were marine and anthropogenic sources in summer and winter, respectively. In winter, Cl- showed a certain degree of enrichment due to the influence of human activities, and the average value of the enrichment factor was 38.5%.

[Source Apportionment and Health Risk Assessment of Polycyclic Aromatic Hydrocarbons in PM2.5 in Changchun City, Autumn of 2017].

In this study, 30 PM2.5 samples were collected from the atmosphere in Changchun City in the autumn of 2017. The concentration and composition characteristics of 17 polycyclic aromatic hydrocarbons (PAHs) in the samples were analyzed by gas chromatography mass spectrometry (GC-MS). The diagnostic ratio and principal component analysis method were used to determine the source of PAHs pollution. The health risk assessment was carried out by both calculating the equivalent carcinogenic concentration of benzo(a)pyrene and the lifetime risk of cancer. Results show that the average PM2.5 concentration in autumn in Changchun is (50.84±12.23) µg·m-3, and the content of organic carbon (OC) and elemental carbon (EC) are (17.07±5.64) µg·m-3 and (1.33±0.75) µg·m-3, respectively, accounting for 37% of the total PM2.5. The total concentration of PAHs is (15.69±5.93) ng·m-3, which was dominated by medium- to high-ring-number PAHs, accounting for 84.26% of total PAHs. The atmospheric PAHs in Changchun mainly originate from motor vehicle exhaust emissions (44.48%) > coal combustion (29.16%) > biomass burning (26.36%), local transportation (gasoline vehicles) emissions being the main source of pollution. The average carcinogenic concentration of benzo(a)pyrene is in the range of 1.55 ng·m-3 and 5.38 ng·m-3, and the average carcinogenic equivalent concentration is (6.44±1.53) ng·m-3, which is generally considered a slight pollution level. The ingestion of PAHs by breathing is the most harmful to the health of adult women, followed by adult males and children, however since the lifetime carcinogenic risk value of the entire population did not exceed 1×10-6, their health risks are considered to be at acceptable levels.

Specific sources of health risks caused by size-resolved PM-bound metals in a typical coal-burning city of northern China during the winter haze event.

High particulate matter (PM) pollution frequently occurs in winter over northern China , resulting in threats to human health. To date, there are limited studies to link source apportionments and health risk assessments in the different size-resolved PM samples during high PM events. In this study, size-segregated PM samples were collected in Linfen, a typical coal-burning city, in northern China during a wintertime haze pollution. In addition to water-soluble ions and carbon contents, metallic elements in the different size-segregated PM samples were also determined for health risk assessments by inhalation of PM. During the sampling period, the average concentration of PM10 was 274 ±â€¯57 µg m-3 with a major fraction (73%) of organic material and secondary-related aerosols, and an insignificant portion of trace elements (TEs, ~ 3%). The size distribution showed that As and Se, markers of coal combustion, exhibited a mono-modal distribution with a major peak at 0.4-0.7 µm and the others mostly possessed mono-/bi-modal patterns with a major peak at 3.3-5.8 µm. The cancer risk (CR) resulted from PM10 metals by inhalation was estimated to be 2.91 × 10-5 for children and 7.75 × 10-5 for adults while non-cancer risk (NCR) was 2.10 for children and 0.70 for adults. Chromium (Cr) was the dominant species (~89%) of cancer risk in PM10. Road dust was a major fraction (~65%) to total metals in coarse PM (dp > 3.3 µm) whereas coal combustion was a dominant source (~55%) in submicron (dp < 1.1 µm) PM metals. However, traffic emissions (40%) and coal combustion (36%) were the dominant sources of CR since both emissions contributed major fractions (74%) to Cr, especially in submicron PM which exhibited high deposition efficiency of TEs into respiratory tracts, resulting in high CR in Linfen City.

Stable Sulfur Isotopes Revealed a Major Role of Transition-Metal Ion-Catalyzed SO2 Oxidation in Haze Episodes.

Secondary sulfate aerosols played an important role in aerosol formation and aging processes, especially during haze episodes in China. Secondary sulfate was formed via atmospheric oxidation of SO2 by OH, O3, H2O2, and transition-metal-catalyzed (TMI) O2. However, the relative importance of these oxidants in haze episodes was strongly debated. Here, we use stable sulfur isotopes (δ34S) of sulfate aerosols and a Rayleigh distillation model to quantify the contributions of each oxidant during a haze episode in Nanjing, a megacity in China. The observed δ34S values of sulfate aerosols showed a negative correlation with sulfur oxidation ratios, which was attributed to the sulfur isotopic fractionations during the sulfate formation processes. Using the average fractionation factor calculated from our observations and zero-dimensional (0-D) atmospheric chemistry modeling estimations, we suggest that OH oxidation was trivial during the haze episode, while the TMI pathway contributed 49 ± 10% of the total sulfate production and O3/H2O2 oxidations accounted for the rest. Our results displayed good agreement with several atmospheric chemistry models that carry aqueous and heterogeneous TMI oxidation pathways, suggesting the role of the TMI pathway was significant during haze episodes.