Significant Increase in Ammonia Emissions in China: Considering Nonagricultural Sectors Based on Isotopic Source Apportionment.

Isotopic source apportionment results revealed that nonagricultural sectors are significant sources of ammonia (NH3) emissions, particularly in urban areas. Unfortunately, nonagricultural sources have been substantially underrepresented in the current anthropogenic NH3 emission inventories (EIs). Here, we propose a novel approach to develop a gridded EI of nonagricultural NH3 in China for 2016 using a combination of isotopic source apportionment results and the emission ratios of carbon monoxide (CO) and NH3. We estimated that isotope-corrected nonagricultural NH3 emissions were 4370 Gg in China in 2016, accounting for an increase in the total NH3 emissions from 7 to 31%. As a result, compared to the original NH3 EI, the annual emissions of total NH3 increased by 35%. Thus, in comparison to the simulation driven by the original NH3 EI, the WRF-Chem model driven by the isotope-corrected NH3 EI has reduced the model biases in the surface concentrations and dry deposition flux of reduced nitrogen (NHx = gaseous NH3 + particulate NH4+) by 23 and 31%, respectively. This study may have wide-ranging implications for formulating targeted strategies for nonagricultural NH3 emissions controls, making it facilitate the achievement of simultaneously alleviating nitrogen deposition and atmospheric pollution in the future.

A New Index Developed for Fast Diagnosis of Meteorological Roles in Ground-Level Ozone Variations.

China experienced worsening ground-level ozone (O3) pollution from 2013 to 2019. In this study, meteorological parameters, including surface temperature (T 2 ), solar radiation (SW), and wind speed (WS), were classified into two aspects, (1) Photochemical Reaction Condition (PRC = T 2 × SW) and (2) Physical Dispersion Capacity (PDC = WS). In this way, a Meteorology Synthetic Index (MSI = PRC/PDC) was developed for the quantification of meteorology-induced ground-level O3 pollution. The positive linear relationship between the 90th percentile of MDA8 (maximum daily 8-h average) O3 concentration and MSI determined that the contribution of meteorological changes to ground-level O-3 varied on a latitudinal gradient, decreasing from ∼40% in southern China to 10%-20% in northern China. Favorable photochemical reaction conditions were more important for ground-level O3 pollution. This study proposes a universally applicable index for fast diagnosis of meteorological roles in ground-level O3 variability, which enables the assessment of the observed effects of precursor emissions reductions that can be used for designing future control policies. ELECTRONIC SUPPLEMENTARY MATERIAL: Supplementary material is available in the online version of this article at 10.1007/s00376-021-1257-x.

Size-distribution and driving factors of aerosol oxidative potential in rural kitchen microenvironments of northeastern India.

This study reports size-resolved dithiothreitol (DTT)-based oxidative potential (OP: total and water-soluble) in rural kitchens using liquefied petroleum gas (LPG), firewood (FW), and mixed biomass (MB) fuels in northeastern (NE) India. In comparison to LPG, volume-normalized total OP (OPtotal(v)DTT) was enhanced by a factor of ∼5 in biomass-using kitchens (74 ± 35 to 78 ± 42 nmol min-1 m-3); however, mass-normalized total OP (OPtotal(m)DTT) was similar between LPG and FW users and higher by a factor of 2 in MB-using kitchens. The water-insoluble OP (OPwi(v, m)DTT) fraction in OPtotal(v, m)DTT was greater than 50% across kitchens. Size distributions across kitchens and OPDTT categories ranged from unimodal to trimodal. OPws(v)DTT was driven by metals as well as organics across size fractions while OPwi(v)DTT was majorly constrained by metals with an increasing importance of organics in fine particles of biomass-using kitchens. Multiple linear regression analysis revealed that Cu and Ba explained 71% of the OPtotal(v)DTT variability in LPG-using kitchens, while water-soluble organic carbon (WSOC) and Ba were responsible for 44% variability in FW-using kitchens. Finally, the high internal dose of OPtotal(v)DTT (28-31 nmol min-1 m-3) in biomass-using kitchens established the severity of oxidative stress on the exposed population.

Contribution of marine biological emissions to gaseous methylamines in the atmosphere: An emission inventory based on multi-source data sets.

Methylamines are a class of highly reactive organic alkaline gases in the atmosphere. At present, the gridded emission inventories of amines used in the atmospheric numerical model is mostly based on the amine/ammonia ratio method and do not consider the air-sea exchange of methylamines, which oversimplifies the emission scenario. Marine biological emissions (MBE), an important source of methylamines, has been insufficiently investigated. These shortcomings in the inventories can limit the simulation of amines by numerical models in the context of compound pollution in China. To acquire a more complete gridded inventory of amines (monomethylamine (MMA), dimethylamines (DMA), and trimethylamines (TMA)), we established a more reasonable MBE inventory of amines by using multi-source data sets (Sea Surface Temperature (SST), Chlorophyll-a (Chla), Sea Surface Salinity (SSS), NH3 column concentration (NH3), and Wind Speed (WS)), and merged it with the anthropogenic emissions (AE) inventory (by adopting the amine/ammonia ratio method and the Multi-resolution Emission Inventory for China (MEIC)). The new methodology can reveal the air-sea exchange fluxes and direction of different amines. Oceans can act as a sink for DMA and source for TMA while it can be either a source or sink for MMA. The concentration of amines above the coastal area increased significantly when the MBE was merged to the AE inventory. TMA and MMA showed significant increases, TMA increased by 43,917.0 %, and 804.0 %, in July 2015 and December 2019, respectively; while MMA increased by 2635.4 % and 0.37 % during the same periods; however, only slight changes were observed in the DMA concentration (-3.9 % in July 2015, and 1.1 % in December 2019). WS, Chla, and the total dissolved concentration of amines ([C+(s)tot]) were found to be the dominant factors affecting MBE fluxes. In addition, the emission fluxes and spatial distribution of AE, and wet deposition also affect the simulation of amines concentration.

Optical source apportionment of aqueous brown carbon (BrC) on a daytime and nighttime basis in the eastern Indo-Gangetic Plain (IGP) and insights from 13C and 15N isotopic signatures.

This study reports day-night and seasonal variations of aqueous brown carbon (BrCaq) and constituent humic-like substances (HULIS) (neutral and acidic HULIS: HULIS-n and HULIS-a) from the eastern Indo-Gangetic Plain (IGP) of India during 2019-2020. This is followed by the application of the receptor model positive matrix factorization (PMF) for optical source apportionment of BrCaq and the use of stable isotopic ratios (δ13C and δ15N) to understand atmospheric processing. Nighttime BrCaq absorption and mass absorption efficiencies (MAE) were enhanced by 40-150 % and 50-190 %, respectively, compared to the daytime across seasons, possibly as a combined effect from daytime photobleaching, dark-phase secondary formation, and increased nighttime emissions. MAE250 nm/MAE365 nm (i.e., E2/E3) ratios and Angstrom Exponents revealed that BrCaq and HULIS-n were relatively more aromatic and conjugated during the biomass burning-dominated periods while BrCaq and HULIS-a were comprised mostly of non-conjugated aliphatic structures from secondary processes during the photochemistry-dominated summer. The relative radiative forcing of BrCaq with respect to elemental carbon (EC) was 10-12 % in the post-monsoon and winter in the 300-400 nm range. Optical source apportionment using PMF revealed that BrCaq absorption at 300, 365 and 420 nm wavelengths in the eastern IGP is mostly from biomass burning (60-75 %), followed by combined marine and fossil fuel-derived sources (24-31 %), and secondary processes (up to 10 %). Source-specific MAEs at 365 nm were estimated to be the highest for the combined marine and fossil fuel source (1.34 m2 g-1) followed by biomass burning (0.78 m2 g-1) and secondary processing (0.13 m2 g-1). Finally, δ13C and δ15N isotopic analysis confirmed the importance of summertime photochemistry and wintertime NO3--dominated chemistry in constraining BrC characteristics. Overall, the quantitative apportionment of BrCaq sources and processing reported here can be expected to lead to targeted source-specific measurements and a better understanding of BrC climate forcing in the future.

Public Concern about Air Pollution and Related Health Outcomes on Social Media in China: An Analysis of Data from Sina Weibo (Chinese Twitter) and Air Monitoring Stations.

To understand the temporal variation, spatial distribution and factors influencing the public's sensitivity to air pollution in China, this study collected air pollution data from 2210 air pollution monitoring sites from around China and used keyword-based filtering to identify individual messages related to air pollution and health on Sina Weibo during 2017-2021. By analyzing correlations between concentrations of air pollutants (PM2.5, PM10, CO, NO2, O3 and SO2) and related microblogs (air-pollution-related and health-related), it was found that the public is most sensitive to changes in PM2.5 concentration from the perspectives of both China as a whole and individual provinces. Correlations between air pollution and related microblogs were also stronger when and where air quality was worse, and they were also affected by socioeconomic factors such as population, economic conditions and education. Based on the results of these correlation analyses, scientists can survey public concern about air pollution and related health outcomes on social media in real time across the country and the government can formulate air quality management measures that are aligned to public sensitivities.

Synergistic effects of biogenic volatile organic compounds and soil nitric oxide emissions on summertime ozone formation in China.

Natural emissions play a key role in modulating the formation of ground-level ozone (O3), especially emissions of biogenic volatile organic compounds (BVOCs) and soil nitric oxide (SNO), and their individual effects on O3 formation have been previously quantified and evaluated. However, their synergistic effects remain unclear and have not yet been well assessed. By applying the Weather Research and Forecasting (WRF) model coupled with the Chemistry-Model of Emissions of Gases and Aerosols from Nature (WRF/Chem-MEGAN) model, this study reveals that in the presence of sufficient BVOC emissions, which act as a fuel, SNO emissions act as a fuel additive and promote the chemical reactions of BVOCs and the subsequent production of O3. Consequently, the synergistic effects of BVOC and SNO emissions on summertime O3 production surpassed the sum of their individual effects by as much as 10-20 µg m-3 in eastern China in 2014. In order to reduce O3 concentration to a level corresponding to no natural emissions of BVOC or SNO (i.e., the BASE scenario), the anthropogenic volatile organic compound (AVOC) emissions in the scenario considers BVOC and SNO emissions must be reduced by 1.76 times that of the BASE scenario. This study demonstrates that the synergistic effects of BVOC and SNO emissions can impede ground-level O3 regulation and can subsequently impose stricter requirements on anthropogenic precursor emission control in China. The results of this study can also inform efforts in other regions that are still combating ground-level O3 pollution.

Seasonal variations in aerosol acidity and its driving factors in the eastern Indo-Gangetic Plain: A quantitative analysis.

This study employs ISORROPIA-II for the evaluation of aerosol acidity and quantification of contributions from chemical species and meteorological parameters to acidity variation in the Indian context. PM2.5 samples collected during summer (April-July 2018), post-monsoon (September-November 2018), and winter (December 2018-January 2019) from a rural receptor location in the eastern Indo-Gangetic Plain (IGP) were analyzed for ionic species, water-soluble organic carbon (WSOC), and organic and elemental carbon (OC, EC) fractions. This was followed by estimation of the in situ aerosol pH and liquid water content (LWC) using the forward mode of ISORROPIA-II, which is less sensitive to measurement uncertainty compared to the reverse mode, for a K+-Ca2+-Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O system. Aerosol pH was moderately acidic (summer: 2.93 ± 0.67; post-monsoon: 2.67 ± 0.23; winter: 3.15 ± 0.34) and was most sensitive to SO42- and total ammonium (TNH3) variation. The LWC of aerosol showed an increasing trend from summer (16.6 ± 13.6 µg m-3) through winter (32.9 ± 10.4 µg m-3). With summer as the baseline, the largest changes in aerosol pH during the other seasons was driven by SO42- (ΔpH: -0.70 to -0.82 units), followed by TNH3 (ΔpH: +0.25 to +0.38 units) with K+ and temperature being significant only during winter (ΔpH: +0.51 and + 0.46 units, respectively). The prevalent acidity regime provided three major insights: i) positive summertime Cl- depletion (49 ± 20%) as a consequence of SO42- substitution increased aerosol pH by 0.03 ± 0.20 units and decreased LWC by 2.4 ± 5.9 µg m-3; ii) the rate of strong acidity (H+str) neutralization and the [H+str]/[SO42-] molar ratio suggested the existence of bounded acidity in ammonium-rich (winter) conditions; and iii) significant correlations between LWC, WSOC, and secondary organics during post-monsoon and winter pointed towards a possible indirect role of WSOC in enhancing LWC of aerosol, thereby increasing pH. Given the inability of proxies such as H+str and charge ratios to accurately represent aerosol pH as demonstrated here, this study emphasizes the need for rigorous thermodynamic model-based evaluation of aerosol acidity in the Indian scenario.

Assessment of background ozone concentrations in China and implications for using region-specific volatile organic compounds emission abatement to mitigate air pollution.

Mitigation of ambient ozone (O3) pollution is a great challenge because it depends heavily on the background O3 which has been poorly evaluated in many regions, including in China. By establishing the relationship between O3 and air temperature near the surface, the mean background O3 mixing ratios in the clean and polluted seasons were determined to be 35-40 and 50-55 ppbv in China during 2013-2019, respectively. Simulations using the chemical transport model (i.e., the Weather Research and Forecasting coupled with Chemistry model, WRF/Chem) suggested that biogenic volatile organic compounds (VOC) emissions were the primary contributor to the increase in the background O3 in the polluted season (BOP) compared to the background O3 in the clean season (BOC), ranging from 8 ppbv to 16 ppbv. More importantly, the BOP continuously increased at a rate of 0.6-8.0 ppbv yr-1 during 2013-2019, while the non-BOP stopped increasing after 2017. Consequently, an additional 2%-16% reduction in anthropogenic VOC emissions is required to reverse the current O3 back to that measured in the period from 2013 to 2017. The results of this study emphasize the importance of the relative contribution of the background O3 to the observed total O3 concentration in the design of anthropogenic precursor emission control strategies for the attainment of O3 standards.

Abundance and fractional solubility of phosphorus and trace metals in combustion ash and desert dust: Implications for bioavailability and reactivity.

Aerosol phosphorus (P) and trace metals derived from natural processes and anthropogenic emissions have considerable impacts on ocean ecosystems, human health, and atmospheric processes. However, the abundance and fractional solubility of P and trace metals in combustion ash and desert dust, which are two of the largest emission sources of aerosols, are still not well understood. In this study, the abundance and fractional solubility of P and trace metals in seven coal fly ash samples, two municipal waste fly ash samples, and three desert dust samples were experimentally examined. It was found that the abundance of aluminum (Al) in combustion ash was comparable or even higher than that in desert dust, and, therefore, care should be taken when using Al as a tracer of desert dust. The abundance and fractional solubility of P were higher in combustion ash, with a soluble P content ~4-6 times higher than that of the desert dust, indicating that combustion ash could be an important source of bioavailable P in the atmosphere. Except for Mn, the abundance and fractional solubility of other heavy metals were higher in the combustion ash compared to the desert dust, indicating the potential importance of combustion ash in ocean ecosystems, human health, and atmospheric processes. In contrast, both the abundance and solubility of Mn were highest in the desert dust, indicating a potentially important source of soluble Mn in the atmosphere. The fractional solubilities of P and trace metals are significantly affected by acidity and ions in the extraction solutions, and it is suggested that a buffer solution can better represent the acidity of the aqueous system in the true atmospheric environment. The results of this study improve our understanding of the sources of bioavailable and reactive P and trace metals in ambient aerosols.

Ozone control strategies for local formation- and regional transport-dominant scenarios in a manufacturing city in southern China.

Given the leveling off of fine particulate matter (PM2.5), ground-level ozone (O3) pollution has become one of the most significant atmospheric pollution issues in the Pearl River Delta (PRD) region in China, especially in the manufacturing city of Dongguan, which faces more severe O3 pollution. The development of strategies to control O3 precursor emissions, including volatile organic compounds (VOCs) and nitrogen oxide (NOx), depends to a large extent on the source region of the O3 pollution. In this study, by combining the Weather Research and Forecasting model coupled with chemistry (WRF-Chem), the Empirical Kinetic Modeling Approach (EKMA), and the Flexible Particle model (FLEXPART), more effective strategies of controlling O3 precursor emissions were identified under two typical types of O3 pollution episodes: local formation (LF)-dominant (8-12 September 2019) and regional transport (RT)-dominant (23-27 October 2017) episodes, distinguished by the WRF-FLEXPART model. During the LF-dominant episode, the EKMA revealed that the O3 formation in Dongguan was in a transitional regime, and the abatement of solvent use-VOCs emissions in the key area of Dongguan was more effective in reducing O3 levels, with an emission reduction benefit 1.7 times that of total VOCs emission sources throughout Dongguan. With respect to the RT-dominant episode, the reduction in VOCs emissions in the local region did not effectively curb O3 pollution, although the photochemical regime of the O3 formation in Dongguan was VOCs-limited. A 50% reduction in NOx emissions in the upwind regions (parts of Guangzhou and Huizhou) effectively decreased the O3 concentration in Dongguan by 17%. The results of this study emphasize the importance of the source region of O3 pollution in the implementation of effective O3 control strategies and provide valuable insights for region-specific precursor emission policy formulation, not only in Dongguan, but also in other regions facing severe O3 pollution.

Are fireworks a significant episodic source of brown carbon?

We hypothesize that firework events involving the combustion of charcoal fuel, organic binders, metal salts, and cellulose-based wrapping material could be significant transient sources of aerosol brown carbon (BrC). To test this, we couple high time-resolution (1 min) measurements of black carbon (BC) and BrC absorption from a 7-wavelength aethalometer with time-integrated (12-24 h) measurements of filter extracts, i.e., UV-visible, fluorescence, and Fourier-transformed infrared (FT-IR) signatures of BrC, total and water-soluble organic carbon (OC and WSOC), ionic species, and firework tracer metals during a sampling campaign covering the Diwali fireworks episode in India. In sharp contrast to BC, BrC absorption shows a distinct and considerable rise of 2-4 times during the Diwali period, especially during the hours of peak firework activity, as compared to the background. Fluorescence profiles suggest enrichment of humic-like substances (HULIS) in the firework plume, while the enhancement of BrC absorption in the 400-500 nm range suggests the presence of nitroaromatic compounds (NACs). Considerable contributions of WSOC and secondary organics to OC (44.1% and 31.2%, respectively) and of the water-soluble fraction of BrC to total BrC absorption (71.0%) during the Diwali period point toward an atmospherically processed, polar signature of firework-related BrC, which is further confirmed by FT-IR profiles. This aqueous BrC exerts a short-lived but strong effect on atmospheric forcing (12.0% vis-à-vis BC in the UV spectrum), which could affect tropospheric chemistry via UV attenuation and lead to a stabilization of the post-Diwali atmosphere, resulting in enhanced pollutant build-up and exposure.

New particle formation (NPF) events in China urban clusters given by sever composite pollution background.

New Particle Formation (NPF) refers to transformation of gaseous precursors in the atmosphere due to nucleation and subsequent growth process through physicochemical interaction. It has generated a lot of interest due to its profound impact on global and regional environment, climate and human health. We reviewed the studies on NPF in three city clusters of China: the North China Plain, the Yangtze River Delta and the Pearl River Delta obtained through experiment simulations (e.g., chamber simulation, flow-tube simulation, etc.), field observations, and numerical simulations. Due to its atmospheric background pollution and strong oxidation capacities resulting in high source rate of precursors, China's atmosphere possesses challenges different from those evaluated in previous studies on cleaning sites and other developing countries. Hence, NPF events can simultaneously exhibit high condensable sink, formation rate and growth rate. In addition, the high intensity of anthropogenic emissions in urban China has led to greater diversity of pollutant species involved in NPF nucleation and subsequent growth, compared to the dominant role of biogenic precursors at cleaning sites. Differences in geographical location and industrial structure also lead to significant distinctions in NPF characteristics of the three city clusters. Consequently, the lack of understanding of nucleation mechanism of complexly polluted background sites makes the global and regional climate models with submodels based on clean background have enormous uncertainty when applied to urban China. The establishment of a mature research ecosystem including field observations, laboratory simulations and numerical simulations is the key to the breakthrough of NPF research in China.

Peat-forest burning smoke in Maritime Continent: Impacts on receptor PM2.5 and implications at emission sources.

This study characterizes the impacts of transported peat-forest (PF) burning smoke on an urban environment and evaluates associated source burning conditions based on carbon properties of PM2.5 at the receptor site. We developed and validated a three-step classification that enables systematic and more rapid identification of PF smoke impacts on a tropical urban environment with diverse emissions and complex atmospheric processes. This approach was used to characterize over 300 daily PM2.5 data collected during 2011-2013, 2015 and 2019 in Singapore. A levoglucosan concentration of ≥0.1 µg/m3 criterion indicates dominant impacts of transported PF smoke on urban fine aerosols. This approach can be used in other ambient environments for practical and location-dependent applications. Organic carbon (OC) concentrations (as OC indicator) can be an alternate to levoglucosan for assessing smoke impacts on urban environments. Applying the OC concentration indicator identifies smoke impacts on ∼80% of daily samples in 2019 and shows an accuracy of 51-86% for hourly evaluation. Following the systematic identification of urban PM2.5 predominantly affected by PF smoke in 2011-2013, 2015 and 2019, we assessed the concentration ratio of char-EC/soot-EC as an indicator of smoldering- or flaming-dominated burning emissions. When under the influence of transported PF smoke, the mean concentration ratio of char-EC to soot-EC in urban PM2.5 decreased by >70% from 8.2 in 2011 to 2.3 in 2015 but increased to 3.8 in 2019 (p < 0.05). The reversed trend with a 65% increase from 2015 to 2019 shows stronger smoldering relative to flaming, indicating a higher level of soil moisture at smoke origins, possibly associated with rewetting and revegetating peatlands since 2016.

A comprehensive evaluation of aerosol extinction apportionment in Beijing using a high-resolution time-of-flight aerosol mass spectrometer.

An aerosol mass spectrometer (AMS) was used to measure the chemical composition of non-refractory submicron particles (NR-PM1) in Beijing from 2012 to 2013. The average concentration of NR-PM1 was 56 µg·m-3, with higher value of 106 µg·m-3 when Beijing was influenced by air masses from south in winter. Organics was the primary chemical component with a concentration of 26 µg·m-3, accounting for 46% of the total NR-PM1. The ratio of NO3-/SO42- was utilized to identify the relative contribution of stationary and traffic related resource to PM pollution. When NR-PM1 concentration was between 50 and 200 µg·m-3, NO3-/SO42-was larger than 1, indicating traffic resource contributed more than stationary resource during the aerosol growth. A new method was developed to calculate aerosol extinction coefficient (σ) as a function of aerosol optical depth (AOD) and the mixing layer height (MLH). σ derived from the new method showed a statistically significant correlation with that obtained from traditional method, which was calculated using visibility (y = 0.99x + 85 R2 = 0.69). Multiple linear regressions in dependence of chemical component were performed to evaluate light extinction apportionment. Under the overall condition, NR-PM1 contributed about 88% to the whole aerosol light extinction; organics, ammonium chloride, ammonium nitrate, ammonium sulfate, black carbon contributed 30%, 6%, 24%, 26% and 6% of the NR-PM1 light extinction, respectively. By further comparing the light extinction apportionment under the different dominated air masses, we concluded that the organics and ammonium sulfate contributed more in polluted days (36% and 23%) than that in clean days (21% and 21%). Mass ratio (MR) between NR-PM1 and black carbon (MR = massNR-PM1/massBC) was used to identify black carbon aging degree, and the result showed that aerosol mass extinction efficiency increased rapidly after MR reached about 7 in the process of black carbon aging.

Deposition of ambient particles in the human respiratory system based on single particle analysis: A case study in the Pearl River Delta, China.

It is important to evaluate how ambient particles are deposited in the human respiratory system in view of the adverse effects they pose to human health. Traditional methods of investigating human exposure to ambient particles suffer from drawbacks related either to the lack of chemical information from particle number-based measurements or to the poor time resolution of mass-based measurements. To address these issues, in this study, human exposure to ambient particulate matter was investigated using single particle analysis, which provided chemical information with a high time resolution. Based on single particle measurements conducted in the Pearl River Delta, China, nine particle types were identified, and EC (elemental carbon) particles were determined to be the most dominant type of particle. In general, the submicron size mode was dominant in terms of the number concentration for all of the particle types, except for Na-rich and dust particles. On average, around 34% of particles were deposited in the human respiratory system with 13.9%, 7.9%, and 12.6% being distributed in the head, tracheobronchial, and pulmonary regions, respectively. The amount of Na-rich particles deposited was the highest, followed by EC. The overall deposition efficiencies of the Na-rich and dust particles were higher than those of the other particle types due to their higher efficiencies in the head region, which could be caused by the greater sedimentation and impaction rates of larger particles. In the head region, the Na-rich particles made the largest contribution (30.5%) due to their high deposition efficiency, whereas in the tracheobronchial and pulmonary regions, EC made the largest contribution due to its high concentration. In summary, the findings of this initial trial demonstrate the applicability of single particle analysis to the assessment of human exposure to ambient particles and its potential to support traditional methods of analysis.

Brown carbon aerosols in the Indo-Gangetic Plain outflow: insights from excitation emission matrix (EEM) fluorescence spectroscopy.

We report the first characterization of the aerosol brown carbon (BrC) composition in the Indian context using excitation emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor (PARAFAC) analysis. We find that biomass burning (BB)-dominated wintertime aerosols in the Indo-Gangetic Plain (IGP) outflow are characterized by two humic-like (HULIS) (C1_aq and C2_aq) and one protein-like/fossil fuel-derived (C3_aq) component for aqueous-extractable BrC (BrCaq), and by one humic-like (C1_me) and one protein-like (C2_me) component for methanol-extractable BrC (BrCme). Strong correlations of the BB tracer nss-K+ with C1_aq and C2_aq (r = 0.75-0.84, p < 0.01) and C1_me (r = 0.77, p < 0.01) point towards the BB-dominated IGP outflow as the major source. This is also supported by the analysis of fluorescence indices, which suggest extensive humification of BB emissions during atmospheric transport. The HULIS components correlate significantly with BrC absorption (r = 0.85-0.94, p < 0.01), and contribute substantially to the BrC relative radiative forcing of 13-24% vis-à-vis elemental carbon (EC). There is strong evidence that the abundant BB-derived NOX leads to NO3- formation in the IGP plume and drives the formation of water-soluble nitroaromatics (NACs) that constrain BrCaq light absorption (r = 0.56, p < 0.01) to a considerable degree. Overall, the study uncovers complex atmospheric processing of the IGP outflow in winter, which has important implications for regional climate.

Sources and atmospheric processing of brown carbon and HULIS in the Indo-Gangetic Plain: Insights from compositional analysis.

We present here spectroscopic compositional analysis of brown carbon (BrC) and humic-like substances (HULIS) in the Indian context under varying conditions of source emissions and atmospheric processing. To this end, we study bulk water-soluble organic matter (WSOM), neutral- and acidic-HULIS (HULIS-n and HULIS-a), and high-polarity (HP)-WSOM collected in the eastern Indo-Gangetic Plain (IGP) with respect to UV-Vis, fluorescence, FT-IR, 1H NMR and 13C characteristics under three aerosol regimes: photochemistry-dominated summer, aged biomass burning (BB)-dominated post-monsoon, and fresh BB-dominated winter. Absorption coefficients (babs_365 nm; Mm-1) of WSOM and HULIS fractions increase by a factor of 2-9 during winter as compared to summer, with HULIS-n dominating total HULIS + HP-WSOM absorption (73-81%). Fluorophores in HULIS-n appear to contain near-similar levels of aromatic and unsaturated aliphatic conjugation across seasons, while HULIS-a exhibits distinctively smaller-chain structures in summer and post-monsoon. FT-IR spectra reveals, among others, strong signatures of aromatic phenols in winter WSOM suggesting a BB-related origin. 1H NMR-based source attribution coupled with back trajectory analysis indicate the presence of secondary and BB-related organic aerosol (SOA and BBOA) in the post-monsoon and winter, and marine-derived OA (MOA) in the summer, which is supported by 13C measurements. Overall, these observations uncover a complex interplay of emissions and atmospheric processing of carbonaceous aerosols in the IGP.

Temporal and spatial patterns of nitrogen wet deposition in different weather types in the Pearl River Delta (PRD), China.

The temporal and spatial patterns of nitrogen wet deposition were investigated in the Pearl River Delta (PRD) under different weather types. The study was carried out in 27 monitoring sites with reliable meteorological data from 2010 to 2017. Large spatial variation data showed that both annual volume weighted mean (VWM) concentrations and fluxes were higher in the central PRD while lower in the outer area. The annual mean concentrations and fluxes were in the range of 0.8-1.3 mg N L-1 and 10.9-20.6 kg N ha-1 yr-1, respectively. The monthly mean concentrations and fluxes ranged from 0.1 to 0.2 mg N L-1 and 0.4 to 2.4 kg N ha-1, respectively. Further the study data revealed that the ratio of NH4+/NO3- was 1.1 which was much lower than the ratio reported in other regions like Northern China, Sichuan Basin, the US and Europe. The flux of NH4+ in urban sites was comparable to rural sites, implying that potential non-agricultural NH3 emissions were likely to be high in the PRD. The top three weather types were E, C and SE, with the total contribution of more than a half to the flux. Multiple linear regression was used to set up an equation to predict the variation of annual fluxes under the changes in weather conditions. The result hints that the variation on annual fluxes in the PRD tends to be stable in the next 30 years. Considering the increasing impact on the ecosystem, more effort should be exerted to reduce nitrogen wet deposition in the future.

Meteorological variations impeded the benefits of recent NOx mitigation in reducing atmospheric nitrate deposition in the Pearl River Delta region, Southeast China.

The trends and variability of atmospheric nitrogen deposition in the Pearl River Delta (PRD) region for the period 2008-2017 were investigated by integrating ground- and satellite-based observations and a chemical transport model, in order to gauge the effects of emission reductions and meteorological variability. We show that dry deposition observation of oxidized nitrogen decreased at the rate of 2.4% yr-1 for a moderate reduction in NOx emissions by 27% in the past decade, while reduced nitrogen presented an increase at the rate of 2.3% yr-1 despite no regulated interventions for NH3 emissions, which is likely related to changes in atmospheric gas-particle partitioning of NH3 as reductions in SO2 and NOx emissions. These results coincide with the trends in ground-level concentrations of oxidized and reduced nitrogen compounds in the atmosphere during 2008-2017. The changes in annual deposition fluxes of total oxidized and reduced nitrogen are not statistically significant trends and largely related with the inter-annual variability in their corresponding wet depositions, which reflects combined effects of variability in precipitation amount, and changes in atmospheric nitrogen compounds which dominates wet deposition of the oxidized and reduced forms. The meteorological conditions can mask 34% and 25% decrease in total oxidized and reduced nitrogen deposition on the decadal timescale, respectively. We conclude that meteorology-driven variability probably have masked the full response of oxidized nitrogen deposition to NOx emissions reduction. Our results also imply that persistent and integrated emission control strategies on NOx and NH3 are needed to effectively reduce total nitrogen deposition fluxes towards the critical limit in the PRD region.