Emission of PAHs, NPAHs and OPAHs from residential honeycomb coal briquette combustion

Coal combustion is one of the most significant sources of air pollution in China. In this study, emission factors (EFs) of 15 polycyclic aromatic hydrocarbons (PAHs), 26 nitrated PAHs (NPAHs) and 6 oxygenated PAHs (OPAHs) were determined in five different coals with different geological maturity (vitrinite reflectance <i>R</i>_O = 0.77–1.88%) burned in the form of honeycomb briquettes. The total EFs ranged from 9.82 to 215 mg kg^–1 for PAHs, 0.14 to 1.88 mg kg^–1 for NPAHs and 4.47 to 20.8 mg kg^–1 for OPAHs. Measured EFs and gas-particle partitioning varied depending on the geological maturity. The lowest EFs were found in anthracite. The proportion of PAHs, NPAHs and OPAHs in gaseous phase increasing with increased geological maturity. The coal with higher geological maturity produced more 3-ring PAHs. On the basis of the statistical analysis for the residential sector of China in 2008, PAHs, NPAHs and OPAHs emitted from residential honeycomb coal briquettes were 4.36 Gg, 0.03 Gg and 0.47 Gg in 2007, respectively. By 2020, the emission would decrease to 2.18 Gg, 0.02 Gg and 0.24 Gg for PAHs, NPAHs and OPAHs due to the increasing usage of new energy resources. If only anthracite is used as the residential coal, 93% PAHs, 87% NPAHs and 71% OPAHs would be reduced in 2020

Measurement report: Molecular characteristics of cloud water in southern China and insights into aqueous-phase processes from Fourier transform ion cyclotron resonance mass spectrometry

Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C$_{5-30}$H$_{4-55}$O$_{1-15}$N$_{0-2}$S$_{0-2}$) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %–65.3 % of relative abundance), followed by CHO (13.8 %–52.1%). S-containing formulas constitute ∼5 %–20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45–0.56, and the double bond equivalent of 5.10–5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM$_{2.5}$. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by −N$_{2}$O$_{5}$ function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions

Impact of in-cloud aqueous processes on the chemical compositions and morphology of individual atmospheric aerosols

The composition, morphology, and mixing structure of individual cloud residues (RES) and interstitial particles (INT) at a mountaintop site were investigated. Eight types of particles were identified, including sulfate-rich (S-rich), S-organic matter (OM), aged soot, aged mineral dust, aged fly ash, aged metal, refractory, and aged refractory mixture. A shift of dominant particle types from S-rich (29 %) and aged soot (27 %) in the INT to aged refractory mixture (23 %) and S-OM (22 %) in the RES is observed. In particular, particles with organic shells are enriched in the RES (27 %) relative to the INT (12 %). Our results highlight that the formation of more oxidized organic matter in the cloud contributes to the existence of organic shells after cloud processing. The fractal dimension (D$_{f}$), a morphologic parameter to represent the branching degree of particles, for soot particles in the RES (1.82 ± 0.12) is lower than that in the INT (2.11 ± 0.09), which indicates that in-cloud processes may result in less compact soot. This research emphasizes the role of in-cloud processes in the chemistry and microphysical properties of individual particles. Given that organic coatings may determine the particle hygroscopicity, activation ability, and heterogeneous chemical reactivity, the increase of OM-shelled particles upon in-cloud processes should have considerable implications

Drug-coated balloons: A better revascularization strategy in patients with multivessel coronary artery disease undergoing one-stop hybrid coronary revascularization surgery

Background: The optimal revascularization strategy for non-left anterior descending coronary artery (LAD) lesions during one-stop hybrid coronary revascularization (HCR) surgery lacks current evidence.Aims: This study aimed to compare the outcomes of the drug-coated balloon (DCB) and drug-eluting stent (DES) strategies in patients with non-small non-LAD lesions undergoing one-stop HCR.Methods: A total of 141 consecutive patients with multivessel coronary artery disease (MVCAD) undergoing one-stop HCR between June 1, 2018 and March 1, 2022 were retrospectively included in this study. In-hospital outcomes and mid-term major adverse cardiovascular and cerebrovascular events (MACCE) were observed. Kaplan-Meier curve analysis was used to evaluate the MACCE-free survival rate. The Cox proportional hazard model was used to identify risk factors of mid-term MACCE.Results: Thirty-eight and 103 patients received only DCB or DES therapy, respectively, in this study. There were no significant differences in demographic characteristics and laboratory parameters between the two groups. The in-hospital MACCE rate in the DES group was numerically higher than that in the DCB group (9.7% vs. 5.3%, respectively), but the difference was not statistically significant (P = 0.4). The incidence of MACCE after patients’ discharge was significantly higher in the DES group (22% vs. 5.3%, respectively, P = 0.02) during a median follow-up of 20 months. After multivariable Cox proportional hazard analysis, DCB therapy was independently associated with reduced risk of mid-term MACCE (hazard ratio, 0.21; 95% confidence interval, 0.06–0.91; P = 0.04).Conclusion: For patients with MVCAD undergoing one-stop HCR, DCB therapy may be the optimal revascularization strategy for non-small non-LAD coronary artery lesions with a significantly lower rate of mid-term MACCE

Measurements of traffic-dominated pollutant emissions in a Chinese megacity

Direct measurements of NOx, CO and aromatic volatile organic compound (VOC) (benzene, toluene, C2-benzenes and C3-benzenes) flux were made for a central area of Beijing using the eddy-covariance technique. Measurements were made during two intensive field campaigns in central Beijing as part of the Air Pollution and Human Health (APHH) project, the first in November–December 2016 and the second during May–June 2017, to contrast wintertime and summertime emission rates. There was little difference in the magnitude of NOx flux between the two seasons (mean NOx flux was 4.41 mg m−2 h−1 in the winter compared to 3.55 mg m−2 h−1in the summer). CO showed greater seasonal variation, with mean CO flux in the winter campaign (34.7 mg m−2 h−1) being over twice that of the summer campaign (15.2 mg m−2 h−1). Larger emissions of aromatic VOCs in summer were attributed to increased evaporation due to higher temperatures. The largest fluxes in NOx and CO generally occurred during the morning and evening rush hour periods, indicating a major traffic source with high midday emissions of CO, indicating an additional influence from cooking fuel. Measured NOx and CO fluxes were then compared to the MEIC 2013 emissions inventory, which was found to significantly overestimate emissions for this region,providing evidence that proxy-based emissions inventories have positive biases in urban centres. This first set of pollutant fluxes measured in Beijing provides an important benchmark of emissions from the city which can help to inform and evaluate current emissions inventories

Volatile organic compound mixing ratios above Beijing in November and December 2016

Volatile organic compounds (VOCs) are emitted into the atmosphere from vegetation and anthropogenic sources such as fossil fuel combustion, biomass burning and the evaporation of petroleum products. These compounds play an important role in the chemistry of the lower atmosphere through secondary organic aerosol (SOA) formation and facilitating the formation of tropospheric ozone. As well as their indirect impact on human health via the formation of ozone and SOA, some VOCs, including benzene, directly affect human health adversely. Here we report VOC mixing ratios measured in Beijing during a 5 week intensive field campaign from the 7th November to the 10th December 2016. This work was carried out as part of the Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing) work project within the Air Pollution and Human Health in a Developing Megacity (APHH-Beijing) research programme. APHH is a large multi-institutional study which aims to record the concentrations and identify the sources of urban air pollutants in Beijing, determine exposure, understand their effects on human health, and to identify solutions. VOC mixing ratios were recorded using a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS, Ionicon Analytik) and a Selected Ion Flow Tube-Mass Spectrometer (SIFT-MS, SYFT Technologies). During the measurement period Beijing was subject to multiple pollution events that alternated with periods of relatively good air quality, allowing the VOCs within the polluted air masses to be identified and quantified. VOCs were sampled at 102 m with additional gradient measurements made at 3, 15, 32 and 64 m providing a vertical profile of VOC mixing ratios. Mixing ratios of methanol, acetonitrile, acetaldehyde, acetone, isoprene and aromatics species will be reported together with a discussion of potential sources. Comparisons will then be drawn with other large cities

Surface-atmosphere fluxes of volatile organic compounds in Beijing

Mixing ratios of volatile organic compounds (VOCs) were recorded in two field campaigns in central Beijing as part of the Air Pollution and Human Health in a Chinese Megacity (APHH) project. These data were used to calculate, for the first time in Beijing, the surface-atmosphere fluxes of VOCs using eddy covariance, giving a top-down estimation of VOC emissions from a central area of the city. The results were then used to evaluate the accuracy of the Multi-resolution Emission Inventory for China (MEIC). The APHH winter and summer campaigns took place in November and December 2016 and May and June 2017, respectively. The largest VOC fluxes observed were of small oxygenated compounds such as methanol, ethanol + formic acid and acetaldehyde, with average emission rates of 8.31±8.5, 3.97±3.9 and 1.83±2.0nmolm-2s-1, respectively, in the summer. A large flux of isoprene was observed in the summer, with an average emission rate of 5.31±7.7nmolm-2s-1. While oxygenated VOCs made up 60% of the molar VOC flux measured, when fluxes were scaled by ozone formation potential and peroxyacyl nitrate (PAN) formation potential the high reactivity of isoprene and monoterpenes meant that these species represented 30% and 28% of the flux contribution to ozone and PAN formation potential, respectively. Comparison of measured fluxes with the emission inventory showed that the inventory failed to capture the magnitude of VOC emissions at the local scale

Atmospheric pollution and human health in a Chinese megacity (APHH-Beijing) programme. Final report

In 2016, over 150 UK and Chinese scientists joined forces to understand the causes and impacts - emission sources, atmospheric processes and health effects - of air pollution in Beijing, with the ultimate aim of informing air pollution solutions and thus improving public health. The Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) research programme succeeded in delivering its objectives and significant additional science, through a large-scale, coordinated multidisciplinary collaboration. In this report are highlighted some of the research outcomes that have potential implications for policymaking

Evaluating the sensitivity of radical chemistry and ozone formation to ambient VOCs and NOxin Beijing

Measurements of OH, HO2, complex RO2 (alkene-and aromatic-related RO2) and total RO2 radicals taken during the integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO) campaign in central Beijing in the summer of 2017, alongside observations of OH reactivity, are presented. The concentrations of radicals were elevated, with OH reaching up to 2:8 × 107 molecule cm-3, HO2 peaking at 1 × 109 molecule cm-3 and the total RO2 concentration reaching 5:5×109 molecule cm-3. OH reactivity (k.OH/) peaked at 89 s-1 during the night, with a minimum during the afternoon of 22s-1 on average. An experimental budget analysis, in which the rates of production and destruction of the radicals are compared, highlighted that although the sources and sinks of OH were balanced under high NO concentrations, the OH sinks exceeded the known sources (by 15 ppbvh-1) under the very low NO conditions (< 0:5ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by 50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (< 1ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concentrations. The model also under-predicted the observed k.OH/consistently by 10s-1 across all NOx levels, highlighting that the good agreement for OH was fortuitous due to a cancellation of missing OH source and sink terms in its budget. Including heterogeneous loss of HO2 to aerosol surfaces did reduce the modelled HO2 concentrations in line with the observations but only at NO mixing ratios < 0:3ppbv. The inclusion of Cl atoms, formed from the photolysis of nitryl chloride, enhanced the modelled RO2 concentration on several mornings when the Cl atom concentration was calculated to exceed 1 × 104 atoms cm-3 and could reconcile the modelled and measured RO2 concentrations at these times. However, on other mornings, when the Cl atom concentration was lower, large under-predictions in total RO2 remained. Furthermore, the inclusion of Cl atom chemistry did not enhance the modelled RO2 beyond the first few hours after sunrise and so was unable to resolve the modelled under-prediction in RO2 observed at other times of the day. Model scenarios, in which missing VOC reactivity was included as an additional reaction that converted OH to RO2, highlighted that the modelled OH, HO2 and RO2 concentrations were sensitive to the choice of RO2 product. The level of modelled to measured agreement for HO2 and RO2 (both complex and simple) could be improved if the missing OH reactivity formed a larger RO2 species that was able to undergo reaction with NO, followed by isomerisation reactions reforming other RO2 species, before eventually generating HO2. In this work an a-pinene-derived RO2 species was used as an example. In this simulation, consistent with the experimental budget analysis, the model underestimated the observed OH, indicating a missing OH source. The model uncertainty, with regards to the types of RO2 species present and the radicals they form upon reaction with NO (HO2 directly or another RO2 species), leads to over an order of magnitude less O3 production calculated from the predicted peroxy radicals than calculated from the observed peroxy radicals at the highest NO concentrations. This demonstrates the rate at which the larger RO2 species propagate to HO2, to another RO2 or indeed to OH needs to be understood to accurately simulate the rate of ozone production in environments such as Beijing, where large multifunctional VOCs are likely present

Using highly time-resolved online mass spectrometry to examine biogenic and anthropogenic contributions to organic aerosol in Beijing

Organic aerosols, a major constituent of fine particulate mass in megacities, can be directly emitted or formed from secondary processing of biogenic and anthropogenic volatile organic compound emissions. The complexity of volatile organic compound emission sources, speciation and oxidation pathways leads to uncertainties in the key sources and chemistry leading to formation of organic aerosol in urban areas. Historically, online measurements of organic aerosol composition have been unable to resolve specific markers of volatile organic compound oxidation, while offline analysis of markers focus on a small proportion of organic aerosol and lack the time resolution to carry out detailed statistical analysis required to study the dynamic changes in aerosol sources and chemistry. Here we use data collected as part of the joint UK–China Air Pollution and Human Health (APHH-Beijing) collaboration during a field campaign in urban Beijing in the summer of 2017 alongside laboratory measurements of secondary organic aerosol from oxidation of key aromatic precursors (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene, isopropyl benzene and 1-methyl naphthalene) to study the anthropogenic and biogenic contributions to organic aerosol. For the first time in Beijing, this study applies positive matrix factorisation to online measurements of organic aerosol composition from a time-of-flight iodide chemical ionisation mass spectrometer fitted with a filter inlet for gases and aerosols (FIGAERO-ToF-I-CIMS). This approach identifies the real-time variations in sources and oxidation processes influencing aerosol composition at a near-molecular level. We identify eight factors with distinct temporal variability, highlighting episodic differences in OA composition attributed to regional influences and in situ formation. These have average carbon numbers ranging from C5–C9 and can be associated with oxidation of anthropogenic aromatic hydrocarbons alongside biogenic emissions of isoprene, α-pinene and sesquiterpenes