Formation Mechanism Of Pollution Research Articles

Investigating the Effect of Ammonia Addition on the Performance of a Heavy-Duty Natural Gas Spark Ignition Engine Operated at Stoichiometric Conditions

Abstract Due to the pressing issue of global warming, there has been a significant focus on zero- and low-carbon fuels globally. Among hydrocarbon fuels, methane is widely used in spark ignition engines due to its abundance and relatively low carbon footprint. However, to further reduce carbon emissions, interest is growing in the use of ammonia, a zero-carbon fuel, as a partial replacement for methane. Consequently, it is crucial to investigate the impact of ammonia addition on the performance of natural gas spark ignition engines. A key challenge in studying ammonia-methane engines is that the introduction of ammonia alters the formation mechanisms of nitrogen-based pollutants, resulting in the coupling of fuel-borne and air-borne nitrogen pollutants. As a result, research on the nitrogen-based emissions of ammonia-methane engines has been limited. This study addresses this issue by differentiating between atmospheric nitrogen and fuel nitrogen elements, effectively decoupling fuel-borne and air-borne nitrogen pollutants. This approach provides valuable insights into the effects of ammonia addition on the nitrogen-based pollutant characteristics of natural gas engines. The results indicate that ammonia addition introduces N2O, a species absent in pure methane engines. The N2O primarily originates from cold wall regions and the partial oxidation of ammonia released from engine crevices during the late oxidation process. Although NO remains the dominant nitrogen-based pollutant and the amount of N2O is small, the significant greenhouse gas potential of N2O warrants further attention. Furthermore, while ammonia addition increases the NO concentration in the burning zone, it slightly reduces the NO concentration at chemical equilibrium under stoichiometric conditions. As a result, engines operating with an ammonia energy substitution ratio of 0.4 exhibit lower NOx emissions compared to those fueled solely by methane. These findings underscore the need for further research into the combustion and emission characteristics of ammonia-methane spark ignition engines.

Investigation of pollution formation mechanism through the application of a diesel surrogate model for developed for a diesel-operated gas turbine system

Investigation of pollution formation mechanism through the application of a diesel surrogate model for developed for a diesel-operated gas turbine system

Spatial Dynamic Interaction Effects and Formation Mechanisms of Air Pollution in the Central Plains Urban Agglomeration in China

Accurately identifying the dynamic interaction effects and network structure characteristics of air pollution is essential for effective collaborative governance. This study investigates the spatial dynamic interactions of air pollution among 30 cities in the Central Plains Urban Agglomeration using convergent cross mapping. Social network analysis is applied to assess the overall and node characteristics of the spatial interaction network, while key driving factors are analyzed using an exponential random graph model. The findings reveal that air pollution levels in the Central Plains Urban Agglomeration initially increase before they decrease, with heavily polluted cities transitioning from centralized to sporadic distribution. Among the interactions, Heze’s air pollution impact on Kaifeng was the strongest, while Xinxiang’s impact on Changzhi was the weakest. The emission and receiving effects peaked during 2010–2012. The air pollution interactions among cities exhibit significant network characteristics, with block model results indicating that emitting and receiving relationships are primarily concentrated in the bidirectional spillover plate. Natural factors such as temperature and precipitation significantly influence the spatial interaction network. Economic and social factors like economic level and industrial sector proportion also have a significant impact. However, population density does not influence the spatial interaction network. This study contributes to understanding the spatial network of air pollution, thereby enhancing strategies for optimizing regional collaborative governance efforts to address air pollution.

Finer Particle Size Distribution and Potential Higher Toxicity of Elemental Carbon and Polycyclic Aromatic Hydrocarbons Emitted by Ships after Fuel Oil Quality Improvement.

Ship emissions are a significant source of air pollution, and the primary policy to control is fuel oil quality improvement. However, the impact of this policy on particle size distribution and composition characteristics remains unclear. Measurements were conducted on nine different vessels (ocean-going vessels, coastal cargo ships, and inland cargo ships) to determine the impact of fuel upgrading (S < 0.1% m/m marine gas oil (MGO) vs S < 0.5% m/m heavy fuel oil (HFO)) on elemental carbon (EC) and polycyclic aromatic hydrocarbons (PAHs) emitted by ships. (1) Fuel improvement significantly reduced EC and PAH emission, by 31 ± 25 and 45 ± 38%, respectively. However, particle size distributions showed a trend toward finer particles, with the peak size decreasing from DP = 0.38-0.60 μm (HFO) to DP = 0.15-0.25 μm (MGO), and the emission factor of DP < 100 nm increased. (2) Changes in emission characteristics led to an increase in the toxicity of ultrafine particulate matter. (3) Ship types and engine conditions affected the EC and PAH particle size distributions. Inland ships have a more concentrated particle size distribution. Higher loads result in higher emissions. (4) The composition and engine conditions of fuel oils jointly affected pollutant formation mechanisms. MGO and HFO exhibited opposite EC emissions when emitting the same level of PAHs.

Synthetically impacts of the topography and typhoon periphery on the atmospheric boundary layer structure and special regional pollution pattern of O3 in North China Plain

Westerly warm advection from the Loess Plateau to the over layer of North China Plain (NCP) suppresses the mixed layer during the daytime in summer, having already be confirmed as an important formation mechanism of regional O3 pollution all over NCP. However, when NCP was simultaneously affected by the westerly warm advection from the Loess Plateau and the typhoon periphery airflow from the Western Pacific tropical cyclone system, a rare pollution pattern of surface O3 was detected, characterized by a very low ozone pool in Beijing (LOP-BJ) contrast to much higher O3 in surrounding areas. To explore the causes and deep formation mechanism to this special pollution phenomenon, regional pollution characteristics of O3, characteristics of the atmospheric boundary layer (ABL) structure and vertical airflows affected by different weather systems were analyzed based on the analysis of observations and three dimensional simulations. It was found that the synthetic impacts of the topography and the typhoon peripheral flow promoted the stabilization of the ABL and introduced a nearly isolated air mass in terms of both thermodynamic and dynamic structures within ABL in Beijing region. In the stable and isolated ABL air masses, the significant lower ozone near the ground was primarily attributed to the strong loss by NO titration consumption from local excessive emissions and extremely weak transport contributions from surrounding areas. The conclusion was also confirmed by the integrated process rate (IPR) analysis results of contributions from chemistry tendency (CHEM) and total transport tendency (TRAN) to surface ozone. Our work insight the understanding of the formation mechanism of regional ozone pollution and improve the forecasting capabilities under comprehensive weather conditions over NCP.

Characteristics and Formation Mechanism of Ozone Pollution in Demonstration Zone of the Yangtze River Delta, China

Emerging research indicates that ground-level ozone (O3) has become a leading contributor to air quality concerns in many Chinese cities, with the Yangtze River Delta (YRD) region facing particular challenges. This study investigated the characterization of air pollutants in Wujiang, which is located within the YRD demonstration zone, during the warm season (April–September) of 2022. The contributions of emission and meteorology to O3 were identified, the O3-NOX-VOC sensitivities were discussed, and the VOC sources and their contributions to O3 formation were analyzed. A random forest model revealed that the high O3 concentration was mainly caused by a combination of increased emission intensity due to the resumption of work and production after the COVID-19 pandemic, along with adverse meteorological conditions. The results revealed more than 92% of the pollution days were related to O3 during the warm season, and the impact of O3 precursor emissions was slightly greater than that of the meteorological conditions. O3 formation was in the VOC-limited regime, and emission reduction strategies targeting VOCs, particularly aromatics such as toluene and xylene, have been identified as the most effective approach for mitigating O3 pollution. Changes in O3-NOX-VOC sensitivity were also observed from the VOC-limited regime to the transitional regime, which was primarily driven by variations in the NOX concentrations. The VOC source analysis results showed that the contributions of gasoline vehicle exhaust and diesel engine exhaust (mobile source emissions) were significantly greater than those of the other sources, accounting for 20.8% and 16.5% of the total VOC emissions, respectively. This study highlights the crucial role of mobile source emission control in mitigating O3 pollution. Furthermore, prioritizing the control of VOC emission sources with minimal NOX contributions is highly recommended within the VOC-limited regime.

Chemical composition, sources and formation mechanism of urban PM2.5 in Southwest China: a case study at the beginning of 2023

Abstract. Despite significant improvements in air quality in recent years, the Sichuan Basin (SCB) is still facing frequent haze pollution in winter, and the causes of severe haze formation have not yet been fully investigated. In this study, the chemical components of PM2.5 (i.e., particulate matter with an aerodynamic diameter of less than 2.5 µm) in a typical pollution period at the beginning of 2023 in Chengdu, a megacity in the SCB, were characterized by bulk-chemical and single-particle analysis, and the PM2.5 sources and formation mechanism of pollution were analyzed. The average mass concentration of PM2.5 during the study period was 95.6 ± 28.7 µg m−3. Organic matter (OM) was the most abundant component (35.3 %), followed by nitrate (22.0 %), sulfate (9.2 %) and ammonium (7.8 %). The individual aerosol particles were classified into five categories, i.e., mineral, OM, secondary inorganic aerosol (SIA), soot and fly ash/metal particles, and most of them were in the state of being internally mixed. The entire observation period could be divided into two non-pollution periods (NP-1 and NP-2) and two haze periods (Haze-1 and Haze-2). With the evolution of pollution, the bulk-chemical and single-particle analysis exhibited similar characteristics, suggesting that Haze-1 was mainly caused by pollutants related to fossil fuel combustion, especially local mobile sources, while Haze-2 was triggered by the rapidly increasing secondary pollutants, which mainly came from regional transmission. The PM2.5 sources included dust (8.5 %), biomass burning (3.5 %), coal combustion (15.4 %), industrial processes (6.5 %), vehicular emissions (25.6 %) and secondary sources (40.5 %). Analysis of Weather Research and Forecasting model with Chemistry (WRF-Chem) model results showed that the average contributions of local sources and regional transmission to pollution in Chengdu were the same (50 % vs. 50 %). In addition, the source composition and WRF-Chem simulation results in different periods confirmed our analysis of the formation mechanisms of the two haze events. This study confirms that further significant reductions in PM2.5 in Chengdu are still needed, and more effective policies for local emission reduction or joint prevention and control of regional air pollution will be necessary in the future.

Photochemical pollution during summertime in a coastal city of Southeast China: Ozone formation and influencing factors

Surface ozone (O3) has a significant impact on the air quality, and its concentrations have been increasing despite a distinct decrease in fine particulate matter (PM2.5) since 2013 in China. However, the formation mechanisms of photochemical O3 pollution in coastal regions are not fully understood. Therefore, an intensive field observation was conducted from July 8th to August 4th 2022 in Xiamen of Southeast China, combining with the observation-based model to reveal the formation and influencing factors of photochemical O3 pollution affected by the Western Pacific Subtropical High (WPSH). Results indicate that O3 pollution episodes were characterized by higher air temperature, lower relative humidity, lower wind speed, and higher concentrations of precursors (including volatile organic compounds (VOCs), NOx, and CO) compared with non-pollution episodes (p < 0.05). Stronger atmospheric oxidation capacity (AOC), OH reactivity, and ROx production rates during the O3 pollution episodes led to the remarkable increases in O3. Additionally, the photolysis of HCHO and other carbonyl compounds (48.6%), as well as O3 photolysis (41.3%) contributed the largest to ROx radical production, promoting the rapid formation of O3 during the pollution episodes. Reducing VOC concentrations not only decreased the net O3 production rates and AOC, but also weakened ROx self-reactions (Self-Rxns). Notably, Self-Rxns were weakened when the reduction percentage of NOx was from 10% to 20%, but decreasing NOx concentrations intensified Self-Rxns in other reduction percentages of NOx. This study provides a better understanding of photochemical O3 pollution mechanisms under the synoptic situation controlled by the WPSH, as well as the urgency of VOC reductions in the rapid development of coastal regions.

Effect of Equivalence Ratio on Pollutant Formation in CH4O/H2/NH3 Blend Combustion.

This paper investigates the effect of equivalence ratio on pollutant formation characteristics of CH4O/H2/NH3 ternary fuel combustion and analyzes the pollutant formation mechanisms of CO, CO2, and NOX at the molecular level. It was found that lowering the equivalence ratio accelerates the decomposition of CH4O, H2, and NH3 in general. The fastest rate of consumption of each fuel was found at φ = 0.33, while the rates of CH4O and NH3 decomposition were similar for the φ = 0.66 and φ = 0.4. CO shows an inverted U-shaped trend with time, and peaks at φ = 0.5. The rate and amount of CO2 formation are inversely proportional to the equivalence ratio. The effect of equivalence ratio on CO2 is obvious when φ > 0.5. NO2 is the main component of NOX. When φ < 0.66, NOX shows a continuous increasing trend, while when φ ≥ 0.66, NOX shows an increasing and then stabilizing trend. Reaction path analysis showed that intermediates such as CH3 and CH4 were added to the CH4O to CH2O conversion stage as the equivalence ratio decreased with φ ≥ 0.5. New pathways, CH4O→CH3→CH2O and CH4O→CH3→CH4→CH2O, were added. At φ ≤ 0.5, new intermediates CHO2 and CH2O2 were added to the CH2O to CO2 conversion stage, and new pathways are added: CH2O→CO→CHO2→CO2, CH2O→CO→CO2, CH2O→CHO→CO→CHO2→CO2, and CH2O→CH2O2→CO2. The reduction in the number of radical reactions required for the conversion of NH3 to NO from five to two directly contributes to the large amount of NOX formation. Equivalent ratios from 1 to 0.33 corresponded to 12%, 21.4%, 34%, 46.95%, and 48.86% of NO2 remaining, respectively. This is due to the fact that as the equivalence ratio decreases, more O2 collides to form OH and some of the O2 is directly involved in the reaction forming NO2.

Ozone Pollution Characteristics and Formation Mechanism in a Typical Tropical Seaside City

To investigate the pollution characteristics and formation mechanism of ambient air ozone(O3) in a typical tropical seaside city, we conducted an observational experiment on O3 and its precursors at an urban site in Haikou, Hainan Province, from June to October 2019. The O3 pollution characteristics were analyzed comprehensively; the O3-NOx-VOCs sensitivities and key precursors were determined, and the control strategies for O3 pollution were carried out. The results were as follows:1 O3 pollution in Haikou mainly occurred in September and October, with daily maximum 8-h O3 concentrations in the range of 39-190 μg·m-3, and the daily variation in O3 was unimodal, peaking at approximately 14:00. 2 The concentrations of NO2 and VOCs were higher during O3 pollution episodes than their respective mean values in Haikou City. The increased O3 precursor concentrations were an important factor leading to O3 pollution, whereas O3 pollution was also influenced by regional transport, with pollutants mainly transported from the northeastern part of Haikou City. 3 O3-NOx-VOCs sensitivity in Haikou City was in the VOCs and NOx transitional regime, and the most sensitive precursors in various months were different. O3 formation in September was sensitive to anthropogenic VOCs the most; however, in October it was sensitive to NOx. 4 In the future, the reduction ratio of VOCs to NOx should be 1:1-4:1 to control O3 pollution effectively in Haikou.

Variation characteristics and coordinated emission reduction of air pollutants in megacity of Chengdu-Chongqing economic circle under dual carbon goal

The air pollution process and impact mechanism of megacities located in complex terrain are particularly complex. As a typical megacity in China, Chengdu has unique topographical and meteorological conditions, and its pollution control is difficult. This study systematically elucidated the variation characteristics of six criteria air pollutants in Chengdu between 2014 and 2020. Besides, the PM&lt;sub&gt;2.5&lt;/sub&gt;/PM&lt;sub&gt;10&lt;/sub&gt; and NO&lt;sub&gt;2&lt;/sub&gt;/SO&lt;sub&gt;2&lt;/sub&gt; ratios were discussed. Furthermore, a detailed analysis of the correlation between air pollutants was carried out. Finally, the collaborative path of carbon reduction and air pollution control is discussed. The results indicated that SO&lt;sub&gt;2&lt;/sub&gt;, PM&lt;sub&gt;2.5&lt;/sub&gt;, PM&lt;sub&gt;10&lt;/sub&gt; and CO were significantly decreased by 62.9%, 50.8%, 45.5%, and 36.7%, respectively. PM&lt;sub&gt;2.5&lt;/sub&gt; and O&lt;sub&gt;3&lt;/sub&gt; compliance rates are very low, and O&lt;sub&gt;3&lt;/sub&gt; increases with fluctuations. SO&lt;sub&gt;2&lt;/sub&gt;, NO&lt;sub&gt;2&lt;/sub&gt;, CO, PM showed a “U-shaped” seasonal variation, and there was a “seesaw” phenomenon between O&lt;sub&gt;3&lt;/sub&gt; and PM&lt;sub&gt;2.5&lt;/sub&gt;. The continuous changing trends also found in the ratios of PM&lt;sub&gt;2.5&lt;/sub&gt;/PM&lt;sub&gt;10&lt;/sub&gt; and NO&lt;sub&gt;2&lt;/sub&gt;/SO&lt;sub&gt;2&lt;/sub&gt;. The results highlight the importance of coordinated reduction of carbon emissions and pollutants in Chengdu. This research can improve the prediction accuracy of air pollution in complex terrain areas under global warming, and improve the understanding of the formation mechanism of air pollution in special terrains around the world.

Case Analysis of Heavy Air Pollution Process in Xi'an Using Multi-source Data

Air pollution continues to be a serious problem in Xi'an. A heavy pollution process and formation mechanism were investigated in Xi'an in January 2019 using multi-source methods (such as material balance and sulfur/nitrogen oxidation rate (SOR/NOR)). The multi-source data included the concentrations of PM2.5, PM10, SO2, NO2, CO, and O3; the chemical components of PM2.5; the meteorological records of ground and vertical observations; the atmospheric reanalysis data. Three phases were obtained including the accumulation phase (P1), maintenance phase (P2), and dispersion phase (P3) during the pollution period. The pollution event was primarily attributed to the superposition of adverse weather conditions and feedback effects. During the periods of P1 and P2, the area of Xi'an was affected by blocking and zonal westerly airflow at 500 hPa (with flat westerly airflow) and uniform-distribution pressure at sea level with a limited pressure gradient and stable weather conditions, and the easterly wind was dominant at 925 hPa; not all of these factors were conducive to the pollutant diffusion. An interaction feedback mechanism between meteorological conditions and heavy pollution could be studied using the ground-based microwave radiometer. The correlations between PM2.5 and inversions of water vapor density, relative humidity, air temperature, and temperature inversion were significant with coefficients of 0.86, 0.62, 0.53, and 0.38, respectively. The feedback mechanism was primarily manifested as follows:with the pollutant accumulation, the radiative cooling effect could lead to or strengthen the occurrence and intensity of temperature inversion, decrease the mixed layer height, and cause moisture accumulation. High humidity could further maintain the pollution by accelerating the secondary formation and promoting the hygroscopic growth of aerosol particles. Therefore, the dominant chemical components to PM2.5were secondary inorganic ions (SO42-+NO3-+NH4+, SNA) and "other" components during the period of P2, with contributions of 43.2% and 23.1%, respectively. In addition, the peak values of PM2.5, SOR, NOR, and the light extinction coefficients all occurred on the same days (January 3 and 6), indicating that the effect of secondary formation was important for both heavy pollution events and visibility. The total contribution of NH4NO3, organic matter (OM), (NH4)2SO4, and EC to the light extinction coefficient was more than 85%. Limited variations in the proportion for components were observed in three phases. During the period of P3, the strong cold air in the mid-lower atmosphere was conducive to the dry and clean air sinking and the pressure gradient at sea level increasing. These were beneficial to the diffusion of air pollutants and water vapor.

Investigation of spatiotemporal distribution and formation mechanisms of ozone pollution in eastern Chinese cities applying convolutional neural network

Severe ground-level ozone (O3) pollution over major Chinese cities has become one of the most challenging problems, which have deleterious effects on human health and the sustainability of society. This study explored the spatiotemporal distribution characteristics of ground-level O3 and its precursors based on conventional pollutant and meteorological monitoring data in Zhejiang Province from 2016 to 2021. Then, a high-performance convolutional neural network (CNN) model was established by expanding the moment and the concentration variations to general factors. Finally, the response mechanism of O3 to the variation with crucial influencing factors is explored by controlling variables and interpolating target variables. The results indicated that the annual average MDA8-90th concentrations in Zhejiang Province are higher in the northern and lower in the southern. When the wind direction (WD) ranges from east to southwest and the wind speed (WS) ranges between 2 and 3 m/sec, higher O3 concentration prone to occur. At different temperatures (T), the O3 concentration showed a trend of first increasing and subsequently decreasing with increasing NO2 concentration, peaks at the NO2 concentration around 0.02 mg/m3. The sensitivity of NO2 to O3 formation is not easily affected by temperature, barometric pressure and dew point temperature. Additionally, there is a minimum IRNO2 at each temperature when the NO2 concentration is 0.03 mg/m3, and this minimum IRNO2 decreases with increasing temperature. The study explores the response mechanism of O3 with the change of driving variables, which can provide a scientific foundation and methodological support for the targeted management of O3 pollution.

Evolution Characteristics of Atmospheric Formaldehyde Emissions in Guangdong Province from 2006 to 2020

Atmospheric formaldehyde, a key precursor for ozone (O3) and secondary PM2.5, is carcinogenic and plays an important role in atmospheric photochemistry and the formation of secondary pollution. However, the lack of understanding of the emission sources of atmospheric formaldehyde limits the study on the formation mechanism of secondary pollution and the formulation of pollution control strategies. This study used the emission factor and source profile methods to establish the emission inventories of formaldehyde in Guangdong Province from 2006 to 2020 and identified the main emission sources of formaldehyde and spatial and temporal evolution characteristics. The results showed that the formaldehyde emissions in Guangdong Province fluctuated in the range of 39000-56000 tons during 2006 to 2020, exhibiting a very weak downward trend. Biomass combustion is an important source of formaldehyde emission in Guangdong Province, of which the contribution decreased from 58% in 2006 to 27% in 2020 owing to effective control measures implemented in Guangdong Province. The solvent use source became the predominant emission source of formaldehyde in 2020 by contributing up to 28%, primarily through plastic products and asphalt paving sources. The construction machinery and trucks fueled by diesel were important contributors of formaldehyde emissions from mobile sources. Although the formaldehyde emissions in the Pearl River Delta and the non-Pearl River Delta were equivalent, the spatial distributions showed that formaldehyde emission hotspots were concentrated in the center of the Pearl River Delta and the eastern and western areas of the non-Pearl River Delta. This was primarily because the solvent use and mobile sources were the main sources of formaldehyde emissions in the Pearl River Delta, whereas the biomass combustion source was the dominant source in the non-Pearl River Delta. Therefore, the formaldehyde emission mitigations of the industrial and mobile sources in the central region of the Pearl River Delta and the biomass combustion source in the western area of Guangdong should be further strengthened in the future.

Practical application for legacy acid mine drainage (AMD) prevention and treatment technologies in karst-dominated regions: A case study

Acid mine drainage (AMD) from abandoned mines in karst-dominated regions in southwestern China was causing contamination of groundwater and surface streams. To avert the unwise decisions of “pollution first before treatment” during pre-mining, mid-mining and post-mining activities, this paper proposes a contaminant migration prevention technical framework covering 4 comprehensive processes. The formation mechanism of spring pollution, engineering remediation processes and contamination treatment effects were described in Longdong Spring. In 2018, the Longdong Spring water had Fe 33.83 mg/L and Mn 3.60 mg/L, exceeding the Chinese surface water standard (0.3 mg/L and 0.1 mg/L in GB 3838–2002) by 112 and 36 times, respectively. In 2020, after grout blocking, in situ treatment and wetland remediation, the highest Fe was 4.5 mg/L in a short period, and the spring water pollution days in this year were 42 days compared with the previous 320 spring water pollution days in 2018. In 2021, two years of remediation with the implementation of terminal remediation wetlands, the Fe was less than 0.03 mg/L compared with the previous 33.83 mg/L, and the water quality reached water standard (less than 0.3 mg/L). At present, Longdong Spring has become one of the most beautiful natural local landscapes.

Performance and emission characteristics of an ammonia/diesel dual-fuel marine engine

This study explores the challenges and possibilities of using ammonia (NH3) as a carbon-free fuel for marine propulsion in a Wärtsilä ammonia/diesel dual-fuel engine using a reactivity-controlled compression ignition (RCCI) concept. The main issues in ammonia RCCI engines are high ammonia slip and high emissions of nitrogen oxides and nitrous oxide. A joint experimental and computational investigation was conducted to understand the combustion process, pollutant and greenhouse gas (GHG) formation mechanisms, and the effects of injector configuration and injection timing on engine performance. A comparative assessment between the ammonia/diesel RCCI engine and a baseline natural gas/diesel RCCI engine showed that, upon replacing premixed natural gas with ammonia and maintaining the same energy share of diesel (8.5% of the total energy from diesel), the engine yielded considerably poor combustion efficiency. Increasing diesel usage to 24% share of the total energy allowed a successful engine operation, cutting GHG by 70%. However, higher diesel usage increased CO and CO2 emissions. N2O emission was attributed to the slow premixed ammonia/air flame propagation and near-wall flame quenching. The primary sources of NO emissions in ammonia/diesel RCCI engines were identified as fuel-NOx from premixed ammonia oxidation and thermal NOx in the diesel flame region. A recommendation was put forth for enhancing the operating conditions and injection strategies of ammonia RCCI engines. The proposed operation and injection strategy results in a 45% reduction in CO emission, a 60% reduction in total GHG emissions, and, notably, an 89% decrease in CO2 emissions compared to the LNG/diesel engine.

Peroxy radical chemistry during ozone photochemical pollution season at a suburban site in the boundary of Jiangsu–Anhui–Shandong–Henan region, China

Ambient peroxy radical (RO2⁎ = HO2 + RO2) concentrations were measured at a suburban site in a major prefecture-level city (Huaibei) in the boundary of Jiangsu–Anhui–Shandong–Henan region, which is the connecting belt of air pollution in the Beijing–Tianjin–Hebei region and the Yangtze River Delta. Measurements were carried out during the period of September to October 2021 to elucidate the formation mechanism of O3 pollution. The observed maximum concentration of peroxy radicals was 73.8 pptv. A zero-dimensional box model (Framework for 0-Dimensional Atmospheric Modeling, F0AM) based on Master Chemical Mechanism (MCM3.3.1) was used to predict radical concentrations for comparison with observations. The model reproduced the daily variation of peroxy radicals well, but discrepancies still appear in the morning hours. As in previous field campaigns, systematic discrepancies between modelled and measured RO2⁎ concentrations are observed in the morning for NO mixing ratios higher than 1 ppbv. Between 6:00 and 9:00 am, the model significantly underpredicts RO2⁎ by a mean factor of 7.2. This underprediction can be explained by a missing RO2⁎ source of 1.2 ppbv h−1 which originated from the photochemical conversion of an alkene-like chemical species. From the model results it shows that the main sources of ROx (= OH + HO2 + RO2) are the photolysis of oxygenated volatile organic compounds (OVOCs, 33 %), O3 and HONO (25 %), and HCHO (24 %). And the major sinks of ROx transitioned from a predominant reaction of radicals with NOx in the morning to a predominant peroxy self- and cross-reaction in the late afternoon. The introduction of an alkene-like species increased RO2 radical concentration and resulted in 14 % increase in net daily integrated ozone production, indicating the possible significance of the mechanism of alkene-like species oxidation to peroxy radicals. This study provides important information for subsequent ozone pollution control policies in Jiangsu–Anhui–Shandong–Henan region.

Meteorological Formation Mechanisms and Potential Sources of an Ozone Pollution Process in Winter of 2022 in Guangdong Province

Meteorological conditions play an important role in seasonal ozone variations. In order to understand the meteorological formation mechanisms of ozone pollution in Guangdong Province in winter, the moderate ozone pollution process in Guangdong Province from January 3-6, 2022 was selected for comparison with that in autumn (high pollution season) of 2015 to 2021. The research was based on ground and vertical sounding data and reanalysis data of air quality and meteorological elements. Eight cities exceeded the standard during the pollution process, among which Zhaoqing showed moderate pollution (219 μg·m-3) on January 4th. The average O3-8h concentration in Guangdong Province was 123 μg·m-3, which was 21% higher than that in historical autumn. However, its scope of pollution was less than the historical pollution processes in autumn. Lower wind speed, longer sunshine hours, and airflow reflux effect under local circulation were the most important ground-level meteorological conditions for the ozone pollution process, whereas lower temperature might be an important reason for its small scope of pollution. Vertical detection analysis showed that the combined effect of low-level temperature inversion layer, stronger downdraft, and lower wind speed kept the NO2 concentrations at a high level, and further induced a higher increment of ozone concentration in the morning (34.2 μg·m-3 higher than that in the non-pollution period). The downward transport of ozone in the residual layer aggravated the ozone pollution on January 4th. The accumulation of ozone and its precursors was an important factor of the aggravation of ozone pollution the following day. Airflow trajectory analysis revealed that the ground-level ozone was affected by horizontal transport and vertical mixing of pollutants. Potential sources at 10 m were mainly distributed in the coastal areas from Fujian to Guangdong, and the scope of potential sources was concentrated in Guangdong as the height increased. Airflow backward trajectories at different heights during the ozone process passed over the areas of potential sources in Guangdong, which indicated that the local emissions in Guangdong had a greater impact on the ozone pollution process.

A mechanistic and kinetic investigation on the oxidative thermal decomposition of decabromodiphenyl ether

The thermal processes of materials containing decabromodiphenyl ether (BDE-209) normally result in the exposure of BDE-209 to high-temperature environments, generating a series of hazardous compounds. However, the evolution mechanisms of BDE-209 during oxidative thermal processes remain unclear. Thus, this paper presents a detailed investigation on the oxidative thermal decomposition mechanism of BDE-209 by utilizing density functional theory methods at the M06/cc-pVDZ theoretical level. The results show that the barrierless fission of the ether linkage dominates the initial degradation of BDE-209 at all temperatures, with branching ratio over 80%. The decomposition of BDE-209 in oxidative thermal processes is mainly along BDE-209 → pentabromophenyl and pentabromophenoxy radicals → pentabromocyclopentadienyl radicals → brominated aliphatic products. Additionally, the study results on the formation mechanisms of several hazardous pollutants indicate that the ortho-phenyl-type radicals created by ortho-C-Br bond fission (branching ratio reached 15.1% at 1600 K) can easily be converted into octabrominated dibenzo-p-dioxin and furan, which require overcoming the energy barriers of 99.0 and 48.2 kJ/mol, respectively. The O/ortho-C coupling of two pentabromophenoxy radicals also acts as a non-negligible pathway for the formation of octabrominated dibenzo-p-dioxin. The synthesis of octabromonaphthalene involves the self-condensation of pentabromocyclopentadienyl radicals, followed by an intricately intramolecular evolution. Results presented in this study can enhance our understanding of the transformation mechanism of BDE-209 in thermal processes, and offer an insight into controlling the emissions of hazardous pollutants.

Toxicological Effects of Secondary Air Pollutants.

Secondary air pollutants, originating from gaseous pollutants and primary particulate matter emitted by natural sources and human activities, undergo complex atmospheric chemical reactions and multiphase processes. Secondary gaseous pollutants represented by ozone and secondary particulate matter, including sulfates, nitrates, ammonium salts, and secondary organic aerosols, are formed in the atmosphere, affecting air quality and human health. This paper summarizes the formation pathways and mechanisms of important atmospheric secondary pollutants. Meanwhile, different secondary pollutants' toxicological effects and corresponding health risks are evaluated. Studies have shown that secondary pollutants are generally more toxic than primary ones. However, due to their diverse source and complex generation mechanism, the study of the toxicological effects of secondary pollutants is still in its early stages. Therefore, this paper first introduces the formation mechanism of secondary gaseous pollutants and focuses mainly on ozone's toxicological effects. In terms of particulate matter, secondary inorganic and organic particulate matters are summarized separately, then the contribution and toxicological effects of secondary components formed from primary carbonaceous aerosols are discussed. Finally, secondary pollutants generated in the indoor environment are briefly introduced. Overall, a comprehensive review of secondary air pollutants may shed light on the future toxicological and health effects research of secondary air pollutants.