Evolution of Ozone Formation Sensitivity during a Persistent Regional Ozone Episode in Northeastern China and Its Implication for a Control Strategy.

In recent years, the magnitude and frequency of regional ozone (O3) episodes have increased in China. We combined ground-based measurements, observation-based model (OBM), and the Weather Research and Forecasting and Community Multiscale Air Quality (WRF-CMAQ) model to analyze a typical persistent O3 episode that occurred across 88 cities in northeastern China during June 19-30, 2021. The meteorological conditions, particularly the wind convergence centers, played crucial roles in the evolution of O3 pollution. Daily analysis of the O3 formation sensitivity showed that O3 formation was in the volatile organic compound (VOC)-limited or transitional regime at the onset of the pollution episode in 92% of the cities. Conversely, it tended to be or eventually became a NOx-limited regime as the episode progressed in the most polluted cities. Based on the emission-reduction scenario simulations, mitigation of the regional O3 pollution was found to be most effective through a phased control strategy, namely, reduction of a high ratio of VOCs to NOx at the onset of the pollution and lower ratio during evolution of the O3 episode. This study presents a new possibility for regional O3 pollution abatement in China based on a reasonable combination of OBM and the WRF-CMAQ model.

Significant contribution of carbonyls to atmospheric oxidation capacity (AOC) during the winter haze pollution over North China Plain.

Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter, for which the reason have not been clearly elucidated. Here we measured carbonyl compounds and other trace gasses together with PM2.5 over urban Jinan in North China Plain during the winter. Markedly higher carbonyl concentrations (average: 14.63 ± 4.21 ppbv) were found during wintertime haze pollution, about one to three-times relative to those on non-haze days, with slight difference in chemical composition except formaldehyde (HCHO). HCHO (3.68 ppbv), acetone (3.17 ppbv), and acetaldehyde (CH3CHO) (2.83 ppbv) were the three most abundant species, accounting for ∼75% of the total carbonylson both haze and non-haze days. Results from observational-based model (OBM) with atmospheric oxidation capacity (AOC) indicated that AOC significantly increased with the increasing carbonyls during the winter haze events. Carbonyl photolysis have supplied key oxidants such as RO2 and HO2, and thereby enhancing the formation of fine particles and secondary organic aerosols, elucidating the observed haze-carbonyls inter-correlation. Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources. 1-butene was further confirmed to be the major precursor for HCHO. This study confirms the great contribution of carbonyls to AOC, and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.

Atmospheric oxidizing capacity in autumn Beijing: Analysis of the O3 and PM2.5 episodes based on observation-based model.

Atmospheric oxidizing capacity (AOC) is the fundamental driving factors of chemistry process (e.g., the formation of ozone (O3) and secondary organic aerosols (SOA)) in the troposphere. However, accurate quantification of AOC still remains uncertainty. In this study, a comprehensive field campaign was conducted during autumn 2019 in downtown of Beijing, where O3 and PM2.5 episodes had been experienced successively. The observation-based model (OBM) is used to quantify the AOC at O3 and PM2.5 episodes. The strong intensity of AOC is found at O3 and PM2.5 episodes, and hydroxyl radical (OH) is the dominating daytime oxidant for both episodes. The photolysis of O3 is main source of OH at O3 episode; the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) plays important role in OH formation at PM2.5 episode. The radicals loss routines vary according to precursor pollutants, resulting in different types of air pollution. O3 budgets and sensitivity analysis indicates that O3 production is transition regime (both VOC and NOx-limited) at O3 episode. The heterogeneous reaction of hydroperoxy radicals (HO2) on aerosol surfaces has significant influence on OH and O3 production rates. The HO2 uptake coefficient (γHO2) is the determining factor and required accurate measurement in real atmospheric environment. Our findings could provide the important bases for coordinated control of PM2.5 and O3 pollution.

Strong ozone production at a rural site in theNorth China Plain: Mixed effects of urban plumesand biogenic emissions.

Regional ozone (O3) pollution has drawn increasing attention in China over the recent decade, but the contributions from urban pollution and biogenic emissions have not been clearly elucidated. To better understand the formation of the regional O3 problem in the North China Plain (NCP), intensive field measurements of O3 and related parameters were conducted at a rural site downwind of Ji'nan, the capital city of Shandong province, in the summer of 2013. Markedly severe O3 pollution was recorded, with the O3 mixing ratios exceeding the Chinese national ambient air quality standard on 28 days (a frequency of 78%) and with a maximum hourly value of 198 ppbv. Extensive regional transport of well-processed urban plumes to the site was identified. An observation-constrained chemical box model was deployed to evaluate in situ photochemical O3 production on two episodes. The results show that the in situ formation accounted for approximately 46% of the observed O3 accumulation, while the remainder (~54%) was contributed by regional transport of the O3-laden urban plumes. The in situ ozone production was in a mixed controlled regime that reducing either NOx or VOCs would lead to a reduction of ozone formation. Biogenic VOCs played an important role in the local ozone formation. This study demonstrates the significant mixed effects of both anthropogenic pollution from urban zones and biogenic emission in rural areas on the regional O3 pollution in the NCP region, and may have general applicability in facilitating the understanding of the formation of secondary pollution over China.

Investigation on the budget of peroxyacetyl nitrate (PAN) in the Yangtze River Delta: Unravelling local photochemistry and regional impact.

Peroxyacetyl nitrate (PAN) is a significant indicator of atmospheric photochemical pollution, which can influence the regional distribution of ozone (O3) and hydroxyl radical (OH) through long-range transport. However, investigations of PAN incorporating comprehensive measurement and explicit modeling analysis are limited, hindering complete understandings of its temporal behavior, sources, and impacts on photochemistry. Here we conducted a 1-year continuous observation of PAN and relative atmospheric species in Nanjing located in Yangtze River Delta (YRD). The annual mean concentration of PAN was 0.62 ± 0.49 ppbv and showed a bimodal monthly variation, peaking in April-June and November-January, respectively. This pattern is different from the typical pattern of photochemistry, suggesting important contributions of other non-photochemical processes. We further analyzed the PAN budget using an observation-based model, by which, PAN from local photochemical production and regional source could be decoupled. Our results revealed that local photochemical production of PAN is the sole contributor to PAN in summer, whereas about half of the total PAN concentration is attributed to regional source in winter. Although the formation of PAN can suppress the atmospheric oxidation capacity by consuming the peroxyacetyl radical and nitrogen dioxide (NO2), our analyses suggested this effect is minor at our station (-3.2 ± 1.1 % in summer and - 7.2 ± 2.8 % in winter for O3 formation). However, it has the potential to enhance O3 and OH formation by 14.16 % and 5.93 %, if transported to cleaner environments with air pollutants halved. Overall, our study highlights the importance of both local photochemistry and regional process in PAN budget and provides a useful evaluation on the impact of PAN on atmospheric oxidation capacity.

[Ozone Pollution in Suzhou During Early Summertime: Formation Mechanism and Interannual Variation].

This study investigated the concentrations of atmospheric pollutants in the urban area of Suzhou from May to June, 2017-2021. The variation characteristics and annual changes of ozone (O3), nitrogen oxide (NOx), total oxidant (Ox), carbon monoxide (CO), and volatile organic compounds (VOCs) were analyzed. The O3 formation mechanism and its annual changes were studied using an Observation-Based Model (OBM), and VOCs source apportionments and their trends were discussed. The results indicated that ① The volume fractions of Ox and the concentrations of NOx and CO have decreased in the urban area of Suzhou in recent years, while the volume fractions of VOCs have increased, and sufficient photochemical conditions for O3 formation still existed during polluted days. ② The O3-NOx-VOCs sensitivity in Suzhou was in the VOCs-limited regime. The long-term reduction ratio between VOCs and NOx should not be less than 5:1, and aromatics and alkenes were the critical VOCs for mitigating O3 pollution. ③ The results of VOCs source apportionment revealed that industrial emissions, gasoline vehicle exhaust, and diesel engine exhaust were the major sources of VOC emissions in Suzhou. Industrial emissions and solvent usage declined from 2017 to 2021; however, gasoline vehicle exhaust and gasoline evaporation, which possess higher O3 formation potential(OFP), increased significantly. ④ The OFP source apportionments results indicated that controlling VOC emissions from solvent usage and gasoline vehicle exhaust is crucial for O3 pollution control in Suzhou.

[Differences of Three Methods in Determining Ozone Sensitivity in Nanjing].

In recent years， ozone （O3） has become an increasingly important air pollutant in China. Identifying the sensitivity of O3 to the precursors volatile organic compounds （VOCs） and nitrogen oxides （NOx） can help make effective abatement strategies. This study compared three methods for determining O3-VOCs-NOx sensitivity： simulated photochemical indicator values and sensitivity coefficients derived from a three-dimensional air quality model and an observation-based model （OBM）， with a case study involving an O3 pollution event that occurred in Nanjing in late July 2017. The results showed that O3 sensitivity based on the photochemical indicator and sensitivity coefficients demonstrated similar spatial variations （over 50% of the grid cells of Nanjing exhibiting identical O3 sensitivity）. However， sensitivity coefficients identified a larger number of areas within a transitional O3 sensitivity regime， as opposed to the VOCs- or NOx-limited regime identified by the photochemical indicator. The determination of the latter was affected by the adopted threshold values. The OBM relied on the quality of the observational data. For example， positive biases in observed NO2 could lead to an underestimation of O3 sensitivity to NOx with the OBM. During the high pollution period， the three methods exhibited significant disparities. The photochemical indicator tended to suggest the VOCs-limited condition， whereas the OBM and sensitivity coefficients indicated the NOx-limited or transitional regimes.

Intercomparison of measured and modelled photochemical ozone production rates: Suggestion of chemistry hypothesis regarding unmeasured VOCs.

Ozone (O3) pollution is a severe environmental problem in China. The incomplete understanding of atmospheric photochemical reaction mechanisms prevents us from accurately understanding the chemistry of O3 production. Here, we used an improved dual-channel reaction chamber technique to measure net photochemical O3 production rate (P(O3)net) directly in Dongguan, a typical industrial city in China. The maximum P(O3)net was 46.3 ppbv h-1 during the observation period, which is at a relatively high level compared to previous observations under different environment worldwide. We employed an observation-based box model coupled with the state-of-the-art atmospheric chemical mechanism (MCM v3.3.1) to investigate the chemistry of O3 production. Under the base scenario, the modelling underestimates P(O3)net by ~30 %. Additionally considering HO2 uptake by ambient aerosols, inorganic deposition, and Cl chemistry only caused a small change (< 13 %) in the simulation of P(O3)net. Further analysis indicates that unmeasured reactive volatile organic compounds (VOCs), such as oxygenated VOCs and branched alkenes are potential contributors to the underestimation of P(O3)net. This study underscores the underestimation of P(O3)net in conventional atmospheric modelling setups, providing a crucial scientific foundation for further investigation aimed at promoting our understanding of photochemical O3 formation.

Two-year online measurements of volatile organic compounds (VOCs) at four sites in a Chinese city: Significant impact of petrochemical industry.

Volatile organic compounds (VOCs) management has been recently given a high priority in China to mitigate ozone (O3) air pollution. However, there is a relatively poor understanding of VOCs due to their complexity and fewer observations. To better understand the pollution characteristics of VOCs and their impact on O3 pollution, two-year continuous measurements were conducted at four representative sites in Ji'nan, eastern China. These four sites cover urban, background, and industrial areas (within a petroleum refinery). Ambient VOCs showed higher concentrations at industrial site than at urban and background sites, owing to intensive emissions from petrochemical industry. The VOCs compositions present spatial heterogeneity with alkenes dominated in total reactivity at urban and background sites, while alkenes and aromatics together dominated at industrial site. The VOCs emission profile from petrochemical industry was calculated based on observational data, which revealed a huge impact on light alkanes (C2-C5), light alkenes (ethene), and aromatics (toluene and m/p-xylene). The positive matrix factorization (PMF) model analysis further refined the impact of different petrochemical industrial processes. Alkanes and alkenes dominated the emissions during refining process, while aromatics dominated during solvent usage process. Analysis by an observation-based model indicated stronger in-situ O3 production and higher sensitivity to nitrogen oxides at industrial site compared to urban and background sites. The reduction of VOCs emissions from petrochemical industry would significantly reduce the O3 concentrations. The analyses underline the significant impact of petrochemical industry on VOCs and O3 pollution, and provide important reference for the formulation of refined and effective control strategies.

Summertime carbonyl compounds in an urban area in the North China Plain: Identification of sources, key precursors and their contribution to O3 formation.

Carbonyl compounds are critical components of volatile organic compounds, which significantly participate in the photochemical formation of atmospheric ozone and thus threaten human health. Here we measured 15 C1-C8 carbonyl compounds at an urban site in Linyi, a typically industrialised city in the North China Plain (NCP). Formaldehyde (3.89 ppbv), acetaldehyde (1.66 ppbv) and acetone (2.03 ppbv) were found to be the top three carbonyl compounds, accounting for 76.11% of the total concentration of carbonyl compounds. Anthropogenic secondary formation was recognised as the main source of the top five carbonyl compounds, which included formaldehyde, acetaldehyde, acetone, butyraldehyde and benzaldehyde, and accounted for 46-54% of all sources. Alkenes were the most important precursors of formaldehyde and acetaldehyde, suggesting that reducing the emission of alkenes from anthropogenic sources is an effective way to control carbonyl compound pollution in Linyi. Furthermore, the photolysis of carbonyl compounds played a significant role (68-75%) as sources of HO2• and RO2• and thus made a significant contribution (14.6%) to the photochemical formation of O3. This study highlights the importance of anthropogenic secondary formation as a source of carbonyl compounds and provides a scientific basis for O3 pollution control in carbonyl compound-enriched cities in the NCP.

[Analysis of O3 Pollution Characteristics, Formation Sensitivity, and Transport Impact in Southern Nanjing].

As one of the most important city clusters in China, surface ozone (O3) pollution in the Yangtze River Delta (YRD) Region has become a prominent air quality problem in recent years. Online observations of ambient O3, nitrogen oxides (NOx), and volatile organic compounds (VOCs) were conducted in southern Nanjing from July-September 2020 and April-May 2021. On this basis, the pollution characteristics of O3 were analyzed. The O3-VOCs-NOx sensitivity and the transport influence of its precursors were further discussed using models. The frequency statistics of the daily maximum 8-hour moving average (DMA-8h O3) and hourly concentration (O3-1h) showed that O3 pollution in southern Nanjing was more serious than that in urban areas. Three typical O3 pollution episodes were selected during the whole observation period, which included August 16th-27th, 2020; September 3rd-11th, 2020; and May 17th-25th, 2021. The O3-VOCs-NOx sensitivities in these three pollution episodes were analyzed using the observation-based model (OBM). The results of the relative incremental reactivity (RIR) and empirical kinetics modeling approach (EKMA) showed that the sensitivities of O3 formation in the three pollution episodes were in the NOx-limited regime, the transition regime, and the VOCs-limited regime, respectively. This difference in O3-VOCs-NOx sensitivity reflects that the site may have been influenced by transport. Therefore, the potential source contribution function (PSCF) and the concentration weighted trajectory (CWT) method were further used to analyze the potential source areas of NOx, VOCs, and O3 in these three pollution episodes. The results showed that there were obvious regional transport effects of NOx, VOCs, and O3 in these three pollution episodes. The location of potential sources differed in these three pollution episodes, which were affected by the eastern cities of the Lishui site; the urban area of Nanjing and eastern area of Anhui Province; and the urban area of Nanjing and the middle of the YRD Region, respectively. The impact of transport on O3 and its precursors also indicated the necessity of regional joint prevention and control of O3 pollution in the YRD Region.

[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.

[Changes in O3-VOCs-NOx Sensitivity and VOCs Sources at an Urban Site of Nanjing Between 2020 and 2021].

The synergistic control of PM2.5 and ozone (O3) are the focus of air quality improvement during the 14th Five-Year Plan in China. The production of O3 shows a highly nonlinear relationship with its precursors volatile organic compounds (VOCs) and nitrogen oxides (NOx). In this study, we conducted online observations of O3, VOCs, and NOx at an urban site in downtown Nanjing from April to September of 2020 and 2021. The average concentrations of O3 and its precursors between these two years were compared, and then the O3-VOCs-NOx sensitivity and the VOCs sources were analyzed using the observation-based box model (OBM) and positive matrix factorization (PMF), respectively. The results showed that the mean daily maximum O3 concentrations, VOCs, and NOx concentrations decreased by 7% (P=0.031), 17.6% (P<0.001), and 14.0% (P=0.004) from April to September of 2021 compared with those from the same period in 2020, respectively. The average relative incremental reactivity (RIR) values of NOx and anthropogenic VOCs during the O3 non-attainment days in 2020 and 2021 were 0.17 and 0.14 and 0.21 and 0.14, respectively. The positive RIR values of NOx and VOCs indicated that O3 production was controlled by both VOCs and NOx. The O3 production potential contours (EKMA curves) based on the 50×50 scenario simulations also supported this conclusion. The PMF results showed that industrial and traffic-related emissions were the main sources of VOCs. The five PMF-resolved factors were identified as industrial emissions, including industrial liquefied petroleum gas (LPG) use, the benzene-related industry, petrochemistry, toluene-related industry, and solvent and paint use, which contributed 55%-57% of the average mass concentration of total VOCs. The summed relative contributions of vehicular exhaust and gasoline evaporation were 43%-45%. Petrochemistry and solvent and paint use showed the two highest RIR values, suggesting that VOCs from these two sources should be reduced with priority to control O3. With the implementation of VOCs and NOx control measures, the O3-VOCs-NOx sensitivity and VOCs sources have changed, and therefore we still need to follow their variations in the future to timely adjust O3 control strategies during the 14th Five-Year Plan.

[Characteristics of VOCs and Assessment of Emission Reduction Effect During the Epidemic Lockdown Period in Shenzhen Urban Area].

To prevent disease spreading during the COVID-19 epidemic, Shenzhen adopted lockdown measures in March of 2022. This provided an opportunity to study the response of changes in anthropogenic volatile organic compounds (AVOCs) in Shenzhen to emission reduction and to evaluate the effectiveness of current emission reduction measures. This study analyzed the variety of AVOCs before, during, and after the epidemic lockdown based on the online observation data of pollutants at Lianhua Station in Shenzhen from March 7, 2022 to March 27, 2022. Additionally, the sensitivity of ozone formation and the assessment of the reduction effect of precursors was conducted by an observation based model(OBM). The results showed that:affected by regional influences and the interference of meteorological conditions, the average value of AVOCs in Shenzhen urban areas did not drop significantly during the lockdown period compared to that before the lockdown. However, the peak of AVOCs at the morning peak time under the influence of "sea and land wind" during the epidemic lockdown period dropped by 46% on average compared with that during the non-lockdown period, and the aromatic hydrocarbon component dropped the most by 59%. Additionally, under the influence of continuous easterly wind, or during the accumulation and increase of AVOCs affected by regional transmission, aromatic components also decreased by an average of 25% and 21%, respectively. During the lockdown period of the epidemic in Shenzhen, the O3 formation in urban areas was still AVOCs-limited. Increasing the emission reduction ratio of AVOCs was the most effective measure to reduce O3 in the short term. In order to ensure the effectiveness of emission reduction, it was recommended that the coordinated emission reduction ratio of AVOCs and NOx should be greater than 1:2. It was only possible to enter the downward channel of O3 if the deep emission reduction was more than 60%. This study revealed that the emission reduction of AVOCs during the morning traffic peak during the epidemic lockdown period was conducive to inhibiting the formation of O3, whereas the control of NOx would promote it. Strengthening the control of local aromatic hydrocarbon components during the regional impact process could also significantly reduce O3 production. At this stage, Shenzhen should strengthen the management and control of industrial solvents, especially to reduce the aromatic hydrocarbon components in the solvent source that have a greater impact on the generation of O3. Further, Shenzhen should continue to promote the reform of the energy structure of motor vehicles to reduce the emission of VOCs in fuel combustion.

Multi-factor reconciliation of discrepancies in ozone-precursor sensitivity retrieved from observation- and emission-based models.

Ground-level O3 pollution has been continuously worsening in China despite gradual improvement in other major pollutant levels. Understanding the sensitivity of O3 production to its precursors (OPS) is a prerequisite for formulating effective O3 control measures, but this has been hampered by significant discrepancies in OPS produced by traditional identification approaches using observation-based models (OBM) and emission-based models (EBM). In this study, by applying OBM and EBM in parallel within a month having significant O3 pollution in Shanghai, China, we demonstrated that a lack of carbonyl input, overestimation in NO2 monitoring data, and differences in simulation period and emission reduction area were the core factors leading to OPS discrepancies, and that a reliable OPS cannot be obtained unless these factors are reconciled. By collectively addressing these factors, the number of days with a consistent OPS from both models increased from 6-7 to 20-21 in a month, and the R value defined to quantify the discrepancy decreased by ∼55%. The contributions of these factors to OPS discrepancy differed greatly in urban and suburban settings, mainly caused by differences in pollutant emission and transport characteristics. Overall, OPS identified solely by OBM or EBM is associated with great uncertainty, while reliable OPS estimation can be achieved by a collective application of OBM and EBM with consensus on the above factors. The method demonstrated here could be applied to other photo-chemically active regions worldwide as part of efforts to address ozone pollution.

Formation of peroxyacetyl nitrate (PAN) and its impact on ozone production in the coastal atmosphere of Qingdao, North China.

Peroxyacetyl nitrate (PAN), acting as a relatively long-lived reservoir for both NOx and radicals, plays a crucial role in ozone (O3) formation in the troposphere. However, its quantitative impacts on radical concentrations and O3 production were rarely studied in the coastal atmosphere. In this study, ambient concentrations of PAN, O3, and related species were simultaneously measured from October 5 to November 10, 2018 (autumn), and July 14 to August 24, 2019 (summer) at a rural coastal site in Qingdao, North China. The formation mechanism of PAN and its impact on in-situ O3 production were explored with an observation-based chemical box model. Photochemical formation of PAN and O3 was controlled by both NOx and VOCs, and acetaldehyde and methylglyoxal were the main contributors to PAN formation. However, the sensitivities of PAN to precursors were larger than that of O3 in autumn while smaller in summer, which was mainly caused by the rapid decomposition of PAN at high temperatures. Zero-out sensitivity simulation showed that PAN could either promote or inhibit the in-situ O3 formation by affecting the radical chemistry. It tended to suppress O3 production by competing with precursors and terminating radical chain reactions under low-NOx and low-ROx circumstances but enhanced O3 production by supplying RO2 radicals under conditions with sufficient NOx. This study provides some new complementary insights into the formation mechanism of PAN and its impacts on O3 production, and has implications for the formulation of control policy to mitigate regional photochemical pollution in northern China.

School formation characteristics and stimuli based modeling of tetra fish.

Self-organizing motion is an important yet inadequately understood phenomena in the field of collective behavior. For birds flocks, insect swarms, and fish schools, group behavior can provide a mechanism for defense against predators, better foraging and mating capabilities and increased hydro/aerodynamic efficiency in long-distance migration events. Although collective motion has received much scientific attention, more work is required to model and understand the mechanisms responsible for school initiation and formation, and information transfer within these groups. Here we investigate schooling of black tetra (Gymnocorymbus ternetzi) fish triggered by startle stimuli in the form of approaching objects. High-speed video and tagging techniques were used to track the school and individual members. We then measured several variables including reaction times, group formation shapes, fish velocity, group density, and leadership within the group. These data reveal three things: (1) information propagates through the group as a wave, indicating that each fish is not reacting individually to the stimulus, (2) the time taken for information to transfer across the group is independent of group density, and (3) information propagates across large groups faster than would be expected if the fish were simply responding to the motion of their nearest neighbor. A model was then built wherein simulated fish have a simple 'stimuli/escape' vector based on a hypothetical field of vision. The model was used to simulate a group of individual fish with initial conditions, size, and stimuli similar to the biological experiments. The model revealed similar behavior to the biological experiments and provide insights into the observed patterns, response times, and wave speeds.

Observations of C1-C5 alkyl nitrates in the Yellow River Delta, northern China: Effects of biomass burning and oil field emissions.

Alkyl nitrates (RONO2) are important reservoirs of nitrogen oxides and play key roles in the tropospheric chemistry. Two phases of intensive campaigns were conducted during February-April and June-July of 2017 at a rural coastal site and in open oil fields of the Yellow River Delta region, northern China. C1-C5 alkyl nitrates showed higher concentration levels in summer than in winter-spring (p < 0.01), whilst their parent hydrocarbons showed an opposite seasonal variation pattern. The C3-C5 RONO2 levels in the oil fields were significantly higher than those in the ambient rural air. Alkyl nitrates showed well-defined diurnal variations, elucidating the effects of in-situ photochemical production and regional transport of aged polluted plumes. Backward trajectory analysis and fire maps revealed the significant contribution of biomass burning to the observed alkyl nitrates and hydrocarbons. A simplified sequential reaction model and an observation-based chemical box model were deployed to diagnose the formation mechanisms of C1-C5 RONO2. The C3-C5 RONO2 were mainly produced from the photochemical oxidation of their parent hydrocarbons (i.e., C3-C5 alkanes), whilst C1-C2 RONO2 compounds have additional sources. In addition to parent hydrocarbons, longer alkanes with >4 carbon atoms were also important precursors of alkyl nitrates in the oil fields. This study demonstrates the significant effects of oil field emissions and biomass burning on the volatile organic compounds and alkyl nitrate formation, and provides scientific support for the formulation of control strategies against photochemical air pollution in the Yellow River Delta region.

Oxidizing capacity of the rural atmosphere in Hong Kong, Southern China.

Atmospheric oxidizing capacity (AOC), dominated by the hydroxyl radical (OH), is an important index of the self-cleaning capacity of atmosphere and plays a vital role in the tropospheric chemistry. To better understand the key processes governing the chemistry of rural atmosphere of southern China, we analyzed the oxidation capacity and radical chemistry at a regional background site in Hong Kong from 23 August to 22 December 2012, which covered the summer, autumn and winter seasons. A chemical box model built on the latest Master Chemical Mechanism (v3.3) was used to elucidate the OH reactivity and sources of ROX radicals (ROX=OH+HO2+RO2). The AOC showed a clear seasonal pattern with stronger intensity in late summer compared to autumn and winter. Reactions with NO2 (30%) and oxygenated volatile organic compounds (OVOCs) (31%) together dominated the OH loss in summer, while reactions with CO (38% in autumn and 39% in winter) and OVOCs (34% in autumn and 25% in winter) made larger contributions in autumn and winter. Photolysis of O3 (36%-47%) presented the major ROX source during all three seasons. The second largest ROx source was HONO photolysis (25%) in summer compared to HCHO photolysis in autumn (20%) and winter (21%). Besides, photolysis of other OVOCs was another important primary source of ROx radicals with average contributions of 14%, 13% and 20% for the summer, autumn and winter cases, respectively. Overall, the present study evaluates the oxidizing capacity of the rural atmosphere of South China and elucidates the varying characteristics of photochemical processes in different air masses.

[Source Analysis of Volatile Organic Compounds in the Nanjing Industrial Area and Evaluation of Their Contribution to Ozone].

Ambient volatile organic compounds (VOCs) were continuously measured during the high ozone (O3) periods from May 1 to May 31 and June 1 to July 16, 2015 at an industrial area in the north suburb of Nanjing. A positive matrix factorization (PMF) model and an observation-based model (OBM) were combined for the first time to investigate the contributions of VOC sources and species to local photochemical O3 formation. The average VOC concentrations in 2014 and 2015 were (36.47±33.44)×10-9 and (34.69±34.08)×10-9, respectively. The VOC sources identified by the PMF model for 2014 and 2015 belonged to 7 source categories, including vehicular emissions, liquefied petroleum gas usage, biogenic emissions, furniture manufacturing industry, chemical industry, chemical coating industry, and chemical materials industry emission sources. The OBM was modified to assess the O3 precursors' relationships. Generally, photochemical O3 production was VOC limited, with positive relative incremental reactivity (RIR) values for VOC species and a negative RIR value for NO. It can be seen that alkenes (1.20-1.79) and aromatics (1.42-1.48) presented higher RIR values and controlling O3 would be the most effective when the VOC emissions from alkenes were reduced by 80%. Vehicle emissions (1.01-1.11), LPG (0.74-0.82), biogenic emissions (0.34-0.42), and furniture manufacturing industry (0.32-0.49) sources were the top four VOC sources making significant contributions to photochemical O3 formation, which suggests that controlling vehicle emissions, biogenic emissions, LPG, and furniture manufacturing industry sources should be the most effective strategy to reduce photochemical O3 formation.