Characteristics of volatile organic compounds, NO2, and effects on ozone formation at a site with high ozone level in Chengdu

Chengdu is a megacity in the southwest of China with high ozone (O₃) mixing ratio. Observation of volatile organic compounds (VOCs), NO₂ and O₃ with high temporal resolution was conducted in Chengdu to investigate the chemical processes and causes of high O₃ levels. The hourly mixing ratios of VOCs, NO₂, and O₃ were monitored by an online system from 28 August to 7 October, 2016. According to meteorological conditions, Chengdu, with relative warm weather and low wind speed, is favorable to O₃ formation. Part of the O₃ in Chengdu may be transported from the downtown area. In O₃ episodes, the average mixing ratios of NO₂ and O₃ were 20.20?ppbv and 47.95?ppbv, respectively. In non-O₃ episodes, the average mixing ratios of NO₂ and O₃ were 16.38?ppbv and 35.15?ppbv, respectively. The average mixing ratio of total VOCs (TVOCs) was 40.29?ppbv in non-O₃ episodes, which was lower than that in O₃ episodes (53.19?ppbv). Alkenes comprised 51.7% of the total O₃ formation potential (OFP) in Chengdu, followed by aromatics which accounted for 24.2%. Ethylene, trans-pentene, propene, and BTEX (benzene, ethylbenzene, toluene, m/p-xylene, o-xylene) were also major contributors to the OFP in Chengdu. In O₃ episodes, intensive secondary formations were observed during the campaign. Oxygenated VOCs (OVOCs), such as acetone, Methylethylketone (MEK), and Methylvinylketone (MVK) were abundant. Isoprene rapidly converted to MVK and Methacrolein (MACR) during O₃ episodes. Acetone was mainly the oxidant of C3-C5 hydrocarbons.     

Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination

In this study, a hydrophobic synthetic zeolite, namely ZSM-5 is chosen as an adsorbent/catalyst for toluene removal. Experimental results showed that toluene adsorption onto ZSM-5 was favourable, following a Langmuir adsorption isotherm model. ZSM-5 zeolite was regenerated using gaseous ozone at low temperature. Adsorbed toluene was oxidised, releasing mainly CO₂ and H₂O. Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone. After four successive cycles of adsorption/ozonation, the adsorption efficiency was not affected (92%–99%). These results showed that volatile organic compound (VOC) removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.     

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China

Ground-level ozone (O₃) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O₃ pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O₃ to its precursors during 2 O₃ pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O₃ formation. The RIR values for NO_X ranged from –0.41%/% to 0.19%/%. The O₃ sensitivity was also analyzed based on relationship of simulated O₃ production rates with reductions of VOC and NO_X derived from scenario analyses. Simulation results illustrate that O₃ formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O₃ formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NO_X reduction schemes suggest that the 5% O₃ control goal can be achieved by reducing VOCs by 20%. To obtain 10% O₃ control goal, VOCs need to be reduced by 30% with VOCs/NO_X larger than 3:1.     

Effect of ozone injection on the long-term performance and microbial community structure of a VOCs biofilter

For biofilters treating waste gases containing volatile organic compounds(VOCs), biomass accumulation is a common problem which will induce bed clogging and significant decrease in VOCs removal efficiency during long-term operation. In this study, ozone injection was developed as a biomass control strategy, and its effects on the biofilter performance and the microbial community structure were investigated in long-term operation. Two biofilters,identified as BF1 and BF2, were operated continuously for 160 days treating gaseous toluene under the same conditions, except that 200 mg/m3 ozone was continuously injected into BF1 during days 45–160. During the operation period, ozone injection did not change the toluene removal efficiency, while the pressure drop of BF1 with ozone injection was significantly lowered compared with BF2. The wet biomass accumulation rate of BF1 was 11 g/m~3/hr, which was only46% of that in BF2. According to the carbon balance result, ozone injection also increased the toluene mineralization rate from 83% to 91%, which could be an important reason for the low biomass accumulation. The PMA-q PCR result indicated that ozone injection increased the microbial viability of the biofilm. The high-throughput sequencing result also revealed that the dominant phyla and genera were not changed significantly by ozone injection, but some ozonetolerant genera such as Rhodanobacter, Dokdonella and Rhodococcus were enhanced by ozone exposure. All the results verified that ozone injection is capable of sustaining the long-term performance of biofilters by lowering the biomass accumulation, increasing the microbial viability and changing the microbial community structure.     

大连星海地区环境空气中挥发性有机物的臭氧生成潜势研究

以该实验的观测资料为基础,通过数据分析表明,对大连星海地区OH自由基消耗的主要环境VOCs组分是烯烃类物质,对O3生成潜势贡献最高的环境VOCs组分是芳香烃类物质;综合LiOH及OFP值评价,识别影响大连星海地区O3生成的关键环境VOCs反应活性物种为丙烯、甲苯、间对二甲苯等物质。     

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.     

Characterization, reactivity, source apportionment, and potential source areas of ambient volatile organic compounds in a typical tropical city

Based on one-year observation, the concentration, sources, and potential source areas of volatile organic compounds (VOCs) were comprehensively analyzed to investigate the pollution characteristics of ambient VOCs in Haikou, China. The results showed that the annual average concentration of total VOCs (TVOCs) was 11.4 ppbV, and the composition was dominated by alkanes (8.2 ppbV, 71.4%) and alkenes (1.3 ppbV, 20.5%). The diurnal variation in the concentration of dominant VOC species showed a distinct bimodal distribution with peaks in the morning and evening. The greatest contribution to ozone formation potential (OFP) was made by alkenes (51.6%), followed by alkanes (27.2%). The concentrations of VOCs and nitrogen dioxide (NO₂) in spring and summer were low, and it was difficult to generate high ozone (O₃) concentrations through photochemical reactions. The significant increase in O₃ concentrations in autumn and winter was mainly related to the transmission of pollutants from the northeast. Traffic sources (40.1%), industrial sources (19.4%), combustion sources (18.6%), solvent usage sources (15.5%) and plant sources (6.4%) were identified as major sources of VOCs through the positive matrix factorization (PMF) model. The southeastern coastal areas of China were identified as major potential source areas of VOCs through the potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) models. Overall, the concentration of ambient VOCs in Haikou was strongly influenced by traffic sources and long-distance transport, and the control of VOCs emitted from vehicles should be strengthened to reduce the active species of ambient VOCs in Haikou, thereby reducing the generation of O₃.     

Machine learning and theoretical analysis release the non-linear relationship among ozone, secondary organic aerosol and volatile organic compounds

Fine particulate matter (PM_2.5) and ozone (O₃) pollutions are prevalent air quality issues in China. Volatile organic compounds (VOCs) have significant impact on the formation of O₃ and secondary organic aerosols (SOA) contributing PM_2.5. Herein, we investigated 54 VOCs, O₃ and SOA in Tianjin from June 2017 to May 2019 to explore the non-linear relationship among O₃, SOA and VOCs. The monthly patterns of VOCs and SOA concentrations were characterized by peak values during October to March and reached a minimum from April to September, but the observed O₃ was exactly the opposite. Machine learning methods resolved the importance of individual VOCs on O₃ and SOA that alkenes (mainly ethylene, propylene, and isoprene) have the highest importance to O₃ formation; alkanes (C_n, n ≥ 6) and aromatics were the main source of SOA formation. Machine learning methods revealed and emphasized the importance of photochemical consumptions of VOCs to O₃ and SOA formation. Ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAFP) calculated by consumed VOCs quantitatively indicated that more than 80% of the consumed VOCs were alkenes which dominated the O₃ formation, and the importance of consumed aromatics and alkenes to SOAFP were 40.84% and 56.65%, respectively. Therein, isoprene contributed the most to OFP at 41.45% regardless of the season, while aromatics (58.27%) contributed the most to SOAFP in winter. Collectively, our findings can provide scientific evidence on policymaking for VOCs controls on seasonal scales to achieve effective reduction in both SOA and O₃.     

天津武清地区夏季臭氧光化学研究

利用2006年8月10日—9月18日的监测数据,分析天津市武清区光化学污染特征. 结果表明:监测期间φ(O₃)的小时均值累积共有26 h超标,超标率为2.7%;光化学污染发生时,ρ(NO_x)和挥发性有机物(VOCs)的反应活性都有所升高,其中ρ(NO₂)平均约升高了20 μg/m3, VOCs的反应活性增加了42%,但是臭氧对于ρ(NO_x)的增加更加敏感. 计算VOCs等效丙烯浓度,发现邻二甲苯的臭氧生成潜势最高. 烯烃的光化学反应活性最强,其次是单环芳烃和烷烃.      

Emission factors, ozone and secondary organic aerosol formation potential of volatile organic compounds emitted from industrial biomass boilers

To evaluate the potential benefits of biomass use for air pollution control, this paper identified and quantified the emissions of major reactive organic compounds anticipated from biomass-fired industrial boilers. Wood pellets(WP) and straw pellets(SP) were burned to determine the volatile organic compound emission profiles for each biomass-boiler combination. More than 100 types of volatile organic compounds(VOCs) were measured from the two biomass boilers. The measured VOC species included alkanes, alkenes and acetylenes, aromatics, halocarbons and carbonyls. A single coal-fired boiler(CB) was also studied to provide a basis for comparison. Biomass boiler 1(BB1) emitted relatively high proportions of alkanes(28.9%–38.1% by mass) and alkenes and acetylenes(23.4%–40.8%),while biomass boiler 2(BB2) emitted relatively high proportions of aromatics(27.9%–29.2%)and oxygenated VOCs(33.0%–44.8%). The total VOC(TVOC) emission factors from BB1(128.59–146.16 mg/kg) were higher than those from BB2(41.26–85.29 mg/kg). The total ozone formation potential(OFP) ranged from 6.26 to 81.75 mg/m~3 with an average of 33.66 mg/m~3 for the two biomass boilers. The total secondary organic aerosol potential(SOAP) ranged from 61.56 to 211.67 mg/m~3 with an average of 142.27 mg/m~3 for the two biomass boilers.The emission factors(EFs) of TVOCs from biomass boilers in this study were similar to those for industrial coal-fired boilers with the same thermal power. These data can supplement existing VOC emission factors for biomass combustion and thus enrich the VOC emission inventory.     

Ambient volatile organic compounds at a receptor site in the Pearl River Delta region: Variations, source apportionment and effects on ozone formation

We present the continuously measurements of volatile organic compounds（VOCs） at a receptor site（Wan Qing Sha, WQS） in the Pearl River Delta（PRD） region from September to November of 2017. The average mixing ratios of total VOCs（TVOCs） was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes（55.5%）, followed by aromatics（33.3%）. The diurnal variation of TVOCs showed a strong photochemical consumption during daytime,resulting in the formation of ozone（O₃）. Five VOC sources were ...     

喷漆车间VOCs防治研究

简述了VOCs的来源和危害及喷喷漆车间VOCs防治研究漆车间的VOCs的特点,介绍了低温冷凝法、溶剂吸收法、吸附法等喷漆车间VOCs的传统治理技术,及近几年来发展起来的新治理技术,如生物法.     

硝基清漆膜厚度对硝基清漆VOCs释放的影响

利用自制的小型环境测试舱,研究了硝基清漆膜厚度对挥发性有机物(VOCs)释放的影响.漆膜厚度分别为296,508,715,799,960μm,测试条件为:温度为25.0℃,相对湿度为23.9%,空气流量为0.75m3/h,空气流速为3.4cm/s,支持板为不锈钢盘.采用真空采样罐采集舱出口空气,用气相色谱(GC-FID)分析测试.确定了5种主要VOCs(甲基环乙烷、甲苯、乙苯、间/对二甲苯和邻二甲苯)的浓度,并以一阶衰减模型对浓度进行模拟计算得到释放速率.结果表明,漆膜厚度并不影响VOCs的峰值浓度和初始释放速率,但漆膜越厚,VOCs的浓度衰减越慢,衰减速率越小.     

北京怀柔O3污染过程初始VOCs浓度特征及来源分析

为了解北京怀柔区夏季典型O₃污染过程中初始VOCs（挥发性有机物）浓度（以φ计）的特征,识别其关键物种及主要来源,于2016年8月3-11日在中国科学院大学雁栖湖校区教学楼顶开展强化观测,利用光化学物种比值法和连续反应模型法测算观测期间大气初始φ（VOCs）,采用MIR（最大增量反应活性）法估算初始VOCs的OFP（O₃生成潜势）,识别关键物种,并应用PMF（正交矩阵因子）模型对初始VOCs的来源进行解析.结果表明:北京怀柔区O₃污染过程中初始φ（VOCs）平均值为25.27×10-9,如忽略化学损失,φ（VOCs）将被低估约18.6%.初始VOCs的总OFP值为144.6×10-9,VOCs物种对总OFP贡献率的顺序依次为醛酮类>烯烃>芳香烃>烷烃,异戊二烯、乙醛、己醛、间/对-二甲苯、甲苯、乙烯、丙烯、1,2,4-三甲苯、丁酮、1,3,5-三甲苯是怀柔区O₃形成的关键活性物种.PMF解析结果显示,机动车尾气源对初始φ（VOCs）的贡献率（23.5%）最高,其次是溶剂使用源（18.3%）、植物排放源（18.1%）、工业过程源（17.6%）、生物质燃烧源（12.1%）和煤炭燃烧源（10.5%）.研究显示,在北京怀柔区典型O₃污染过程中,减少机动车尾气源、溶剂使用源、上风向工业过程源的排放是控制怀柔区VOCs的有效措施,而控制异戊二烯、乙醛、己醛、间/对-二甲苯、甲苯等关键活性物种则是有效抑制VOCs排放对O₃生成贡献的重要手段.      

唐山市和北京市夏秋季节大气VOCs组成及浓度变化

2007年和2008年6～9月,利用前级浓缩-气相色谱/质谱法,对唐山市大气中挥发性有机物的组成及浓度变化进行了采样分析研究.2008唐山市大气VOCs平均浓度为163.5×10-9C(碳单位体积比,下同),其中饱和烷烃占45.9%、芳香烃占29.9%、烯烃占5.9%、卤代烃占18.8%;相对2007年同期唐山大气VOCs平均浓度340.4×10-9C下降了51.9%,苯系物下降幅度最大为66.5%,卤代烃中工业排放的二氯苯浓度有所上升;2008唐山市大气VOCs比同期北京大气VOCs浓度低8.5%,奥运时段VOCs变化表明,唐山市大气VOCs除交通源外工业排放也是大气污染的重要来源.     

Ozone and secondary organic aerosol formation potential from anthropogenic volatile organic compounds emissions in China

Volatile organic compounds (VOCs) are major precursors for ozone and secondary organic aerosol (SOA), both of which greatly harm human health and significantly affect the Earth''s climate. We simultaneously estimated ozone and SOA formation from anthropogenic VOCs emissions in China by employing photochemical ozone creation potential (POCP) values and SOA yields. We gave special attention to large molecular species and adopted the SOA yield curves from latest smog chamber experiments. The estimation shows that alkylbenzenes are greatest contributors to both ozone and SOA formation (36.0% and 51.6%, respectively), while toluene and xylenes are largest contributing individual VOCs. Industry solvent use, industry process and domestic combustion are three sectors with the largest contributions to both ozone (24.7%, 23.0% and 17.8%, respectively) and SOA (22.9%, 34.6% and 19.6%, respectively) formation. In terms of the formation potential per unit VOCs emission, ozone is sensitive to open biomass burning, transportation, and domestic solvent use, and SOA is sensitive to industry process, domestic solvent use, and domestic combustion. Biomass stoves, paint application in industrial protection and buildings, adhesives application are key individual sources to ozone and SOA formation, whether measured by total contribution or contribution per unit VOCs emission. The results imply that current VOCs control policies should be extended to cover most important industrial sources, and the control measures for biomass stoves should be tightened. Finally, discrepant VOCs control policies should be implemented in different regions based on their ozone/aerosol concentration levels and dominant emission sources for ozone and SOA formation potential.     

工业VOCs排放源废气排放特征调查与分析

在大量调研工业挥发性有机物(VOCs)排放源案例的基础上,将工业VOCs排放源分为溶剂产品使用源、化工产品生产源、废物处理源和存储输送源4类,并对不同类型工业VOCs源的废气排放特征进行了分析.结果表明,大多数有组织排放的工业VOCs源的废气流量>1000m3/h,总挥发性有机物(TVOC)浓度100000m3/h的VOCs源以溶剂产品使用源为主;流量10000mg/m3或<100mg/m3的工业VOCs源,均以化工产品生产源为主.在工业VOCs源排放的各种VOCs组分中,以苯系物最为常见     

吹扫/捕集与气质联用技术测定水中挥发性有机物

以美国EPA524．2方法为依据，用Purge／Trap—GC／MS技术检测水源水中挥发性有机物（VOCs），通过多次实验寻求所测有机物质分离检测的最佳条件。     

Vertical distribution of volatile organic compounds conducted by tethered balloon in the Beijing-Tianjin-Hebei region of China

Volatile organic compounds (VOCs) as precursors of ozone and secondary organic aerosols can cause adverse effects on the environment and human health. However, knowledge of the VOC vertical profile in the lower troposphere of major Chinese cities is poorly understood. In this study, tethered balloon flights were conducted over the juncture of Beijing-Tianjin-Hebei in China during the winter of 2016. Thirty-six vertical air samples were collected on selected heavy and light pollution days at altitudes of 50-1000 meters above ground level. On average, the concentration of total VOCs (TVOCs) at 50-100 m was 4.9 times higher than at 900-1000 m (46.9 ppbV vs. 8.0 ppbV). TVOC concentrations changed rapidly from altitudes of 50-100 to 401-500 m, with an average decrease of 72%. With further altitude increase, the TVOC concentration gradually decreased. The xylene/benzene ratios of 34/36 air samples were lower than 1.1, and the benzene/toluene ratios of 34/36 samples were higher than 0.4, indicating the occurrence of aged air mass during the sampling period. Alkenes contributed most in terms of both OH loss rate (39%-71%) and ozone formation potential (40%-72%), followed by aromatics (6%-38%). Finally, the main factors affecting the vertical distributions of VOCs were local source emission and negative dispersion conditions on polluted days. These data could advance our scientific understanding of VOC vertical distribution.     

CuMnO_x/γ-Al_2O_3对含甲苯废气催化燃烧的性能研究

利用浸渍法制备催化剂CuO/γ-Al2O3、MnOx/γ-Al2O3、CuMnOx/γ-Al2O3,通过实验研究表明:CuMnOx/γ-Al2O3具有更高的催化活性,其T99比其他两种催化剂要低50℃以上。在焙烧温度300、400、500、600℃下制备CuMnOx/γ-Al2O3,比较其催化活性,发现在600℃制备的催化剂要比其他温度下制备的同等催化剂的催化活性高,证明了尖晶石结构在催化燃烧中起着很大的作用。