The underappreciated role of fugitive VOCs in ozone formation and health risk assessment emitted from seven typical industries in China

Fugitive emission from industrial sources may result in ozone formation and health risk,while the exact contribution of this source remains incompletely understood.In this study,emission characteristics,ozone formation potential(OFP)and health risk of fugitive VOCs in7 representative industries were investigated.Chemical material industry was the dominant contributor to VOCs of fugitive emission in comparison with other industries.The OFP of VOCs from fugitive emission was in the range of 1.45×10^(3)-3.98×10^(5)μg/m^(3),with a higher value than that of organized emission in seven industries except for the coking industry and the chemical material industry,suggesting that fugitive VOCs should be taken into account while developing control strategies.Acetaldehyde,m,p-xylene,n-nonane,ethylene,vinyl chloridethe and other high OFP-contributing species were the major reactive species that should be targeted.Health risk assessment investigated non-cancer and cancer risks of fugitive VOCs in 7 industries were all above safe level(HR>1 and LCR>1×10^(-4)),posing remarkable health threats to human health.OVOCs were the main contributor to non-cancer risk,while halohydrocarbons and aromatics contributed most to cancer risks,posing remarkable health threat on human health.Our findings highlighted the contribution of fugitive VOCs on ozone formation and health risk was underestimated,indicating which should be considered in emission control strategies of industrial sources.

Formation and emission characteristics of VOCs from a coal-fired power plant

On-site measurements of volatile organic compounds(VOCs)in different streams of flue gas were carried out on a real coal-fired power plant using sampling bags and SUMMA canisters to collect gas samples,filters to collect particle samples.Gas chromatography-flame ionization detector/mass spectrometry and gas chromatography-mass spectrometry was the offline analysis method.We found that the total mass concentration of the tested 102 VOC species at the outlet of wet flue gas desulfuration device was(13456±47)μg·m^(-3),which contained aliphatic hydrocarbons(57.9%),aromatic hydrocarbons(26.8%),halogen-containing species(14.5%),and a small amount of oxygen-containing and nitrogencontaining species.The most abundant species were 1-hexene,n-hexane and 2-methylpentane.The top ten species in terms of mass fraction(with a total mass fraction of 75.3%)were mainly hydrocarbons with a carbon number of 6 or higher and halogenated hydrocarbons with a lower carbon number.The mass concentration of VOC species in the particle phase was significantly lower than that in the gas phase.The change of VOC mass concentrations along the air pollution control devices indicates that conventional pollutant control equipment had a limited effect on VOC reduction.Ozone formation potential calculations showed that aromatic hydrocarbons contributed the highest ozone formation(46.4%)due to their relatively high mass concentrations and MIR(maximum increment reactivity)values.

上海某居民区恶臭污染溯源、臭氧生成潜势及健康风险评估

针对上海某居民区恶臭投诉问题,对恶臭物质来源、特征及其风险评估展开相关研究。利用正定矩阵因子分解(positive matrix factorization,PMF)模型对居民区恶臭点连续监测数据进行来源解析,共识别出3个排放源,分别为餐厨垃圾源(41.24%)、农业源(32.85%)、二次生成和尾气排放混合源(25.91%),确定餐厨垃圾源为居民区恶臭的主要来源。通过分析监测点位间主要致臭物质异味活度值(odor active value,OAV)的相关性,可知居民区受到餐厨垃圾预处理车间和生化车间的恶臭污染为主,全天受影响程度具有间歇式变化特征。通过计算预处理、生化处理和深加工3个车间排气筒的恶臭物质的臭氧生成潜势(ozone formation potential,OFP),可知各物质种类对OFP的贡献率从大到小依次为羰基类(37.46%)、醇类(21.38%)、烯烃类(15.52%)、挥发性脂肪酸类(13.70%)、芳香烃类(4.02%)、含氮化合物(3.90%)、烷烃类(1.77%)、酯类(1.29%)、硫化物(0.95%)、含氯有机物(0.01%),羰基类、醇类、烯烃类、挥发性脂肪酸类为该厂区OFP贡献的代表物质种类。各车间的OFP从高到低依次为预处理车间(27051.82μg/m^(3))、生化车间(7547.51μg/m^(3))、深加工车间(1647.14μg/m^(3)),乙醛、丙烯酸、1-丁烯、甲醛、乙醇、丙烯和苯酚对OFP的贡献率在3个排气筒中均较高,是该餐厨垃圾处理厂区生成臭氧的主要污染物质,并且乙醛对OFP的贡献率最高。敏感点恶臭物质的健康风险评估结果表明,监测期间累计非致癌风险指数与致癌风险指数均超过美国国家环境保护局(U.S.Environmental Protection Agency,U.S.EPA)推荐的安全阈值,主要贡献物质分别为丙烯醛和甲醛。因此,乙醛、丙烯醛和甲醛应作为餐厨垃圾处理厂中恶臭物质的优先监控指标。

Comparative investigation of coal-and oil-fired boilers based on emission factors,ozone and secondary organic aerosol formation potentials of VOCs

Volatile organic compounds(VOCs)are the important precursors of the tropospheric ozone(O3)and secondary organic aerosols(SOA),both of which are known to harm human health and disrupt the earth’s climate system.In this study,VOC emission factors,O3 and SOA formation potentials were estimated for two types of industrial boilers:coal-fired boilers(n=3)and oil-fired boilers(n=3).Results showed that EVOCs concentrations were more than nine times higher for oil-fire d boilers compared to those for coal-fired boilers.Emission factors ofΣVOCs were found to be higher for oil-fired boilers(9.26-32.83 mg-VOC/kg)than for coal-fired boilers(1.57-4.13 mg-VOC/kg).Alkanes and aromatics were obtained as the most abundant groups in coal-fired boilers,while oxygenated organics and aromatics were the most contributing groups in oil-fired boilers.Benzene,n-hexane and o-ethyl toluene were the abundant VOC species in coal-fired boiler emissions,whereas toluene was the most abundant VOC species emitted from oil-fired boilers.O3 and SOA formation potentials were found 12 and 18 times,respectively,higher for oil-fired than for coal-fired boilers.Total OFP ranged from 3.99 to 11.39 mg-O3/kg for coal-fired boilers.For oil-fired boilers,total OFP ranged from 36.16 to 131.93 mg-O3/kg.Moreover,total secondary organic aerosol potential(SOAP)ranged from 65.4 to 122.5 mg-SOA/kg and 779.9 to 2252.5 mg-SOA/kg for the coal-fired and oil-fired boilers,respectively.

Characteristics and source apportionment of ambient volatile organic compounds and ozone generation sensitivity in urban Jiaozuo,China

In recent years,many cities have taken measures to reduce volatile organic compounds(VOCs),an important precursor of ozone(O_(3)),to alleviate O_(3) pollution in China.116 VOC species were measured by online and offline methods in the urban area of Jiaozuo from May to October in 2021 to analyze the compositional characteristics.VOC sources were analyzed by a positive matrix factorization(PMF)model,and the sensitivity of ozone generation was determined by ozone isopleth plotting research(OZIPR)simulation.The results showed that the average volume concentration of total VOCs was 30.54 ppbv and showed a bimodal feature due to the rush-hour traffic in the morning and at nightfall.The most dominant VOC groups were oxygenated VOCs(OVOCs,29.3%)and alkanes(26.7%),and the most abundant VOC species were acetone and acetylene.However,based on the maximum incremental reactivity(MIR)method,the major VOC groups in terms of ozone formation potential(OFP)contribution were OVOCs(68.09μg/m^(3),31.5%),aromatics(62.90μg/m^(3),29.1%)and alkene/alkynes(54.90μg/m^(3),25.4%).This indicates that the control of OVOCs,aromatics and alkene/alkynes should take priority.Five sources of VOCs were quantified by PMF,including fixed sources of fossil fuel combustion(27.8%),industrial processes(25.9%),vehicle exhaust(19.7%),natural and secondary formation(13.9%)and solvent usage(12.7%).The empirical kinetic modeling approach(EKMA)curve obtained by OZIPR on O_(3) exceedance days indicated that the O_(3) sensitivity varied in different months.The results provide theoretical support for O_(3) pollution prevention and control in Jiaozuo.

Reactivity of ambient volatile organic compounds(VOCs) in summer of 2004 in Beijing

Ambient volatile organic compounds （VOCs） were sampled at six sites in Beijing in the summer of 2004 and analyzed by GCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates （LOH） and ozone formation potentials （OFPs）. Top 15 reactive species, mainly alkenes and aromatics, were identified by these two methods, and accounted for more than 70% of total reactivity of VOCs. In urban areas, isoprene was the most reactive species in term of OH loss rate, contributing 11.4% to the LOH of VOCs. While toluene, accounting for 9.4% of OFPs, appeared to have a long-time role in the photochemical processes. Tongzhou site is obviously influenced by local chemical industry, but the other five sites showed typical urban features influenced mainly by vehicular emissions.

Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential

Fifteen heavy-duty diesel vehicles were tested on chassis dynamometer by using typical heavy duty driving cycle and fuel economy cycle. The air from the exhaust was sampled by 2,4- dinitrophenyhydrazine cartridge and 23 carbonyl compounds were analyzed by high performance liquid chromatography. The average emission factor of carbonyls was 97.2 mg/km, higher than that of light-duty diesel vehicles and gasoline-powered vehicles. Formaldehyde, acetaldehyde, acetone and propionaidehyde were the species with the highest emission factors. Main influencing factors for carbonyl emissions were vehicle type, average speed and regulated emission standard, and the impact of vehicle loading was not evident in this study. National emission of carbonyls from diesel vehicles exhaust was calculated for China, 2011, based on both vehicle miles traveled and fuel consumption. Carbonyl emission of diesel vehicle was estimated to be 45.8 Gg, and was comparable to gasolinepowered vehicles （58.4 Gg）. The emissions of formaldehyde, acetaldehyde and acetone were 12.6, 6.9, 3.8 Gg, respectively. The ozone formation potential of carbonyls from diesel vehicles exhaust was 537 mg O3/km, higher than 497 mg O3/km of none-methane hydrocarbons emitted from diesel vehicles.

Characteristics of ozone pollution and the sensitivity to precursors during early summer in central plain, China

In this study,we conducted an observation experiment from May 1 to June 30,2018 in Zhengzhou,a major city in central China,where ground ozone(O3)pollution has become serious in recent years.The concentrations of O3 and its precursors,as well as H2O_(2) and meteorological data were obtained from the urban site(Yanchang,YC),suburban(Zhengzhou University,ZZU)and background sites(Ganglishuiku,GLSK).Result showed that the rates of O3 concentration exceeded Chinese National Air Quality Standard GradeⅡ(93.3 ppbv)were 59.0%,52.5%,and 55.7%at the above three sites with good consistency,respectively,indicating that O3 pollution is a regional problem in Zhengzhou.The daily peak O3 appeared at 15:00-16:00,which was opposite to VOCs,NOx,and CO and consistent with H2O_(2).The exhaustive statistical analysis of meteorological factors and chemical effects on O3 formation at YC was advanced.The high concentration of precursors,high temperature,low relative humidity,and moderately high wind speed together with the wind direction dominated by south and southeast wind contribute to urban O3 episodes in Zhengzhou.O3 formation analysis showed that reactive alkenes such as isoprene and cis-2-butene contributed most to O3 formation.The VOCs/NOx ratio and smog production model were used to determine O3-VOC-NOx sensitivity.The O3 formation in Zhengzhou during early summer was mainly under VOC-limited and transition regions alternately,which implies that the simultaneous emission reduction of alkenes and NOx is effective in reducing O3 pollution in Zhengzhou.

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(O_(3))pollutions are prevalent air quality issues in China.Volatile organic compounds(VOCs)have significant impact on the formation of O_(3)and secondary organic aerosols(SOA)contributing PM_(2.5).Herein,we investigated 54 VOCs,O_(3)and SOA in Tianjin from June 2017 to May 2019 to explore the non-linear relationship among O_(3),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 O_(3)was exactly the opposite.Machine learning methods resolved the importance of individual VOCs on O_(3)and SOA that alkenes(mainly ethylene,propylene,and isoprene)have the highest importance to O_(3)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 O_(3)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 O_(3)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 O_(3).

Chemical characterization of volatile organic compounds (VOCs) emitted from multiple cooking cuisines and purification efficiency assessments

Cooking process can produce abundant volatile organic compounds(VOCs),which are harmful to environment and human health.Therefore,we conducted a comprehensive analysis in which VOCs emissions from multiple cuisines have been sampled based on the simulation and acquisition platform,involving concentration characteristics,ozone formation potential(OFP)and purification efficiency assessments.VOCs emissions varied from 1828.5 to 14,355.1μg/m^(3),with the maximumand minimumvalues fromBarbecue and Family cuisine,respectively.Alkanes and alcohol had higher contributions to VOCs from Sichuan and Hunan cuisine(64.1%),Family cuisine(66.3%),Shandong cuisine(69.1%)and Cantonese cuisine(69.8%),with the dominant VOCs species of ethanol,isobutane and n-butane.In comparison,alcohols(79.5%)were abundant for Huaiyang cuisine,while alkanes(19.7%),alkenes(35.9%)and haloalkanes(22.9%)accounted for higher proportions from Barbecue.Specially,carbon tetrachloride,n-hexylene and 1-butene were the most abundant VOCs species for Barbecue,ranging from 8.8%to 14.6%.The highest OFP occurred in Barbecue.The sensitive species of OFP for Huaiyang cuisine were alcohols,while other cuisines were alkenes.Purification efficiency assessments shed light on the removal differences of individual and synergistic control technologies.VOCs emissions exhibited a strong dependence on the photocatalytic oxidation,with the removal efficiencies of 29.0%–54.4%.However,the high voltage electrostatic,wet purification and mechanical separation techniques played a mediocre or even counterproductive role in the VOCs reduction,meanwhile collaborative control technologies could not significantly improve the removal efficiency.Our results identifiedmore effective control technologies,which were conductive to alleviating air pollution from cooking emissions.

Environmental impact and health risk assessment of volatile organic compound emissions during different seasons in Beijing

Volatile organic compounds(VOCs)are major contributors to air pollution.Based on the emission characteristics of 99 VOCs that daily measured at 10 am in winter from 15 December 2015 to 17 January 2016 and in summer from 21 July to 25 August 2016 in Beijing,the environmental impact and health risk of VOC were assessed.In the winter polluted days,the secondary organic aerosol formation potential(SOAP)of VOC(199.70±15.05 mg/m^3)was significantly higher than that on other days.And aromatics were the primary contributor(98.03%)to the SOAP during the observation period.Additionally,the result of the ozone formation potential(OFP)showed that ethylene contributed the most to OFP in winter(26.00%and 27.64%on the normal and polluted days).In summer,however,acetaldehyde was the primary contributor to OFP(22.00%and 21.61%on the normal and polluted days).Simultaneously,study showed that hazard ratios and lifetime cancer risk values of acrolein,chloroform,benzene,1,2-dichloroethane,acetaldehyde and 1,3-butadiene exceeded the thresholds established by USEPA,thereby presenting a health risk to the residents.Besides,the ratio of toluene-to-benzene indicated that vehicle exhausts were the main source of VOC pollution in Beijing.The ratio of m-/p-xylene-toethylbenzene demonstrated that there were more prominent atmospheric photochemical reactions in summer than that in winter.Finally,according to the potential source contribution function(PSCF)results,compared with local pollution sources,the spread of pollution from long-distance VOCs had a greater impact on Beijing.

VOCs evaporative emissions from vehicles in China:Species characteristics of different emission processes

Vehicle evaporation is an essential source of VOCs in cities but is not well understood in China.Reported emission factors from previous studies are not enough for understanding the atmospheric chemical process of vehicular evaporative VOCs.In this work,a serious of detailed VOCs speciation profiles are developed based on test processes and emission processes.A mass balance method was used to divide different emission processes during diurnal tests.The results show that headspace vapor of gasoline cannot represent the real-world vehicle evaporation because of the significant differences in VOCs speciation profiles,especially for aromatics.To further distinguish emissions from evaporation and exhaust,only the ratios of MTBE/benzene and MTBE/toluene can serve as indicators when considering species from all evaporative processes.Besides,emissions from different sources change significantly with the seasons.To solve these problems,we developed a monthly comprehensive evaporation speciation profile.The individual profiles at the emission processes are weighted by the emission of the in-use vehicle fleet in Beijing to derive the comprehensive speciation profile of evaporative VOCs.Ozone formation potential(OFP)and secondary organic aerosol potential(SOAP)were used to evaluate the environmental impact.For SOAP,100 g evaporative emissions are equal to 6.05-12.71 g toluene in different months,much higher than that given using headspace vapors,especially in winter(7.2 times higher in December).These findings would improve our understanding of the evaporative VOCs emissions in China and their environmental impacts(e.g.,O3 and SOA formation).

On-board measurements of gaseous pollutant emission characteristics under real driving conditions from light-duty diesel vehicles in Chinese cities

A total of 15 light-duty diesel vehicles（LDDVs） were tested with the goal of understanding the emission factors of real-world vehicles by conducting on-board emission measurements. The emission characteristics of hydrocarbons（HC） and nitrogen oxides（NOx） at different speeds, chemical species profiles and ozone formation potential（OFP） of volatile organic compounds（VOCs） emitted from diesel vehicles with different emission standards were analyzed. The results demonstrated that emission reductions of HC and NOxhad been achieved as the control technology became more rigorous from Stage I to Stage IV. It was also found that the HC and NOxemissions and percentage of O2 dropped with the increase of speed, while the percentage of CO2 increased. The abundance of alkanes was significantly higher in diesel vehicle emissions, approximately accounting for 41.1%–45.2%, followed by aromatics and alkenes. The most abundant species were propene,ethane, n-decane, n-undecane, and n-dodecane. The maximum incremental reactivity（MIR）method was adopted to evaluate the contributions of individual VOCs to OFP. The results indicated that the largest contributors to O3 production were alkenes and aromatics, which accounted for 87.7%–91.5%. Propene, ethene, 1,2,4-trimethylbenzene, 1-butene, and1,2,3-trimethylbenzene were the top five VOC species based on their OFP, and accounted for 54.0%-64.8% of the total OFP. The threshold dilution factor was applied to analyze the possibility of VOC stench pollution. The majority of stench components emitted from vehicle exhaust were aromatics, especially p-diethylbenzene, propylbenzene, m-ethyltoluene, and p-ethyltoluene.