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In between, photochemistry plays an important role on both sources and sinks of O 3 , subjected to the atmospheric NO x levels 4 , 6. Xue et al. In urban site, the mixing ratio of NO x is often high up to 70 ppbv due to large quantities of emissions from heavy industries and vehicular engines. Under short term regulatory measures, reduction of anthropogenic VOCs emission is efficient in shrinking of O 3 peak.
Understanding of the sources of VOCs is a base for O 3 pollution control. Common anthropogenic activities include coal burning from industrial and residential uses, vehicle exhausts, gasoline volatilization, solvent use, petrochemical manufacturing and biomass burning 10 , 11 , 12 , 13 , 14 , 15 , 16 , In addition, biogenic source, in particular of vegetation emission, is a vital factor in VOCs budget 18 , 19 , In Northern China e. However, solvent use was the major source contributor reported in Pearl River Delta PRD region in China, where influenced by the emissions from a large number of factories e.
Fine particle and ground-level O 3 are the causes for severe air pollutions, which pose high health risk as well 29 , 30 , In the recent years, the surface O 3 level has been continuously increasing in most Chinese cities In northern region, the concentration in rural site had an increasing rate of 1. And in the urban site, it was found that surface O 3 increased as rate of 1.
Baoji is an industrial city in the western edge of Guanzhong basin, and was in Shaanxi province in Northwestern China. The main industries include power plants, coal chemical industry, metal smelting, and coke productions The consumption of coal from industry sector is about ten millions tons annually from the official statistic collected by Baoji Municipal Environmental Protection Bureau, not published yet. And the emissions plumes from both industry and traffic emissions can highly impact the air quality and elevate the surface O 3 pollution to downwind regions 5 , 37 , 38 , In summer, the mixing ratios of surface O 3 in Baoji increased with ambient temperature and radiation.
Either speciation or evaluation of VOCs was sparsely conducted in Northwestern China 40 , and no any data were even reported in Baoji. A one-week simultaneous observation was used to evaluate the levels and compositions of both VOCs and O 3 in this industrial city in summer, This study aims to investigate the impacts of VOCs emissions on the pollution in this typical industrial city. A total number of 57 VOCs that contributed mostly on the O 3 formation in atmosphere were quantified Temporal variation and potential pollution sources were identified.
Isoprene is classified separately from alkenes to evaluate its strong indication from biogenic sources. The highest levels of aromatics and alkenes were observed in the Weibin site, with the mixing ratios of The high abundances can be ascribed to the existence of fossil fuel combustion sources installed in the industries nearby the site 10 , Particularly, aromatics had a molar contribution of Benzene, the most abundant aromatic in the samples of Weibin site, is an well-known tracer for the emissions of coal, biomass burning, and automobile Propene was the next abundant compound, followed by undecane, 2-methylhexane, toluene, and iso-pentane.
This distribution was consistent with the emission profiles of metal smelt, coke production and power plants, which were located at the upwind position of the Weibin site The result also implies that the strong impacts from combustion sources such as industrial coal burning and vehicular emission.
This finding was relatable to the facts that the Chencang site was next to two highways Lian-huo highway and Bao-han highway and less factories nearby. At the Miaogou site, the mixing ratios of most VOCs PAMS were the lowest among the three sites, with exceptions of toluene, styrene, undecane, isoprene, and p-diethylbenzene. Toluene and styrene are universal components in solvents used in manufactures 43 , while C 9 -C 12 alkanes and isoprene are tracers for diesel exhaust and biogenic sources, respectively 10 , Scattered small-scale paint factories presented around the site in the on-site survey, and the plants in the forests can contribute greatly on the biogenic emissions 10 , Dense power plants, metal smelt, coke production and coal chemical industries were located in the eastern and northeastern regions of Baoji.
The high-frequency easterly surface winds could thus bring up those discharged pollutants to the downwind locations. The consequent effects can be also reflected on the significant elevation of corresponding marker species such as benzene and propene.
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This could also demonstrate the strong impact from the industrial emissions. Propane and n -butane are important VOCs from vehicular emissions, and their correlation acts a useful indicator for traffic contribution 10 , In the current study, propane was well-correlated with n -butane at both sites 0. The regressions of aromatics and long-chain alkanes e.
Benzene is a typical VOCs PAMS emitted from diesel-fueled engine, coal combustion, biomass burning, and natural gas combustion 10 , 42 , 44 , 45 , 46 , while gasoline-fueled engine emission, paint production, printing, and other solvent involved activities release more toluene, ethylbenzene, xylene and styrene in composition 10 , Those correlations not only prove the high contribution of combustion sources in the Weibin site, and also suggest that the ambient levels of toluene, ethylbenzene, xylenes, styrene, 1,3,5-trimethylbenzene and n -decane might be additionally elevated by solvent-related industries 10 , In contrast to the Weibin site, the mixing ratios of toluene, styrene and dodecane were unexpectedly high in the Miaogou site.
This also indicates that the solvent involved manufacture processes in the scattered paint and printing factories had a large contribution to the emissions of toluene and other aromatics In this study, the ratios of xylenes to ethylbenzene were both high at the Weibin site and Chencang sites 1.
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However, a much low average ratio was found in the Miaogou site 0. It is reasonable that relatively more aged air mass in Miaogou region due to its geographical position 48 , even though its average VOCs PAMS levels were close to that at Chencang site. Source apportionment was conducted with PMF receptor model. Calibration was run for 3—7 factors and with random seeds.
The seven factors solution produced mathematical [ Q values both robust and true close to the theoretical Q value] with reasonable explanation.
The results are illustrated in Fig. In Factor 1, it has high loadings of benzene, propylene, 1-butene and 1-pentene in a descending order in mixing ratios, that was close to the profile of coal combustion emissions Factor 2 is filled with propane, n-butane, n-pentane, iso-pentane and toluene. Factor 3 is characterized by n-decane, undecane, xylenes, ethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, p-diethylbenzene, 3-methylpentane, ethylene, 1-pentene.
The composite was corresponding to and dominated by the diesel-fuel combustion However, it must be noted that 3-methylpentane, a common marker for gasoline exhaust, was unexpectedly high in this factor. Even though the major contribution of Factor 3 could be characterized by the diesel combustion, the gasoline emission might still contribute a few. Factor 4 is consistent with a typical gasoline exhaust profile. Factor 5 is singly filled with high abundance of iso-butane but no representative source could be identified, thus is marked as others.
Isoprene is the major component in vegetation emission, even it is always detected in the vehicle exhaust Considering that high contribution of vegetation, isoprene is identified as a biogenic source marker. Factor 7 can be identified as biogenic source since isoprene had the highest contribution Taking all of the samples in accounting, vehicle exhaust As mentioned above, Baoji is a typical industrial city, and the main industries include power plants, coal chemical industry, metal smelting, and coke productions Most of the related industries use coal as fuel or feed, this could cause high level of benzene in ambient air.
In addition, heavy industries induce dense heavy truck usage for transport in the city Baoji. These together makes high contribution of industrial and diesel vehicle exhaust. The industry emission and gasoline-related sources were the two largest contributors In the Chencang, diesel exhaust was the most important source, contributing to Solvent-related emission contributed Covering with a high density of forest area, the mixing ratio of isoprene at the Miaogou was high.
Therefore, a stronger strength of biogenic emission of The L OH in Weibin site was mainly dominated by the groups of alkenes and aromatics due to the strong influences of industrial and traffic emissions. In addition to their high chemical reactivity, the two pollution sources are thus considered to play key roles on hydroxyl radical-driven oxidations in Weibin site Baoji. The air quality at the Chencang was less impacted by the direct industrial activities, and the L OH was thus less than half of that in the Weibin site.
The group of alkanes, which has a lower chemical reactivity, was the major contributor At the remote site, even though the mixing ratios of most VOCs PAMS were relatively low, the high abundance of extremely-reactive isoprene dominated Considering that alkenes play important roles on the chemical reactivity, the contributions of the most significant individuals at different concentration levels were displaced in Fig. At a low mixing ratio region 0—35 ppbv , mostly in samples collected in the Chencang and Miaogou, the biogenic-emitted compounds i. The variations of surface O 3 at the three sites were depicted in Fig.
In typical, double concentration peaks could be identified during this time interval.
The first peak appeared around , and the next one was recorded between — The surface O 3 concentrations decreased gradually after and the lowest values at the Weibin site and Miaogou sites were often observed at and , respectively. It should be noted that the surface O 3 levels were significantly lower at the Weibin site than Miaogou site during the nighttime. The cases have been detailly explained in following sections. The correlations between surface O 3 and important meteorological parameters were fully studied.
High O 3 concentrations were often detected under high ambient temperatures and low RHs, which offer favor conditions for either formation or reservation of O 3 50 , Besides, water vapor could scavenge O 3 and its precursors in atmosphere by wet deposition The O 3 levels were also coincided with the surface zonal winds within our observation period Fig. More obvious impacts from the direction of surface winds could be seen at the Miaogou site.
Five episodes were defined between Jun 16 and Jun 20, when the O 3 levels increased with easterly winds and under higher ambient temperatures. Particularly, the double O 3 peaks occurred in the afternoon on Jun 16, Jun17 and Jun 19, while strong northeasterly and northerly winds were dominated. This suggested that the polluted air masses were transported from the Weibin site and industrial zone in the northeastern region of Baoji. The results of our study were consistent with the findings. The first O 3 peak in the afternoon was reasonably initiated by the formations from the local pollutants i.
The MIRs were obtained from Carter The highest overall OFP The marker species of propene and m -diethylbenzene were the two most important VOCs PAMS which contributed to more than half of overall OFPs, indicating that vehicle and industrial emissions greatly affected the surface O 3 formation.
At the Miaogou site, isoprene and solvent-characterized VOCs such as toluene, styrene, xylenes, and long-chain alkanes contributed most of OFPs loading. In another aspect, air mass aging can also contribute the variation of OFPs Even though the overall estimated OFPs was low at the Miaogou site, the actual O 3 levels were not the lowest as expected Fig. This can be ascribed to the transport of O 3 from other upwind districts 3.
The results from the current study concluded that the fresh plume from industrial and traffic sources at the upwind location could highly impact on the air quality in Baoji, and lead the occurrence of O 3 episodes in residential areas in summer. Ozone pollution control is a challenging task in China, partly due to a huge number of VOCs emissions. In this study, the high levels and compositions of alkenes and aromatics in the the ambient of Baoji suggest the large contributions from the combustion sources in surrounding industries.
The temporal variations of VOCs PAMS were driven by the directions of surface winds, in which the pollutants were transported from upwind regions. Aging of air mass was much obviously at the Miaogou site owing to its location distanced from the dense pollution origins.
The O 3 formation in Baoji was influenced by both export of well-processed industry plume and photochemical reactions. More long-term VOCs monitoring and environmental assessment are thus needed to interpret the characteristic roles of VOCs in the production of surface O 3 in different regions in China.
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Development of mathematical models is vital to conclude the data in assistance to solve the related environmental issue. No any anthropogenic pollution sources rather than vehicular emission were observed around this site. The location is surrounded by Qin Mountain where the forests dominated the most land covers. Very scattered factories were found nearby this region.
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Samplings were conducted at —, —, — and —, respectively, from June 15 to June 21, Two sorbent tube samples were thus collected in each time interval. The sampling inlet was set-up at 1. Prior to the sampling, all sorbent tubes were cleaned in a thermal conditioner TC20, Markes International Ltd.
All pre-conditioned and sampled tubes were sealed with Difflok caps Markes International Ltd. The desiccators were filled with silica gel and activated carbon to avoid passive absorption of any water vapor and VOCs, respectively. One field blank was collected on each sampling day.
The sorbent samples were properly transported to the laboratory for chemical analysis. Real-time concentrations of the trace gases were monitored continuously during the sampling event. The meteorological data i. A total of 72 valid sorbent tube samples were collected.
The chemical analysis procedure can be found in our previous work The constant flow rate of He carrier gas was 1. Identification was achieved by comparing the mass spectra and retention times of the chromatographic peaks with those authentic standards. The minimum detection limits MDLs were in the range of 0. A standard receptor model of PMF Version 3.
EPA was used for source apportionment in this study. In principle, the PMF model is based on the following equations:. Q is the weighted sum of squares of differences between the PMF output and the original data sets.
One of the objectives of PMF analysis is to minimize the Q value. Chan, C. Characteristics of biomass burning emission sources, transport, and chemical speciation in enhanced springtime tropospheric ozone profile over Hong Kong. Stohl, A. Xue, L. Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes.
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Sillman, S. The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments. Brune, W. Ozone production chemistry in the presence of urban plumes. Faraday Discussions. Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Concern for the Environment We believe it is our duty to protect the environment and we do this by complying with all applicable environmental laws and regulations.
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