Quantitative relationship between visibility and mass concentration of PM2.5 in Beijing

The pollution of particulate matter less than 2.5μm （PM2.5） is a serious environmental problem in Beijing. The annual average concentration of PM2.5 in 2001 from seasonal monitor results was more than 6 times that of the U,S, national ambient air quality standards proposed by U.S. EPA. The major contributors to mass of PM2.5 were organics, crustal elements and sulfate. The chemical composition of PM2.5 varied largely with season, but was similar at different monitor stations in the same season. The fine particles （PM2.5） cause atmospheric visibility deterioration through light extinction, The mass concentrations of PM2.5 were anti-correlated to the visibility, the best fits between atmospheric visibility and the mass concentrations of PM2.5 were somehow different： power in spring, exponential in summer, logarithmic in autumn, power or exponential in winter. As in each season the meteorological parameters such as air temperature and relative humidity change from day to day, probably the reason of above correlations between PM2.5 and visibility obtained at different seasons come from the differences in chemical compositions of PM2.5.

Structural effect and reaction mechanism of MnO_2 catalysts in the catalytic oxidation of chlorinated aromatics

Various MnO2 structures have been extensively applied in catalysis. In this study,γ-MnO2,α-MnO2, and δ-MnO2 with corresponding rod, tube, and hierarchical architecture morphologies were prepared and applied for the catalytic oxidation of chlorobenzene (CB). The redox ability, H2O activation behavior, and acidity of MnO2 were analyzed using a range of techniques, including TPR, H2O-TPD, XPS, and pyridine-IR. The catalytic activities in CB oxidation were assessed;this revealed that γ-MnO2 exhibited the highest activity and best stability, owing to its enriched surface oxygen vacancies that functioned to activate O2 and H2O, and capture labile chlorine, which reacted with dissociated H2O to form HCl. All the MnO2 phases generated toxic polychlorinated by-products, including CHCl3, CCl4, C2HCl3, and C2Cl4, indicating the occurrence of electrophilic chlorination during CB oxidation. In particular, the dichlorobenzene detected in the effluents of α-MnO2 might generate unintended dioxins via a nucleophilic substitution reaction.

Distributions of dimethylsulfide in the Bohai Sea and Yellow Sea of China

Dimethylsulfide(DMS) measurements in the surface seawater of China eastern coastline were conducted during March 9—10, 1993 in Bohai Sea along the cruise from Dalian to Tianjin and during September 24—25, 1994 in Yellow Sea along the cruise from Shanghai to Qingdao. On the cruise in Bohai Sea DMS concentrations varied from 0.11 to 2.63 nmol/L with an average of 1.31 nmol/L, while DMS flux was estimated to be 0.85 μmol/(m 2·d) with the range of 0.04—3.12 μmol/(m 2·d). On the cruise in Yellow Sea DMS concentrations varied from 0.95 to 7.48 nmol/L with an average of 2.89 nmol/L, and DMS flux was estimated to be 7.94 μmol/(m 2·d) with the range of 0.11—18.88 μmol/(m 2·d). Variations in DMS concentrations along the latitude in Yellow Sea were observed larger than those along the longitude in Bohai Sea. DMS concentrations and fluxes had a similar spatial trend both in Bohai Sea and Yellow Sea with the correlation coefficients of 0.75 and 0.64, respectively.

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.

Estimation and prediction of black carbon emissions in Beijing City

Black carbon is a by-product of incomplete combustion of carbon containing fuels. It can alter atmos-pheric radiation property and make adverse impacts on human health. The energy consumption in Beijing City depends largely on coal burning. Recently,Beijing City has been performing the municipal energy structure adjustment as a tool for air pollution abatement,aiming at the air quality goal for the Beijing 2008 Olympic Games. Based on Beijing energy use data in 2000,combined with emission fac-tors of major sources of black carbon,the emission of black carbon in Beijing City is estimated to be 7.77 Gg. Coke,raw coal and biomass as non-commercial energy are the main contributors to municipal black carbon emissions. Based on Beijing energy planning in the year 2008,the emission of black carbon in 2008 will be 2.97 Gg if the contribution from biomass is not taken into account. Assuming that the black carbon emission from rural biomass in 2008 is the same as that in 2004,the biomass burning will be the largest emitter of black carbon to Beijing City in 2008.

Major reactive species of ambient volatile organic compounds (VOCs) and their sources in Beijing

Volatile organic compounds(VOCs)are important precursors of atmospheric chemical processes.As a whole mixture,the ambient VOCs show very strong chemical reactivity.Based on OH radical loss rates in the air,the chemical reactivity of VOCs in Beijing was calculated.The results revealed that alkenes,accounting for only about 15%in the mixing ratio of VOCs,provide nearly 75%of the reactivity of ambient VOCs and the C4 to C5 alkenes were the major reactive species among the alkenes.The study of emission characteristics of various VOCs sources indicated that these alkenes are mainly from vehicle exhaust and gasoline evaporation.The reduction of alkene species in these two sources will be effective in photochemical pollution control in Beijing.

Characteristics of carbonyls and volatile organic compounds （VOCs） in residences in Beijing, China

Volatile organic compounds （VOCs） and carbonyl compounds were measured both indoors and outdoors in 50 residences of Beijing in heating （December, 2011） and non-heating seasons （April/May, 2012）. SUMMA canisters for VOCs and diffusive samplers for carbonyl compounds were deployed for 24 h at each site, and 94 compounds were quantified. Formaldehyde, acetone and acetaldehyde were the most abundant carbonyl compounds both indoors and outdoors with indoor median concentrations being 32.1, 21.7 and 15.3 μg·m-3, respec- tively. Ethane （17.6 μg·m-3）, toluene （14.4 μg·m-3）, pro- pane （11.2 μg·m-3）, ethene （8.40 μg·m-3）, n-butane （6.87 μg·m-3）, and benzene （5.95 μg·m-3） showed the high median concentrations in indoor air. Dichloromethane, p- dichlorobenzene （p-DCB） and toluene exhibited extremely high levels in some residences, which were related with a number of indoor emission sources. Moreover, isoprene, p- dichlorobenzene and carbonyls showed median indoor/ outdoor （I/O） ratios larger than 3, indicating their indoor sources were prevailing. Chlorinated compounds like CFCs were mainly from outdoor sources for their I/O ratios being less than 1. In addition, indoor concentrations between two sampling seasons varied with different compounds. Carbonyl compounds and some chlorinated compounds had higher concentrations in the non-heating season, while alkanes, alkenes, aromatic compounds showed an increase in the heating season. Indoor concentration of VOCs and carbonyls were influenced by locations, interior decorations and indoor activities, however the specific sources for indoor VOCs and carbonyls could not be easily identified. The findings obtained in this study would significantly enhance our understandings on the prevalent and abundant species of VOCs as well as their concentrations and sources in Beijing residences.

Chemical speciation and anthropogenic sources of ambient volatile organic compounds (VOCs) during summer in Beijing, 2004

Volatile organic compounds(VOCs)were measured at six sites in Beijing in August,2004.Up to 148 VOC species,including C_(3) to C_(12) alkanes,C_(3) to C_(11) alkenes,C_(6) to C_(12) aromatics,and halogenated hydrocarbons,were quantified.Although the concentrations differed at the sites,the chemical compositions were similar,except for the Tongzhou site where aromatics were significantly high in the air.Based on the source profiles measured from previous studies,the source apportionment of ambient VOCs was preformed by deploying the chemical mass balance(CMB)model.The results show that urban VOCs are predominant from mobile source emissions,which contribute more than 50% of the VOCs(in mass concentrations)to ambient air at most sites.Other important sources are gasoline evaporation,painting,and solvents.The exception is at the Tongzhou site where vehicle exhaust,painting,and solvents have about equal contribution,around 35% of the ambient VOC concen-tration.As the receptor model is not valid for deriving the sources of reactive species,such as isoprene and 1,3-butadiene,other methodologies need to be further explored.

Screening the emission sources of volatile organic compounds （VOCs） in China by multi-effects evaluation

Volatile organic compounds （VOCs） play important roles in the atmosphere via three main pathways： photochemical ozone formation, secondary organic aerosol production, and direct toxicity to humans. Fewstudies have integrated these effect, s to prioritize control measures for VOC.s sources. In this study,we developed a multi-effects evaluation methodology based on updated emission inventories and source profiles, by combining the ozone formation potential （OFP）, secondary organic aerosol potential （SOAP）, and VOC toxicity data. We derived species-specific emission inventories for 152 sources. The OFPs, SOAPs, and toxicity of each source were estimated, the contribution and sharing of source to each of these adverse effects were calculated. Weightings were given to the three adverse effects by expert scoring, and then the integrated effect was determined. Taking 2012 as the base year,solvent use and industrial process were found to be the most important anthropogenic sources, accounting for 24.2% and 23.1% of the integrated effect, respectively, followed by biomass burning, transportation, and fossil fuel combustion, each had a similar contribution ranging from 16.7% to 18.6%. The top five industrial sources, including plastic products, rubber products, chemical fiberproducts, the chemical industry, and oil refining, accounted for nearly 70.0% of industrial emissions. Beijing, Chongqing, Shanghai, Jiangsu, and Guangdong were the five provinces contributing the largest integrated effects. For the VOC species from emissions showed the largest contributions were styrene, toluene, ethylene, benzene, and m/p-xylene.

Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons,and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25 th to 27 th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th–8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene（T/B） during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was5.8 ppb/ppb, significantly higher than the values of 0.2–1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.

Evidence of coal combustion contribution to ambient VOCs during winter in Beijing

Volatile organic compounds （VOCs） play ,an important role in ozone and secondary organic aerosol （SOA） formation, but VOCs sources during winter are not fully understood. To investigate VOCs sources during winter, mixing ratios of C2-C12 VOCs were measured at an urban site in Beijing from December 29, 2011 to January 17, 2012. Correlation analysis of toluene to benzene and i-pentane to n-pentane suggest that coal combustion could also be an important source for VOCs besides vehicular emissions. Source apportionment results show that coal combustion and vehicular emissions contributed 28%-39% and 31%-45% to ambient VOCs during winter, respectively. Backward trajectory analyses demonstrated that contributions from the burning of coal were higher when air masses came from southern regions outside Beijing. Close attention should be paid to VOCs emissions from coal combustion in Beijing city and the vicinity to the South.

Estimation of dry deposition fluxes of major inorganic species by canopy throughfall approach

Dry deposition in China has not yet been intensively studied even though it constitutes an important pathway for acid deposition. The total deposition was monitored at Tieshanping catchment, a regional remote site in Chongqing City. The dry deposition loads of sulphur, calcium and nitrogen are estimated by using a canopy throughfall approach. The results indicate that the annual dry deposition loads of sulphur and calcium at Tieshanping site are much higher than those measured in forestry areas in other countries, while the dry deposition flux of ni- trogen is at a comparable level. The dry deposition loads of sulphur, calcium and nitrogen are all higher than the wet deposition loads. Applying a canopy budget model has proven that the routine, simplified canopy throughfall approach may underestimate the dry deposition flux of nitrogen-containing species.

Quantification of acetone emission from pine plants

Acetone emission from pine plants (pinus sylvestris) is measured by continuously stirred tank reactor. Under a constant light intensity, acetone emission rates increase exponentially with leaf temperature. When leaf temperature is kept constant, acetone emission increases with light intensity. And acetone emission in darkness is also detected. Acetone emitted from pine is quickly labeled by 13C when the plants are exposed to air with 630 mg/m3 13CO2. However, no more than 20% of acetone is 13C labeled. Acetone emission from pine may be due to both leaf temperature- controlled process and light intensity-controlled process. Based on these understandings, an algorithm is used to describe the short term acetone emission rates from pine.

Missing in total OH reactivity of VOCs from gasoline evaporation

Gasoline evaporation is an important anthropogenic source of atmospheric volatile organic compounds（VOCs）. Total OH reactivity for gasoline vapor was measured from 4 kinds of gasoline for the first time by comparative reactivity method（CRM） using proton transfer reaction mass spectrometer（PTR-MS）.Compositions of 56 PAMS（photochemical assessment monitoring station） nonmethane hydrocarbons（NMHCs） were measured for both liquid and headspace of gasoline. We found high abundance of alkenes and aromatics in gasoline. The calculated OH reactivity derived from quantified NMHCs speciation accounted for only 57 ？ 4% of total reactivity obtained from CRM method. N-Alkenes, only 6 wt% in liquid gasoline, contributed to 70% of calculated reactivity. We assume that the undetected branched alkenes are the possible reason for the missing reactivity. We suggest that the priority of gasoline quality improvement is to reduce alkenes content in gasoline in term of reactivity-based control.

Quantifying the ambient formaldehyde sources utilizing tracers

Formaldehyde（HCHO） is one of the most important intermediate products of atmospheric photochemical reactions in the troposphere, therefore understanding of HCHO sources is essential for effective ozone control measures. The objective of this work is to distinguish between primary and secondary sources of HCHO. Based on about one month of online measurements in winter in Ziyang,Sichuan, the multi-linear regression analysis of ambient concentrations of HCHO and possible tracers（acetonitrile, propane and peroxyacetyl nitrate） was performed. The results show that during winter in Ziyang, biomass burning contributed an average of 53.2% to ambient HCHO levels, while secondary processes contributed about 30.1%, and vehicular sources accounted for 7.1%.