Weekday/Weekend Differences in OH Reactivity with VOCs and CO in Baltimore,Maryland

ABSTRACT

This study compared the first-order frequencies for OH associated with volatile organic compounds (VOCs) and CO (hereafter called OH reactivity with VOCs or CO), the product of the VOC or CO concentration, and their respective k_OH value, on an average weekday with that on an average weekend day at a core urban site in Baltimore, MD. The average daytime concentrations were calculated for each of the 55 available Photochemical Assessment Monitoring Station (PAMS) VOCs using data from the Baltimore site. The data were sorted in descending order to highlight the important species based on concentration. The OH reactivity with VOCs was sorted in descending order to identify the important species based on the magnitude of the OH reactivity. A similar process was followed for the OH reactivity with CO. The contribution of the significant species to the weekday/weekend difference in OH reactivity was examined.

The OH reactivity with C₅H₈ was the largest among the OH reactivity with the PAMS' VOCs and was the same on the weekday and weekend. The weekday/weekend difference in OH reactivity with VOCs was entirely due to differences in concentrations of the anthropogenic VOCs. The OH reactivity with VOCs was 11% larger on the weekday. When OH reactivity with CO was included, the OH reactivity was 13% larger on the weekday.     

Weekday/weekend differences in OH reactivity with VOCs and CO in Baltimore, Maryland

This study compared the first-order frequencies for OH associated with volatile organic compounds (VOCs) and CO (hereafter called OH reactivity with VOCs or CO), the product of the VOC or CO concentration, and their respective kOH value, on an average weekday with that on an average weekend day at a core urban site in Baltimore, MD. The average daytime concentrations were calculated for each of the 55 available Photochemical Assessment Monitoring Station (PAMS) VOCs using data from the Baltimore site. The data were sorted in descending order to highlight the important species based on concentration. The OH reactivity with VOCs was sorted in descending order to identify the important species based on the magnitude of the OH reactivity. A similar process was followed for the OH reactivity with CO. The contribution of the significant species to the weekday/weekend difference in OH reactivity was examined. The OH reactivity with C5H8 was the largest among the OH reactivity with the PAMS' VOCs and was the same on the weekday and weekend. The weekday/weekend difference in OH reactivity with VOCs was entirely due to differences in concentrations of the anthropogenic VOCs. The OH reactivity with VOCs was 11% larger on the weekday. When OH reactivity with CO was included, the OH reactivity was 13% larger on the weekday.     

An experimental investigation of incremental reactivities of volatile organic compounds

California has adopted a set of VOC reactivity factors for regulatory purposes that is based on a model of the ozone formation process. These incremental reactivity factors (derived by Carter) describe the amount of ozone each exhaust VOC will form under a certain set of conditions in an urban atmosphere. The main objective of this study is to measure reactivity factors using smog chamber experiments, and to compare the measurements to the Carter factors. A new facility was constructed explicitly for this study. The facility has four identical smog chambers and a temperature-controlled enclosure for the chambers. The chambers are irradiated using a set of filtered xenon arc lamps to approximate “sunlight”. The reactivities of 14 individual VOCs representative of those found in automobile exhaust and several mixtures of VOCs have been measured. The measured and Carter-reactivity factors were highly correlated, suggesting that the chemical model used by Carter accounts for the reactivities of a wide range of compounds with dramatically different uncertainties in their mechanisms. The measured results, in general, are consistent with the Carter-reactivity factors for comparing the relative reactivities of VOCs in the atmosphere. However, additional kinetic and mechanistic studies of many VOC species including aromatic isomers are needed to improve reactivity scales.     

Gas- and particle-phase distribution of polycyclic aromatic hydrocarbons in two-stroke, 50-cm3 moped emissions

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) concentrations evaluated in the exhaust of 10 two-stroke, 50-cm³ mopeds belonging to three different levels of emission legislation (EURO-0, EURO-1 and EURO-2) were used to assess the prevalent mechanism driving the gas/particle partitioning of PAHs in moped exhaust. Sampling was performed on a dynamometer bench both during the “cold-start” and the “hot” phases of the ECE-47 driving cycle. Gas and particulate phase PAHs were collected on polyurethane foam (PUF) plugs and 47-mm Pallflex T60A20 filters, respectively, under isokinetic conditions by using sampling probes inserted into the dilution tunnel of a Constant Volume Sampling – Critical Flow Venturi (CVS–CFV) system.The results show that semi-volatile PAHs were predominantly partitioned to the particle phase. The soluble organic fraction (SOF) of the collected particulates ranged between 72 and 98%. Measured total suspended particulate matter normalized partition coefficients (K_p) were predicted within a factor of 3–5 by assuming absorption into the organic fraction according to a model developed by Harner and Bidleman [Harner, T., Bidleman, T.F., 1998. Octanol–air partition coefficient for describing particle/gas partitioning of aromatic compounds in urban air. Environmental Science & Technology 32, 1494–1502.]. This suggests that the gas/particle partitioning in moped exhaust is mainly driven by the high fraction of organic matter of the emitted particles and that absorption could be the main partitioning mechanism of PAHs.     

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

Effects of Fuel Type,Driving Cycle,and Emission Status on In-Use Vehicle Exhaust Reactivity

ABSTRACT

The introduction of reformulated gasolines significantly reduced exhaust hydrocarbon (HC) mass emissions, but few data are available concerning how these new fuels affect exhaust reactivity. Similarly, while it is well established that high-emitting vehicles contribute a significant portion of total mobile source HC mass emissions, it is also important to evaluate the exhaust reactivity from these vehicles. The objective of this study was to evaluate the relative influence on in-use vehicle exhaust reactivity of three critical factors: fuel, driving cycle, and vehicle emission status. Nineteen in-use vehicles were tested with seven randomly assigned fuel types and two driving cycles: the Federal Test Procedure (FTP) and the Unified Cycle (UC). Total exhaust reactivity was not statistically different between the FTP and UC cycles but was significantly affected by fuel type. On average, the exhaust reactivity for California Phase 2 fuel was the lowest (16 % below the highest fuel type) among the seven fuels tested for cold start emissions. The average exhaust reactivity for high-emitting vehicles was significantly higher for hot stabilized (11%) and hot start (15%) emissions than for low-emitting vehicles. The exhaust reactivities for the FTP and UC cycles for light-end HCs and carbonyls were significantly different for the hot stabilized mode. There was a significant fuel effect on the mean specific reactivity (SR) for the mid-range HCs, but not for light-end HCs or carbonyls, while vehicle emission status affected the mean SR for all three HC compound classes.     

Airshed Model Evaluation of Reactivity Adjustment Factors Calculated with the Maximum Incremental Reactivity Scale for Transitional-Low Emission Vehicles

Abstract

The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactivity at other conditions, i.e., where NO_x is the limiting precursor.

This study used the Carnegie/California Institute of Technology airshed model to evaluate whether the RAF-adjusted AFV emissions result in ozone impacts equivalent to those of CFV emissions. A matrix of two ozone episodes in the South Coast Air Basin (SoCAB) of California, two base emission inventories, and exhaust emissions from three alternative fuels that meet the first level of the low emission vehicle standards bounds the expected range of conditions. Although very good agreement was found previously for individual NMOG species,² this study noted deviations of up to ±15 percent from the equal ozone impacts for any vehicle/fuel combination required by the California regulations. These deviations appear to be attributable to differences in spatial and temporal patterns of emissions between vehicle fleets, rather than a problem with the MIR approach. The first formally adopted RAF, a value of 0.41 for 85 percent methanol/15 percent gasoline-fueled vehicles, includes a 10 percent increase based on the airshed modeling. The correction to the RAF is different for other fuels and may be different for air basins other than the SoCAB.     

A study of extractive and remote-sensing sampling and measurement of emissions from military aircraft engines

Aircraft emissions contribute to the increased atmospheric burden of particulate matter (PM) that plays an important role in air quality, human health, visibility, contrail formation and climate change. Sampling and measurement of modern aircraft emissions at the engine exhaust plane (EEP) for engine and fuel certification remains challenging, as no agency-certified method is available. In this paper we summarize the results of three recent field studies devoted to investigate the consistency and applicability of “extractive” and “optical remote-sensing” (ORS) technologies in the sampling and measurement of gaseous and PM emitted by a number of military aircraft engines. Three classes of military engines were investigated; these include T56, TF33, and T700 & T701C types of engines, which consume 70–80% of the military aviation fuel each year. JP-8 and Fischer–Tropsch (FT)-derived paraffinic fuels were used to study the effect of fuels. It was found that non-volatile particles in the engine emissions were in the 20 nm range for the low power condition of new helicopter engines to 80 nm for the high power condition of legacy engines. Elemental analysis indicated little metals were present on particles, while most of the materials on the exhaust particles were carbon and sulfate based. Alkanes, carbon monoxide, carbon dioxide, nitrogen oxides, sulfur dioxide, formaldehyde, ethylene, acetylene and propylene were detected. The last five species were most noticeable only under low engine power. The emission indices calculated based on the ORS data deviate significantly from those based on the extractive data. Nevertheless, the ORS techniques were useful in the sense that it provided non-intrusive real-time detection of species in the exhaust plume, which warrants further development. The results obtained in this program help validate sampling methodology and measurement techniques used for non-volatile PM aircraft emissions as described in the SAE AIR6037 (2009).     

Fast and quantitative measurement of benzene,toluene and C2-benzenes in automotive exhaust during transient engine operation with and without catalytic exhaust gas treatment

Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C₂-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.     

Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies

Both similarities and differences in summertime atmospheric photochemical oxidation appear in the comparison of four field studies: TEXAQS2000 (Houston, 2000), NYC2001 (New York City, 2001), MCMA2003 (Mexico City, 2003), and TRAMP2006 (Houston, 2006). The compared photochemical indicators are OH and HO₂ abundances, OH reactivity (the inverse of the OH lifetime), HO_x budget, OH chain length (ratio of OH cycling to OH loss), calculated ozone production, and ozone sensitivity. In terms of photochemical activity, Houston is much more like Mexico City than New York City. These relationships result from the ratio of volatile organic compounds (VOCs) to nitrogen oxides (NO_x), which are comparable in Houston and Mexico City, but much lower in New York City. Compared to New York City, Houston and Mexico City also have higher levels of OH and HO₂, longer OH chain lengths, a smaller contribution of reactions with NO_x to the OH reactivity, and NO_x-sensitivity for ozone production during the day. In all four studies, the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) are significant, if not dominant, HO_x sources. A problematic result in all four studies is the greater OH production than OH loss during morning rush hour, even though OH production and loss are expected to always be in balance because of the short OH lifetime. The cause of this discrepancy is not understood, but may be related to the under-predicted HO₂ in high NO_x conditions, which could have implications for ozone production. Three photochemical indicators show particularly high photochemical activity in Houston during the TRAMP2006 study: the long portion of the day for which ozone production was NO_x-sensitive, the calculated ozone production rate that was second only to Mexico City's, and the OH chain length that was twice that of any other location. These results on photochemical activity provide additional support for regulatory actions to reduce reactive VOCs in Houston in order to reduce ozone and other pollutants.     

浙江省某印染企业VOCs的产生特征及去除特性

为探究印染行业生产过程中挥发性有机物(volatile organic compounds, VOCs)的产生特征及现有控制措施对VOCs的去除效果,选取浙江某典型印染企业作为研究对象,调查了该企业主要VOCs污染源(包括定型机、配料间及污水站)的废气产生特征,测定和评价了各废气处理装置对VOCs的去除效果。结果表明,该企业定型机、配料间及污水站产生的有组织废气总流量分别为8.6×10⁵、7.4×10⁴、2.8×10⁴ m³·h⁻¹,产生的VOCs平均浓度分别为14.7、9.0和14.9 mg·m⁻³,有组织废气源VOCs的年产生总量约为80 t。定型车间、印染车间和污水站附近无组织VOCs的平均浓度分别约为0.66、0.16和0.59 mg·m⁻³。产生的典型VOCs包括苯甲酸苄酯、五氟丙酸三十八烷酯、乙二醇单丁醚、十六烷、异喹啉等。定型机废气采用“冷却+静电”或“喷淋+静电”工艺处理,其对VOCs的去除率仅为2%~6%。配料间和污水站产生废气采用“碱洗+次氯酸钠洗涤”工艺处理,其对VOCs的去除率为8%~58%。研究结果可为印染行业VOCs污染控制提供参考。     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

Microwave Plasma Conversion of Volatile Organic Compounds

Abstract

A microwave-induced, steam/Ar/O₂ , plasma “torch” was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N₂ can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NO_x ) is avoided in the plasma.

The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O₂ and steam.The O₂ was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500–600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O₂ was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Current and future emission estimates of exhaust gases and particles from shipping at the largest port in Korea

The emissions of exhaust gases (NO _x , SO₂, VOCs, and CO₂) and particles (e.g., PM) from ships traversing Busan Port in Korea were estimated over three different years (the years 2006, 2008, and 2009). This analysis was performed according to the ship operational modes (“at sea,” “maneuvering,” and “in port”) and ship types based on an activity-based method. The ship emissions for current (base year 2009) and future scenarios (years 2020 and 2050) were also compared. The annual emissions of SO₂, VOCs, PM, and CO₂ were highest (9.6?×?10³, 374, 1.2?×?10³, and 5.6?×?10⁵ ton year^?1, respectively) in 2008. In contrast, the annual NO _x emissions were highest (11.7?×?10³ ton year^?1) in 2006 due mainly to the high NO _x emission factor. The emissions of air pollutants for each ship operational mode differed considerably, with the largest emission observed in “in port” mode. In addition, the largest fraction (approximately 45–67 %) of the emissions of all air pollutants during the study period was emitted from container ships. The future ship emissions of most pollutants (except for SO₂ and PM) in 2020 and 2050 are estimated to be 1.4–1.8 and 4.7–6.1 times higher than those in 2009 (base year), respectively.     

微米级雾滴协同液相吸收柴油机尾气中的VOCs

针对柴油机尾气中多组分混合的挥发性有机污染物 (VOCs) 开展净化去除研究,整体基于电声换能超声波雾化-超重力收集器联用技术,提出微米级雾滴协同液相吸收脱除柴油机尾气VOCs的应用方案。在对柴油机尾气VOCs排放特征定性与定量分析的基础上,选用不同种类的吸收剂、吸收浓度与分配比助剂,得到吸收剂的最佳使用条件。进而优化运行参数,获得最优工况条件。结果表明：在15%柠檬酸钠作为主吸收剂,0.22%柠檬酸与1%氯化钠作为助剂组成的最佳吸收剂与设定雾滴粒径为5 μm、雾化量为71 mL·min⁻¹,以及雾化后尾气停留1 s的最优运行条件下,本系统对柴油机尾气VOCs的综合吸收效率达到了58.5%。本研究可为移动源尾气VOCs的减排净化提供参考。     

蓄热式氧化炉在无机材料煅烧尾气处理中的应用

分子筛煅烧尾气中含有三乙胺、正丁胺等挥发性有机化合物（VOCs）,严重影响厂区及周边环境。为彻底治理有机废气污染,采用三床式蓄热式氧化炉（RTO）处理有机废气,通过优化调整控制工艺,以排烟温度控制法替代原有的排烟时间控制法。结果表明：排烟温度控制法可确保排烟温度保持在设计范围内,有效降低了排烟热损失;蓄热式氧化炉通过吸热-燃烧-放热周期性稳定运行,在天然气平均耗量4.5 m3·h-1的情况下,获得99%以上的VOCs去除效率,达到预期目标。蓄热式氧化法是一种经济、高效、稳定和安全的有机废气处理技术。     

Particulate Matter in New Technology Diesel Exhaust (NTDE) is Quantitatively and Qualitatively Very Different from that Found in Traditional Diesel Exhaust (TDE)

ABSTRACT

Diesel exhaust (DE) characteristic of pre-1988 engines is classified as a “probable” human carcinogen (Group 2A) by the International Agency for Research on Cancer (IARC), and the U.S. Environmental Protection Agency has classified DE as “likely to be carcinogenic to humans.” These classifications were based on the large body of health effect studies conducted on DE over the past 30 or so years. However, increasingly stringent U.S. emissions standards (1988–2010) for particulate matter (PM) and nitrogen oxides (NO_x) in diesel exhaust have helped stimulate major technological advances in diesel engine technology and diesel fuel/lubricant composition, resulting in the emergence of what has been termed New Technology Diesel Exhaust, or NTDE. NTDE is defined as DE from post-2006 and older retrofit diesel engines that incorporate a variety of technological advancements, including electronic controls, ultra-low-sulfur diesel fuel, oxidation catalysts, and wall-flow diesel particulate filters (DPFs). As discussed in a prior review (T. W. Hesterberg et al.; Environ. Sci. Technol. 2008, 42, 6437-6445), numerous emissions characterization studies have demonstrated marked differences in regulated and unregulated emissions between NTDE and “traditional diesel exhaust” (TDE) from pre-1988 diesel engines. Now there exist even more data demonstrating significant chemical and physical distinctions between the diesel exhaust particulate (DEP) in NTDE versus DEP from pre-2007 diesel technology, and its greater resemblance to particulate emissions from compressed natural gas (CNG) or gasoline engines. Furthermore, preliminary toxicological data suggest that the changes to the physical and chemical composition of NTDE lead to differences in biological responses between NTDE versus TDE exposure. Ongoing studies are expected to address some of the remaining data gaps in the understanding of possible NTDE health effects, but there is now sufficient evidence to conclude that health effects studies of pre-2007 DE likely have little relevance in assessing the potential health risks of NTDE exposures.

IMPLICATIONS Based on the distinct physical and chemical properties of New Technology Diesel Exhaust (NTDE), it has become clear that findings from the health effects studies conducted on traditional DE (TDE) over the last 30 years have little relevance to NTDE, which is more similar to the exhaust from compressed natural gas (CNG) or gasoline engine emissions than to traditional TDE. Once sufficient health effects data are available for NTDE, it will thus be necessary to conduct new hazard and risk assessments for NTDE that are independent of the DE toxicological database acquired on emissions from pre–2007 diesel technology.     

Real-world vehicle emissions and VOCs profile in the Taipei tunnel located at Taiwan Taipei area

An in situ field experiment was conducted in a highway road tunnel in the Taipei City to determine the motor vehicle emission factors (EF) of different kinds of air pollution species. These are carbon monoxide (CO), oxides of nitrogen (NO_x), non-methane hydrocarbons (NMHC) and VOCs species. About 56 species of VOCs were sampled by canister sampler and followed by the GC-MS analyzing. Furthermore, the tunnel-drafting rate was determined by SF₆ tracer method.The EF for the highway vehicles determined from this experiment are 3.64, 0.90, 0.44 and 0.24 gm km⁻¹ veh⁻¹ for CO, NO_x, NMHC and the totally measured VOCs, respectively. A comparison of the EFs from the road tunnel experiment to the estimates by the USEPA MOBILE5b (M5b) and the modified Taiwan EPA MOBILE-TAIWAN2.0 (MT2.0) provides a first-hand evaluation of the model characteristics. M5b and MT2.0 both tend to underpredict CO by 10% and 20%, respectively. While M5b overpredicts NO_x and NMHC by 40% and 20%, respectively; MT2.0 has fairly good predictions for these two species. From the GC-MS analysis of the canister samples, it was found that the most abundant species from the traffic-emitted VOCs in Taipei road tunnel are toluene, ethene and 1,2,4-trimethyl-benzene (1,2,4-TMB) by the weight basis. However, ethene, acetylene and toluene are the most abundant in VOCs based on volume. The VOCs’ weight composition in terms of the carbon bond classification is 28% by the paraffins, 33% by the olefins and 39% by the aromatics, respectively. In order to evaluate the ozone formation potential from the typical road emission in Taipei area, the maximum increment reactivity is calculated. It was found that about 1015 mg of O₃ is induced by per vehicle per kilometer traveled emission. Among them, ethene, 1,2,4-TMB and propene from the road vehicle's emission contribute most to the ozone-formation reactivity.     

某石化企业三类成品油装载环节的有机污染物排放特征、环境影响及控制措施

石化行业的成品油装载环节是有机污染物的重点排放源,包括挥发性有机物(VOCs)和甲烷等。对我国某石化企业的汽油、航煤和柴油三类成品油在装载过程中外排的尾气进行了监测,并采用·OH损失速率和最大增量反应活性法,重点分析了装载过程中VOCs和甲烷的排放特征、大气反应活性及环境影响,并提出相关控制措施。结果表明,成品油装载环节外排的VOCs以烷烃为主。每吨成品油在装载过程中排放的VOCs强度达到2.2~36.4 g,其中汽油排放强度最高。丁烷、戊烷和己烷等C₄~C₆烃是主要烷烃组分;丙酮是含量最高含氧物质;丁烯、异戊二烯和戊烯是最主要的烯烃组分。这类VOCs具有较高大气光化学反应活性和臭氧生成潜势(OFP),大气活性与二甲苯活性相当。VOCs的OFP(即每克VOCs可产生的O₃质量)达到1.4~2.7 g·g⁻¹。航煤装载环节外排VOCs的反应活性与臭氧潜势高于汽油和柴油。装载环节外排VOCs的反应活性及臭氧生成潜势主要源于烷烃和烯烃组分,异戊烷、C₄~C₅烯烃和甲苯等是需优先控制的高活性物质。本研究可为石化企业从源头开展VOCs等有机污染物的精准管控提供参考。     

Application of OMI observations to a space-based indicator of NOx and VOC controls on surface ozone formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the “Ratio”) from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios <1 and NO_x at Ratios >2; both NO_x and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria, the OMI data indicate that ozone formation became: 1. more sensitive to NO_x over most of the United States from 2005 to 2007 because of the substantial decrease in NO_x emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO₂, and 2. more sensitive to NO_x with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g., Chicago), the data clearly indicate that ozone formation became more sensitive to NO_x from 2005 to 2007. In cities with relatively high isoprene emissions (e.g., Atlanta), we found that the increase in the Ratio due to decreasing NO_x emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.