Speciation and chemical evolution of nitrogen oxides in aircraft exhaust near airports

Measurements of nitrogen oxides from a variety of commercial aircraft engines as part of the JETS-APEX2 and APEX3 campaigns show that NOx (NOx [triple bond] NO + NO2) is emitted primarily in the form of NO2 at idle thrust and NO at high thrust. A chemical kinetics combustion model reproduces the observed NO2 and NOx trends with engine power and sheds light on the relevant chemical mechanisms. Experimental evidence is presented of rapid conversion of NO to NO2 in the exhaust plume from engines at low thrust. The rapid conversion and the high NO2/NOx emission ratios observed are unrelated to ozone chemistry. NO2 emissions from a CFM56-3B1 engine account for approximately 25% of the NOx emitted below 3000 feet (916 m) and 50% of NOx emitted below 500 feet (153 m) during a standard ICAO (International Civil Aviation Organization) landing-takeoff cycle. Nitrous acid (HONO) accounts for 0.5% to 7% of NOy emissions from aircraft exhaust depending on thrust and engine type. Implications for photochemistry near airports resulting from aircraft emissions are discussed.     

Commercial aircraft engine emissions characterization of in-use aircraft at Hartsfield-Jackson Atlanta International Airport

The emissions from in-use commercial aircraft engines have been analyzed for selected gas-phase species and particulate characteristics using continuous extractive sampling 1-2 min downwind from operational taxi- and runways at Hartsfield-Jackson Atlanta International Airport. Using the aircraft tail numbers, 376 plumes were associated with specific engine models. In general, for takeoff plumes, the measured NOx emission index is lower (approximately 18%) than that predicted by engine certification data corrected for ambient conditions. These results are an in-service observation of the practice of "reduced thrust takeoff". The CO emission index observed in ground idle plumes was greater (up to 100%) than predicted by engine certification data for the 7% thrust condition. Significant differences are observed in the emissions of black carbon and particle number among different engine models/technologies. The presence of a mode at approximately 65 nm (mobility diameter) associated with takeoff plumes and a smaller mode at approximately 25 nm associated with idle plumes has been observed. An anticorrelation between particle mass loading and particle number concentration is observed.     

Measurements of in-use emissions from modern vehicles using an on-board measurement system

Emissions from "low emitting" modern vehicles were measured on-road using a Fourier transform infrared (FTIR) on-board emissions measurement system. Twenty vehicles were tested on road and on a chassis dynamometer. A subset of four vehicles was tested on a test track as well as on the dynamometer. Comparison of on-board measurements with laboratory measurements while operating on the dynamometer showed agreement within measurement and test to test variability. Comparison of dynamometer measurements with test track measurements showed some larger differences attributable to track test conditions. On-road and dynamometer tests were conducted on the remaining 16 vehicles, with the on-road testing including freeway, arterial, and residential streets. The on-road testing showed that most of the low emitting vehicles under most operating conditions are operating below certification levels. Most vehicles reached a hot stabilized condition within 60 to 100 s. Hot running emissions were on average very low once the catalyst lights off. For NMHC, the majority of the "certification" emissions occur during the start-up, especially for PZEVs. NOx and CO also showed a high fraction of "certification" emissions during start-up, but also showed emission spikes under hot running conditions, especially during transients.     

Near-field commercial aircraft contribution to nitrogen oxides by engine, aircraft type, and airline by individual plume sampling

Nitrogen oxides (NOx) concentrations were measured in individual plumes from aircraft departing on the northern runway at Heathrow Airport in west London. Over a period of four weeks 5618 individual plumes were sampled by a chemiluminescence monitor located 180 m from the runway. Results were processed and matched with detailed aircraft movement and aircraft engine data using chromatographic techniques. Peak concentrations associated with 29 commonly used engines were calculated and found to have a good relationship with N0x emissions taken from the International Civil Aviation Organization (ICAO) databank. However, it is found that engines with higher reported NOx emissions result in proportionately lower NOx concentrations than engines with lower emissions. We show that it is likely that aircraft operational factors such as takeoff weight and aircraftthrust setting have a measurable and important effect on concentrations of N0x. For example, NOx concentrations can differ by up to 41% for aircraft using the same airframe and engine type, while those due to the same engine type in different airframes can differ by 28%. These differences are as great as, if not greater than, the reported differences in NOx emissions between different engine manufacturers for engines used on the same airframe.     

Hydrocarbon emissions from in-use commercial aircraft during airport operations

The emissions of selected hydrocarbons from in-use commercial aircraft at a major airport in the United States were characterized using proton-transfer reaction mass spectrometry (PTR-MS) and tunable infrared differential absorption spectroscopy (TILDAS) to probe the composition of diluted exhaust plumes downwind. The emission indices for formaldehyde, acetaldehyde, benzene, and toluene, as well as other hydrocarbon species, were determined through analysis of 45 intercepted plumes identified as being associated with specific aircraft. As would have been predicted for high bypass turbine engines, the hydrocarbon emission index was greater in idle and taxiway acceleration plumes relative to approach and takeoff plumes. The opposite was seen in total NOy emission index, which increased from idle to takeoff. Within the idle plumes sampled in this study, the median emission index for formaldehyde was 1.1 g of HCHO per kg of fuel. For the subset of hydrocarbons measured in this work, the idle emissions levels relative to formaldehyde agree well with those of previous studies. The projected total unburned hydrocarbons (UHC) deduced from the range of in-use idle plumes analyzed in this work is greater than a plausible range of engine types using the defined idle condition (7% of rated engine thrust) in the International Civil Aviation Organization (ICAO) databank reference.     

Real-time gaseous, PM and ultrafine particle emissions from a modern marine engine operating on biodiesel

Emissions from harbor-craft significantly affect air quality in populated regions near ports and inland waterways. This research measured regulated and unregulated emissions from an in-use EPA Tier 2 marine propulsion engine on a ferry operating in a bay following standard methods. A special effort was made to monitor continuously both the total Particulate Mass (PM) mass emissions and the real-time Particle Size Distribution (PSD). The engine was operated following the loads in ISO 8178-4 E3 cycle for comparison with the certification standards and across biodiesel blends. Real-time measurements were also made during a typical cruise in the bay. Results showed the in-use nitrogen oxide (NOx) and PM(2.5) emission factors were within the not to exceed standard for Tier 2 marine engines. Comparing across fuels we observed the following: a) no statistically significant change in NO(x) emissions with biodiesel blends (B20, B50); b) ～ 16% and ～ 25% reduction of PM(2.5) mass emissions with B20 and B50 respectively; c) a larger organic carbon (OC) to elemental carbon (EC) ratio and organic mass (OM) to OC ratio with B50 compared to B20 and B0; d) a significant number of ultrafine nuclei and a smaller mass mean diameter with increasing blend-levels of biodiesel. The real-time monitoring of gaseous and particulate emissions during a typical cruise in the San Francisco Bay (in-use cycle) revealed important effects of ocean/bay currents on emissions: NO(x) and CO(2) increased 3-fold; PM(2.5) mass increased 6-fold; and ultrafine particles disappeared due to the effect of bay currents. This finding has implications on the use of certification values instead of actual in-use emission values when developing inventories. Emission factors for some volatile organic compounds (VOCs), carbonyls, and poly aromatic hydrocarbons (PAHs) are reported as supplemental data.     

Measurements of nitrous acid in commercial aircraft exhaust at the Alternative Aviation Fuel Experiment

The Alternative Aviation Fuel Experiment (AAFEX), conducted in January of 2009 in Palmdale, California, quantified aerosol and gaseous emissions from a DC-8 aircraft equipped with CFM56-2C1 engines using both traditional and synthetic fuels. This study examines the emissions of nitrous acid (HONO) and nitrogen oxides (NO(x) = NO + NO(2)) measured 145 m behind the grounded aircraft. The fuel-based emission index (EI) for HONO increases approximately 6-fold from idle to takeoff conditions but plateaus between 65 and 100% of maximum rated engine thrust, while the EI for NO(x) increases continuously. At high engine power, NO(x) EI is greater when combusting traditional (JP-8) rather than Fischer-Tropsch fuels, while HONO exhibits the opposite trend. Additionally, hydrogen peroxide (H(2)O(2)) was identified in exhaust plumes emitted only during engine idle. Chemical reactions responsible for emissions and comparison to previous measurement studies are discussed.     

Remote sensing of in-use heavy-duty diesel trucks

On-road measurements in 2005 of carbon monoxide (CO), hydrocarbons, nitric oxide, nitrogen dioxide, and sulfur dioxide from 1641 individually identified heavy-duty diesel trucks at two locations in Colorado are reported. Carbon monoxide and nitric oxide show increasing emissions with increased altitude. Oxides of nitrogen (NOx) emissions have decreased with more recent model years over the last 10 years but are the same as vehicles that are 20 years old. At the Golden, CO site, there was a statistically significant decrease in fleet emissions of CO and NOx since a similar study in 1999. There was no emission trend for CO or NOx with gross vehicle weight or odometer in units of grams of pollutant per kilogram of fuel consumed. Data from this study suggest that on-road remote sensing can detect illegal, high sulfur fuel use from individual heavy-duty diesel trucks. Ammonia emissions from this study were below the detection limit of the instrument but will be useful as a baseline value for future comparison.     

Real-time measurements of nitrogen oxide emissions from in-use New York City transit buses using a chase vehicle

New diesel engine technologies and alternative fuel engines are being introduced into fleets of mass transit buses to try to meet stricter emission regulations of nitrogen oxides and particulates: Real-time instruments including an Aerodyne Research tunable infrared laser differential absorption spectrometer (TILDAS) were deployed in a mobile laboratory to assess the impact of the implementation of the new technologies on nitrogen oxide emissions in real world driving conditions. Using a "chase" vehicle sampling strategy, the mobile laboratory followed target vehicles, repeatedly sampling their exhaust. Nitrogen oxides from approximately 170 in-use New York City mass transit buses were sampled during the field campaigns. Emissions from conventional diesel buses, diesel buses with continuously regenerating technology (CRT), diesel hybrid electric buses, and compressed natural gas (CNG) buses were compared. The chase vehicle sampling method yields real world emissions that can be included in more realistic emission inventories. The NO, emissions from the diesel and CNG buses were comparable. The hybrid electric buses had approximately one-half the NOx emissions. In CRT diesels, NO2 accounts for about one-third of the NOx emitted in the exhaust, while for non-CRT buses the NO2 fraction is less than 10%.     

Cavity ring-down spectroscopy of ambient NO2 with quantification and elimination of interferences

Ambientdetection of NO2 by cavity ring-down spectroscopy is examined in the wavelength region near 405.23 nm, and possible interferences by particulates, water vapor, and carbon dioxide are characterized. Particulates can be efficiently removed by the use of a 0.45 microm fluoropolymer filter. Water vapor has a response of 2.8 ppb (NO2 equivalent) for 1.0% water vapor (80% relative humidity at 10 degrees C) in air at 405.23 nm in a broad continuous absorption feature. Carbon dioxide has a response of 0.8 ppb (NO2 equivalent) for 1.0% CO2 attributable to Rayleigh scattering and would not contribute significant interference in ambient measurements due to the lower ambient CO2 levels. Water vapor interference and in general broad background in the absorption spectrum can be accounted for by removing NO2 selectively in the ambient air stream with an annular denuder coated with sodium hydroxide and methoxyphenol (guiacol). Subtraction of the resulting background signal provides NO2 measurements with a limit of detection of 150 ppt/10 s (SIN = 3). Reliable NO2 measurements could be obtained by this method without the need for frequent calibration with calibration gas. Ambient NO2 measurements are carried out to demonstrate this method.     

Removal of NOx from lean exhaust gas by storage/reduction on H3PW12O40 x 6H2O supported on Ce(x)Zr4-xO8

We have demonstrated the interest of using Zr-Ce mixed oxides as supports for the system H3PW12O40 x 6H2O (HPW) and Pt for the storage (absorption into HPW and adsorption on Zr-Ce support)-reduction of NOx. Zr-Ce oxides adsorb NOx (mainly NO2) as nitrates, which are desorbed thermally as NO2 and NO (12 mg of NOx x g(-1)). On (HPW-Pt)/Zr-Ce system, NO and NO2 are stored equimolarly by substitution of water molecules of the HPW structure. The Zr/Ce support molar ratio has an important influence on the quantity of NOx stored with a maximum for the system Zr/Ce = 0.5. The presence of Pt has no influence on storage capacity but rather on its efficiency, and it is essential when reducing. Pt strongly accelerates both NOx desorption and reduction processes. Reduction of NOx occurs with H2, CO, or an H2/CO mixture. With H2, NO2 is reduced to NO. With CO, it seems reasonable that the mechanism of NO2 reduction concerns its reaction with CO to produce CO2 and NO. Addition of H2 to CO accelerates the reduction process. However, the difference between NOx stored and desorbed implies also the presence of another reduction step. This could be related to an NO interaction with an active site which produces its decomposition with nitrogen as product. The catalytic system proposed is highly selective since no N2O formation was detected.     

High sensitivity in situ monitoring of NO3 in an atmospheric simulation chamber using incoherent broadband cavity-enhanced absorption spectroscopy

We describe the application of incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) for the in situ detection of atmospheric trace gases and radicals (NO3, NO2, O3, H2O) in an atmospheric simulation chamber under realistic atmospheric conditions. The length of the optical cavity across the reaction chamber is 4.5 m, which is significantly longer than in previous studies that use high finesse optical cavities to achieve high absorption sensitivity. Using a straightforward spectrometer configuration, we show that detection limits corresponding to typical atmospheric concentrations can be achieved with a measurement time of seconds to a few minutes. In particular, with only moderate reflectivity mirrors, we report a measured sensitivity of 4 pptv to NO3 in a 1 min acquisition time. The high spatial and temporal resolution of the IBBCEAS method and its pptv sensitivity to NO3 makes it useful in laboratory studies of atmospheric processes as well as having obvious potential for field measurements.     

生物柴油掺氨对均质压燃发动机燃烧及排放性能的影响

为提升燃料的综合燃烧品质和性能,进一步降低有害物质排放和缓解温室效应,以燃烧动力学和化学反应机制作为理论基础,采用Chemkin软件将生物柴油替代物和氨气充分融合,模拟并计算氨气掺混比例分别为0、5%、10%、15%、20%的5组燃料在均质压燃发动机模式下燃烧和排放指标的数值,对比分析得到不同掺混比例对发动机燃烧和排放的影响和变化规律。结果表明：随着氨气掺混比例增加,燃料的点火滞燃期有所缩短,缸内燃烧最高温度升高,排温降低;排放方面,NO_x的排放升高,CO₂、CO和总碳氢化合物(THC)的排放均明显降低;生物柴油掺混氨气的最佳比例为20%,此时发动机功率下降12百分点,NO的单位功率排放升高了0.003 kW^-1,而CO₂和THC的单位功率排放分别降低了0.01 kW^-1和0.001 3 kW^-1。综上,生物柴油掺混氨气后改善了燃烧性能,降低了排放量,具有良好的应用前景。     

Carbonyl and nitrogen dioxide emissions from gasoline- and diesel-powered motor vehicles

Carbonyls can be toxic and highly reactive in the atmosphere. To quantify trends in carbonyl emissions from light-duty (LD) vehicles, measurements were made in a San Francisco Bay area highwaytunnel bore containing essentially all LD vehicles during the summers of 1999, 2001, and 2006. The LD vehicle emission factor for formaldehyde, the most abundant carbonyl, did not change between 1999 and 2001, then decreased by 61 +/- 7% between 2001 and 2006. This reduction was due to fleet turnover and the removal of MTBE from gasoline. Acetaldehyde emissions decreased by 19 +/- 2% between 1999 and 2001 and by the same amount between 2001 and 2006. Absent the increased use of ethanol in gasoline after 2003, acetaldehyde emissions would have further decreased by 2006. Carbonyl emission factors for medium- (MD) and heavy-duty (HD) diesel trucks were measured in 2006 in a separate mixed-traffic bore of the tunnel. Emission factors for diesel trucks were higher than those for LD vehicles for all reported carbonyls. Diesel engine exhaust dominates over gasoline engines as a direct source of carbonyl emissions in California. Carbonyl concentrations were also measured in liquid-gasoline samples and were found to be low (< 20 ppm). The gasoline brands that contained ethanol showed higher concentrations of acetaldehyde in unburned fuel versus gasoline that was formulated without ethanol. Measurements of NO2 showed a yearly rate of decrease for LD vehicle emissions similar to that of total NOx in this study. The observed NO2/NOx ratio was 1.2 +/- 0.3% and 3.7 +/- 0.3% for LD vehicles and diesel trucks, respectively.     

Aircraft emissions of methane and nitrous oxide during the alternative aviation fuel experiment

Given the predicted growth of aviation and the recent developments of alternative aviation fuels, quantifying methane (CH(4)) and nitrous oxide (N(2)O) emission ratios for various aircraft engines and fuels can help constrain projected impacts of aviation on the Earth's radiative balance. Fuel-based emission indices for CH(4) and N(2)O were quantified from CFM56-2C1 engines aboard the NASA DC-8 aircraft during the first Alternative Aviation Fuel Experiment (AAFEX-I) in 2009. The measurements of JP-8 fuel combustion products indicate that at low thrust engine states (idle and taxi, or 4% and 7% maximum rated thrusts, respectively) the engines emit both CH(4) and N(2)O at a mean ± 1σ rate of 170 ± 160 mg CH(4) (kg Fuel)(-1) and 110 ± 50 mg N(2)O (kg Fuel)(-1), respectively. At higher thrust levels corresponding to greater fuel flow and higher engine temperatures, CH(4) concentrations in engine exhaust were lower than ambient concentrations. Average emission indices for JP-8 fuel combusted at engine thrusts between 30% and 100% of maximum rating were -54 ± 33 mg CH(4) (kg Fuel)(-1) and 32 ± 18 mg N(2)O (kg Fuel)(-1), where the negative sign indicates consumption of atmospheric CH(4) in the engine. Emission factors for the synthetic Fischer-Tropsch fuels were statistically indistinguishable from those for JP-8.     

A plume capture technique for the remote characterization of aircraft engine emissions

A technique for capturing and analyzing plumes from unmodified aircraft or other combustion sources under real world conditions is described and applied to the task of characterizing plumes from commercial aircraft during the taxiing phase of the Landing/Take-Off (LTO) cycle. The method utilizes a Plume Capture and Analysis System (PCAS) mounted in a four-wheel drive vehicle which is positioned in the airfield 60 to 180 m downwind of aircraft operations. The approach offers low test turnaround times with the ability to complete careful measurements of particle and gaseous emission factors and sequentially scanned particle size distributions without distortion due to plume concentration fluctuations. These measurements can be performed for individual aircraft movements at five minute intervals. A Plume Capture Device (PCD) collected samples of the naturally diluted plume in a 200 L conductive membrane conforming to a defined shape. Samples from over 60 aircraft movements were collected and analyzed in situ for particulate and gaseous concentrations and for particle size distribution using a Scanning Particle Mobility Sizer (SMPS). Emission factors are derived for particle number, NO(x), and PM2.5 for a widely used commercial aircraft type, Boeing 737 airframes with predominantly CFM56 class engines, during taxiing. The practical advantages of the PCAS include the capacity to perform well targeted and controlled emission factor and size distribution measurements using instrumentation with varying response times within an airport facility, in close proximity to aircraft during their normal operations.     

Emission factors for gas-powered vehicles traveling through road tunnels in São Paulo, Brazil

The objective of this study was to improve the vehicular emissions inventory for the light- and heavy-duty fleet in the metropolitan area of S?o Paulo (MASP), Brazil. To that end, we measured vehicle emissions in road tunnels located in the MASP. On March 22-26, 2004 and May 04-07, 2004, respectively, CO, CO2, NOx, SO2, and volatile organic compounds (VOCs) emissions were measured in two tunnels: the Janio Quadros, which carries light-dutyvehicles; and the Maria Maluf, which carries light-duty vehicles and heavy-duty diesel trucks. Pollutant concentrations were measured inside the tunnels, and background pollutant concentrations were measured outside of the tunnels. The mean CO and NOx emission factors (in g km(-1)) were, respectively, 14.6 +/- 2.3 and 1.6 +/- 0.3 for light-duty vehicles, compared with 20.6 +/- 4.7 and 22.3 +/- 9.8 for heavy-duty vehicles. The total VOCs emission factor for the Maria Maluf tunnel was 1.4 +/- 1.3 g km(-1). The main VOCs classes identified were aromatic, alkane, and aldehyde compounds. For the heavy-duty fleet, NOx emission factors were approximately 14 times higher than those found for the light-duty fleet. This was attributed to the high levels of NOx emissions from diesel vehicles.     

Changes in motor vehicle emissions on diurnal to decadal time scales and effects on atmospheric composition

Emissions from gasoline and diesel engines vary on time scales including diurnal, weekly, and decadal. Temporal patterns differ for these two engine types that are used predominantly for passenger travel and goods movement, respectively. Rapid growth in diesel fuel use and decreasing NOx emission rates from gasoline engines have led to altered emission profiles. During the 1990s, on-road use of diesel fuel grew 3 times faster than gasoline. Over the same time period, the NOx emission rate from gasoline engines in California was reduced by a factor of approximately 2, while the NOx emission rate from diesel engines decreased only slightly. Diesel engines therefore grew in both relative and absolute terms as a source of NOx, accounting for about half of all on-road NO, emissions as of 2000. Diesel truck emissions decrease by 60-80% on weekends. Counterintuitive responses to these emission changes are seen in measured concentrations of ozone. In contrast, elemental carbon (EC) concentrations decrease on weekends as expected. Weekly and diurnal patterns in diesel truck activity contribute to variability in the ratio of organic carbon (OC) to EC in primary source emissions, and this could be a source of bias in assessments of the importance of secondary organic aerosol.     

Quantifying the emission benefits of opacity testing and repair of heavy-duty diesel vehicles

The objective of this study was to begin to quantify the benefits of a smoke opacity-based (SAE J1667 test) inspection and maintenance program. Twenty-six vehicles exhibiting visible smoke emissions were recruited: 14 pre-1991 vehicles and 12 1991 and later model year vehicles. Smoke opacity and regulated pollutant emissions via chassis dynamometer were measured, with testing conducted at 1609 m above sea level. Twenty of the vehicles were then repaired with the goal of lowering visible smoke emission, and the smoke opacity testing and pollutant emissions measurements were repeated. For the pre-1991 vehicles actually repaired, pre-repair smoke opacity averaged 39% and PM averaged 5.6 g/mi. NOx emissions averaged 22.1 g/mi. After repair, the average smoke opacity had declined to 26% and PM declined to 3.3 g/mi, while NOx emissions increased to 30.9 g/mi. For the 1991 and newer vehicles repaired, pre-repair smoke opacity averaged 59% and PM averaged 2.2 g/mi. NOx emissions averaged 12.1 g/mi. After repair, the average opacity had declined to 30% and PM declined to 1.3 g/mi, while NOx increased slightly to 14.4 g/mi. For vehicles failing the California opacity test at >55% for pre-1991 and >40% for 1991 and later model years, the changes in emissions exhibited a high degree of statistical significance. The average cost of repairs was 1088 dollars, and the average is very similar for both the pre-1991 and 1991+ model year groups. Smoke opacity was shown to be a relatively poor predictor of driving cycle PM emissions. Peak CO or peak CO and THC as measured during a snap-acceleration were much better predictors of driving cycle PM emissions.     

Prediction of in-use emissions of heavy-duty diesel vehicles from engine testing

A model of a heavy-duty vehicle driveline with automatic transmission has been developed for estimating engine speed and load from vehicle speed. The model has been validated using emissions tests conducted on three diesel vehicles on a chassis dynamometer and then on the engines removed from the vehicles tested on an engine dynamometer. Nitrogen oxide (NOx) emissions were proportional to work done by the engine. For two of the engines, the NOx/horsepower(HP) ratio was the same on the engine and on the chassis dynamometer tests. For the third engine NOx/HP was significantly higher from the chassis test, possibly due to the use of dual engine maps. The engine certification test generated consistently less particulate matter emissions on a gram per brake horsepower-hour basis than the Heavy Duty Transient and Central Business District chassis cycles. A good linear correlation (r2 = 0.97 and 0.91) was found between rates of HP increase integrated over the test cycle and PM emissions for both the chassis and the engine tests for two of the vehicles. The model also shows how small changes in vehicle speeds can lead to a doubling of load on the engine. Additionally, the model showed that it is impossible to drive a vehicle cycle equivalent to the heavy-duty engine federal test procedure on these vehicles.