Parameterization of H2SO4 and organic contributions to volatile PM in aircraft plumes at ground idle.

Volatile Particulate Matter (vPM) emissions are challenging to measure and quantify, since they are not present in the condensed form at the engine exit plane and they evolve to first form in the aircraft plume and then continue to grow and change as they mix and dilute in the ambient atmosphere. To better understand the issues associated with the initial formation and growth of vPM, a modeling study has been undertaken to examine several key parameters that affect the formation and properties of the vPM that is created in the initial cooling and dilution of the aircraft exhaust. A modeling tool (Aerosol Dynamic Simulation Code, ADSC) that was developed and enhanced over a series of past research projects supported by NASA, DoD's SERDP/ESTCP, and FAA (Wong et al. 2010, 2014, 2015) was used to perform a parametric analysis of vPM. The parameters of fuel sulfur content (FSC), emitted condensable hydrocarbon (HC) concentrations, and the species profile of the HCs were used to construct a computational matrix that framed a wide range of expected parameter values. This computational matrix was executed for two representative commercial aircraft engines at ground idle and results were obtained for distances of 250 m and 1000 m downstream. From prior results, the most significant vPM emissions occur at the lowest power settings, so an engine power condition of 7% rated thrust was used. A primary goal of the parametric study is to develop an updated vPM modeling methodology and also to help interpret data collected in experimental campaigns. The parameterization proposed here allows the vPM emission composition and particle numbers to be estimated in greater detail than current methods. The aim is to provide additional understanding on how the vPM properties vary with fuel and engine parameters to increase the utility of vPM predictions.Implications: Volatile ParticulateMatter (vPM) is an important contribution to the total PM emitted by aviationengines. While vPM is not currently a part of engine emissions certificationregulations, vPM is used in aviation environmental impact assessments and forair quality modeling in and around airports. Current methods in use, such asFOA (Wayson et al. 2009), were developed before many recent advances inexperimental data acquisition and in understanding of vPM processes. Theparameterization proposed here allows the vPM emission composition and particlenumbers to be estimated in greater detail than current methods. These estimatescan be used to develop inventories and provide a better estimate of total PMemission for most aviation engines. Its use in international regulatory toolscan inform possible future regulatory actions regarding vPM.

Assessment of a regulatory measurement system for the determination of the non-volatile particulate matter emissions from commercial aircraft engines.

The SAE International has published Aerospace Information Report (AIR) 6241 which outlined the design and operation of a standardized measurement system for measuring non-volatile particulate matter (nvPM) mass and number emissions from commercial aircraft engines. Prior to this research, evaluation of this system by various investigators revealed differences in nvPM mass emissions measurement on the order of 15-30% both within a single sampling system and between two systems operating in parallel and measuring nvPM mass emissions from the same source. To investigate this issue, the U. S. Environmental Protection Agency in collaboration with the U. S. Air Force's Arnold Engineering Development Complex initiated the VAriable Response In Aircraft nvPM Testing (VARIAnT) research program to compare nvPM measurements within and between AIR-compliant sampling systems used for measuring combustion aerosols generated both by a 5201 Mini-CAST soot generator and a J85-GE-5 turbojet engine burning multiple fuels. The VARIAnT research program has conducted four test campaigns to date. The first campaign (VARIAnT 1) compared two essentially identical commercial versions of the sampling system while the second campaign (VARIAnT 2) compared a commercial system to the custom-designed Missouri University of Science and Technology's North American Reference System (NARS) built to the same specifications. Comparisons of nvPM particle mass (i.e., black carbon), number, and size were conducted in both campaigns. Additionally, the sensitivity to variation in system operational parameters was evaluated in VARIAnT 1. Results from both campaigns revealed agreement of about 12% between the two sampling systems, irrespective of manufacturer, in all aspects except for black carbon determination. The major source of measurement differences (20-70%) was due to low BC mass measurements made by the Artium Technologies LII-300 as compared to the AVL 483 Micro-Soot Sensor, the Aerodyne Cavity Attenuated Phase Shift (CAPS PMSSA) monitor, and the thermal-optical reference method for elemental carbon (EC) determination, which was used as the BC reference.

SCOPE11 Method for Estimating Aircraft Black Carbon Mass and Particle Number Emissions.

Black carbon (BC) emissions from aircraft engines lead to an increase in the atmospheric burden of fine particulate matter (PM2.5). Exposure to PM2.5 from sources, including aviation, is associated with an increased risk of premature mortality, and BC suspended in the atmosphere has a warming impact on the climate. BC particles emitted from aircraft also serve as nuclei for contrail ice particles, which are a major component of aviation's climate impact. To facilitate the evaluation of these impacts, we have developed a method to estimate BC mass and number emissions at the engine exit plane, referred to as the Smoke Correlation for Particle Emissions-CAEP11 (SCOPE11). We use a data set consisting of SN-BC mass concentration pairs, collected using certification-compliant measurement systems, to develop a new relationship between smoke number (SN) and BC mass concentration. In addition, we use a complementary data set to estimate measurement system loss correction factors and particle geometric mean diameters to estimate BC number emissions at the engine exit plane. Using this method, we estimate global BC emissions from aircraft landing and takeoff (LTO) operations for 2015 to be 0.74 Gg/year (95% CI = 0.64-0.84) and 2.85 × 1025 particles/year (95% CI = 1.86-4.49 × 1025).

Measurement of naphthalene uptake by combustion soot particles.

In this study, we designed and constructed an experimental laboratory apparatus to measure the uptake of volatile organic compounds (VOCs) by soot particles. Results for the uptake of naphthalene (C10H8) by soot particles typical of those found in the exhaust of an aircraft engine are reported in this paper. The naphthalene concentration in the gas phase and naphthalene attached to the particles were measured simultaneously by a heated flame ionization detector (HFID) and a time-of-flight aerosol mass spectrometer (ToF AMS), respectively. The uptake coefficient for naphthalene on soot of (1.11 ± 0.06) × 10(-5) at 293 K was determined by fitting the HFID and AMS measurements of gaseous and particulate naphthalene to a kinetic model of uptake. When the gaseous concentration of naphthalene is kept below the saturation limit during these experiments, the uptake of naphthalene can be considered the dry mass accommodation coefficient.

An algorithm to estimate aircraft cruise black carbon emissions for use in developing a cruise emissions inventory.

UNLABELLED: To provide accurate input parameters to the large-scale global climate simulation models, an algorithm was developed to estimate the black carbon (BC) mass emission index for engines in the commercial fleet at cruise. Using a high-dimensional model representation (HDMR) global sensitivity analysis, relevant engine specification/operation parameters were ranked, and the most important parameters were selected. Simple algebraic formulas were then constructed based on those important parameters. The algorithm takes the cruise power (alternatively, fuel flow rate), altitude, and Mach number as inputs, and calculates BC emission index for a given engine/airframe combination using the engine property parameters, such as the smoke number, available in the International Civil Aviation Organization (ICAO) engine certification databank. The algorithm can be interfaced with state-of-the-art aircraft emissions inventory development tools, and will greatly improve the global climate simulations that currently use a single fleet average value for all airplanes. IMPLICATIONS: An algorithm to estimate the cruise condition black carbon emission index for commercial aircraft engines was developed. Using the ICAO certification data, the algorithm can evaluate the black carbon emission at given cruise altitude and speed.

Identification of lubrication oil in the particulate matter emissions from engine exhaust of in-service commercial aircraft.

Lubrication oil was identified in the organic particulate matter (PM) emissions of engine exhaust plumes from in-service commercial aircraft at Chicago Midway Airport (MDW) and O'Hare International Airport (ORD). This is the first field study focused on aircraft lubrication oil emissions, and all of the observed plumes described in this work were due to near-idle engine operations. The identification was carried out with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF AMS) via a collaborative laboratory and field investigation. A characteristic mass marker of lubrication oil, I(85)/I(71), the ratio of ion fragment intensity between m/z = 85 and 71, was used to distinguish lubrication oil from jet engine combustion products. This AMS marker was based on ion fragmentation patterns measured using electron impact ionization for two brands of widely used lubrication oil in a laboratory study. The AMS measurements of exhaust plumes from commercial aircraft in this airport field study reveal that lubrication oil is commonly present in organic PM emissions that are associated with emitted soot particles, unlike the purely oil droplets observed at the lubrication system vent. The characteristic oil marker, I(85)/I(71), was applied to quantitatively determine the contribution from lubrication oil in measured aircraft plumes, which ranges from 5% to 100%.

Determination of the emissions from an aircraft auxiliary power unit (APU) during the Alternative Aviation Fuel Experiment (AAFEX).

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.

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.

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.

Evolution of vehicle exhaust particles in the atmosphere.

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.

Characterization of lubrication oil emissions from aircraft engines.

In this first ever study, particulate matter (PM) emitted from the lubrication system overboard breather vent for two different models of aircraft engines has been systematically characterized. Lubrication oil was confirmed as the predominant component of the emitted particulate matter based upon the characteristic mass spectrum of the pure oil. Total particulate mass and size distributions of the emitted oil are also investigated by several high-sensitivity aerosol characterization instruments. The emission index (EI) of lubrication oil at engine idle is in the range of 2-12 mg kg(-1) and increases with engine power. The chemical composition of the oil droplets is essentially independent of engine thrust, suggesting that engine oil does not undergo thermally driven chemical transformations during the ∼4 h test window. Volumetric mean diameter is around 250-350 nm for all engine power conditions with a slight power dependence.

Aircraft hydrocarbon emissions at Oakland International Airport.

To help airports improve emission inventory data, speciated hydrocarbon emission indices have been measured from in-use commercial, airfreight, and general aviation aircraft at Oakland International Airport. The compounds reported here include formaldehyde, acetaldehyde, ethene, propene, and benzene. At idle, the magnitude of hydrocarbon emission indices was variable and reflected differences in engine technology, actual throttle setting, and ambient temperature. Scaling the measured emission indices to the simultaneously measured formaldehyde (HCHO) emission index eliminated most of the observed variability. This result supports a uniform hydrocarbon emissions profile across engine types when the engine is operating near idle, which can greatly simplify how speciated hydrocarbons are handled in emission inventories. The magnitude of the measured hydrocarbon emission index observed in these measurements (ambient temperature range 12-22 degrees C) is a factor of 1.5-2.2 times larger than the certification benchmarks. Using estimates of operational fuel flow rates at idle, this analysis suggests that current emission inventories at the temperatures encountered at this airport underestimate hydrocarbon emissions from the idle phase of operation by 16-45%.

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.

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.

Laboratory evaluation of an aldehyde scrubber system specifically for the detection of acrolein.

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.

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.

NO and NO2 emission ratios measured from in-use commercial aircraft during taxi and takeoff.

In August 2001, the Aerodyne Mobile Laboratory simultaneously measured NO, NO2, and CO2 within 350 m of a taxiway and 550 m of a runway at John F. Kennedy Airport. The meteorological conditions were such that taxi and takeoff plumes from individual aircraft were clearly resolved against background levels. NO and NO2 concentrations were measured with 1 s time resolution using a dual tunable infrared laser differential absorption spectroscopy instrument, utilizing an astigmatic multipass Herriott cell. The CO2 measurements were also obtained at 1 s time resolution using a commercial non-dispersive infrared absorption instrument. Plumes were measured from over 30 individual planes, ranging from turbo props to jumbo jets. NOx emission indices were determined by examining the correlation between NOx (NO + NO2) and CO2 during the plume measurements. Several aircraft tail numbers were unambiguously identified, allowing those specific airframe/engine combinations to be determined. The resulting NOx emission indices from positively identified in-service operating airplanes are compared with the published International Civil Aviation Organization engine certification test database collected on new engines in certification test cells.