Plume Age Research Articles

Photochemical evolution of organic aerosols observed in urban plumes from Hong Kong and the Pearl River Delta of China

Organic aerosols influence human health and global radiative forcing. However, their sources and evolution processes in the atmosphere are not completely understood. To study the aging and production of organic aerosols in a subtropical environment, we measured hourly resolved organic carbon (OC) and element carbon (EC) in PM2.5 at a receptor site (Tung Chung, TC) in Hong Kong from August 2011 to May 2012. The average OC concentrations exhibited the highest values in late autumn and were higher during the daytime than at night. The secondary organic carbon (SOC) concentrations, which were estimated using an EC-tracer method, comprised approximately half of the total OC on average. The SOC showed good correlation with odd oxygen (Ox = O3 + NO2) in the summer and autumn seasons, suggestive of contribution of photochemical activities to the formation of secondary organic aerosols (SOA). We calculated production rates of SOA using the photochemical age (defined as –Log10(NOx/NOy)) in urban plumes from the Pearl River Delta (PRD) region and Hong Kong during pollution episodes in summer and autumn. The CO-normalized SOC increased with the photochemical age, with production rates ranging from 1.31 to 1.82 μg m−3 ppmv−1 h−1 in autumn and with a larger rate in summer (3.86 μg m−3 ppmv−1 h−1). The rates are in the range of the rates observed in the outflow from Mexico City, the eastern U.S. and Los Angeles. Microscopic analyses of the individual aerosol particles revealed large contrasts of aerosol physico-chemical properties on clean and smoggy days, with thick organic coatings internally mixed with inorganic sulfate for all particle sizes in the aged plumes from the PRD region.

Reductions in aircraft particulate emissions due to the use of Fischer–Tropsch fuels

Abstract. The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability, and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January–February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer–Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions in mass of 86% averaged over all powers) and blended fuels (66%) relative to the JP-8 baseline with the largest reductions at idle conditions. At 7% power, this corresponds to a reduction from 7.6 mg kg−1 for JP-8 to 1.2 mg kg−1 for the natural gas FT fuel. At full power, soot emissions were reduced from 103 to 24 mg kg−1 (JP-8 and natural gas FT, respectively). The alternative fuels also produced smaller soot (e.g., at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the natural gas FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the feedstock. As the plume cools downwind of the engine, nucleation-mode aerosols form. For the pure FT fuels, reductions (94% averaged over all powers) in downwind particle number emissions were similar to those measured at the exhaust plane (84%). However, the blended fuels had less of a reduction (reductions of 30–44%) than initially measured (64%). The likely explanation is that the reduced soot emissions in the blended fuel exhaust plume results in promotion of new particle formation microphysics, rather than coating on pre-existing soot particles, which is dominant in the JP-8 exhaust plume. Downwind particle volume emissions were reduced for both the pure (79 and 86% reductions) and blended FT fuels (36 and 46%) due to the large reductions in soot emissions. In addition, the alternative fuels had reduced particulate sulfate production (near zero for FT fuels) due to decreased fuel sulfur content. To study the formation of volatile aerosols (defined as any aerosol formed as the plume ages) in more detail, tests were performed at varying ambient temperatures (−4 to 20 °C). At idle, particle number and volume emissions were reduced linearly with increasing ambient temperature, with best fit slopes corresponding to −8 × 1014 particles (kg fuel)−1 °C−1 for particle number emissions and −10 mm3 (kg fuel)−1 °C−1 for particle volume emissions. The temperature dependency of aerosol formation can have large effects on local air quality surrounding airports in cold regions. Aircraft-produced aerosols in these regions will be much larger than levels expected based solely on measurements made directly at the engine exit plane. The majority (90% at idle) of the volatile aerosol mass formed as nucleation-mode aerosols, with a smaller fraction as a soot coating. Conversion efficiencies of up to 2.8% were measured for the partitioning of gas-phase precursors (unburned hydrocarbons and SO2) to form volatile aerosols. Highest conversion efficiencies were measured at 45% power.

Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

Abstract. Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27–29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4–15.7%), and the most aged samples from CARES contained fewer carbon–carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements will allow for a comprehensive evaluation of aerosol process models used in climate research.

Laboratory and modeling studies on the effects of water and soot emissions and ambient conditions on the properties of contrail ice particles in the jet regime

Abstract. Contrails and contrail-induced cirrus clouds are identified as the most uncertain components in determining aviation impacts on global climate change. Parameters affecting contrail ice particle formation immediately after the engine exit plane (< 5 s in plume age) may be critical to ice particle properties used in large-scale models predicting contrail radiative forcing. Despite this, detailed understanding of these parametric effects is still limited. In this paper, we present results from recent laboratory and modeling studies conducted to investigate the effects of water and soot emissions and ambient conditions on near-field formation of contrail ice particles and ice particle properties. The Particle Aerosol Laboratory (PAL) at the NASA Glenn Research Center and the Aerodyne microphysical parcel model for contrail ice particle formation were employed. Our studies show that exhaust water concentration has a significant impact on contrail ice particle formation and properties. When soot particles were introduced, ice particle formation was observed only when exhaust water concentration was above a critical level. When no soot or sulfuric acid was introduced, no ice particle formation was observed, suggesting that ice particle formation from homogeneous nucleation followed by homogeneous freezing of liquid water was unfavorable. Soot particles were found to compete for water vapor condensation, and higher soot concentrations emitted into the chamber resulted in smaller ice particles being formed. Chamber conditions corresponding to higher cruising altitudes were found to favor ice particle formation. The microphysical model captures trends of particle extinction measurements well, but discrepancies between the model and the optical particle counter measurements exist as the model predicts narrower ice particle size distributions and ice particle sizes nearly a factor of two larger than measured. These discrepancies are likely due to particle loss and scatter during the experimental sampling process and the lack of treatment of turbulent mixing in the model. Our combined experimental and modeling work demonstrates that formation of contrail ice particles can be reproduced in the NASA PAL facility, and the parametric understanding of the ice particle properties from the model and experiments can potentially be used in large-scale models to provide better estimates of the impact of aviation contrails on climate change.

Reply to the “Comment by Delmelle et al. (2013) on ‘Scavenging of sulfur, halogens and trace metals by volcanic ash: The 2010 Eyjafjallajökull eruption’ by Bagnato et al. (2013)”

With this short communication we address the principal issues raised by Delmelle et al. (2014) in relation to the work of Bagnato et al. (2013) concerning the 2010 eruption of Eyjafjallajökull, Iceland. The principal conclusions of the work of Bagnato et al. (2013) include the observation that protracted gas-aerosol interaction in the plume promotes selective leaching of cation species from ash, with alkalis and Ca (and, among trace elements, Zn and Cu) being more rapidly re-mobilized (and transferred to soluble surface salts) relative to more inert elements (Mg, Ti). They also observed that adsorption onto ash surfaces is a major atmospheric sink of volcanic acidic gases, with 282tons of elemental sulfur and 605–691tons of halogens being daily ground deposited via ash over Iceland in early May 2010. Acidic gas adsorption onto ash increases almost linearly with plume aging (e.g., upon increasing in-plume residence times of ash and gases), and is seen to proceed at about 3 time faster rates for HF than for SO2 and HCl. However, Delmelle et al. (2014) criticized our strategies for data acquisition, processing and interpretation. They also raised some objections concerning several key topics explored by Bagnato et al. (2013), with a special focus on the discussion of rates of interaction between ash particles and gases in a volcanic cloud, and the consequent formation of soluble salts on ash surfaces. They also considered incorrect the estimate of depositional fluxes and volatile budget for the Eyjafjallajökull eruption. While we appreciate the in-depth analysis of Delmelle et al. (2014), we show that most of their criticisms derive from a partial and sometimes incorrect understanding of the work of Bagnato et al. (2013), which overall led to unsupported conclusions and misleading analysis of the original results. Here, we present a detailed response to the comments of Delmelle et al. (2014), accompanied by additional explicative material. The principal conclusions presented in Bagnato et al. (2013) are given additional support by this complementary note.

Hygroscopic properties of smoke-generated organic aerosol particles emitted in the marine atmosphere

Abstract. During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE), a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs): between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH) of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm−3), which lead to substantially increased cloud condensation nuclei (CCN) concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C) and water-soluble organic mass (WSOM) increased with plume age: from < 0.001 to 0.2, and from 2.42 to 4.96 μg m−3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94). High-resolution aerosol mass spectrometer (AMS) spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.

Ozone photochemistry in boreal biomass burning plumes

Abstract. We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

ACE-FTS observations of pyrogenic trace species in boreal biomass burning plumes during BORTAS

Abstract. To further our understanding of the effects of biomass burning emissions on atmospheric composition, the BORTAS campaign (BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) was conducted on 12 July to 3 August 2011 during the boreal forest fire season in Canada. The simultaneous aerial, ground and satellite measurement campaign sought to record instances of boreal biomass burning to measure the tropospheric volume mixing ratios (VMRs) of short- and long-lived trace molecular species from biomass burning emissions. The goal was to investigate the connection between the composition and the distribution of these pyrogenic outflows and their resulting perturbation to atmospheric chemistry, with particular focus on oxidant species to determine the overall impact on the oxidizing capacity of the free troposphere. Measurements of pyrogenic trace species in boreal biomass burning plumes were made by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) onboard the Canadian Space Agency (CSA) SCISAT-1 satellite during the BORTAS campaign. Even though biomass burning emissions are typically confined to the boundary layer, outflows are often injected into the upper troposphere by isolated convection and fire-related convective processes, thus allowing space-borne instruments to measure these pyrogenic outflows. An extensive set of 14 molecules – CH3OH, C2H2, C2H6, C3H6O, CO, HCN, HCOOH, HNO3, H2CO, NO, NO2, OCS, O3, and PAN – have been analysed. Included in this analysis is the calculation of age-dependent sets of enhancement ratios for each of the species originating from fires in North America (Canada, Alaska) and Siberia for a period of up to 7 days. Ratio values for the shorter lived primary pyrogenic species decrease over time primarily due to oxidation by the OH radical as the plume ages and values for longer lived species such as HCN and C2H6 remain relatively unchanged. Increasing negative values are observed for the oxidant species, including O3, indicating a destruction process in the plume as it ages such that concentrations of the oxidant species have dropped below their off-plume values. Results from previous campaigns have indicated that values for the molar ratios of ΔO3 /ΔO obtained from the measurements of the pyrogenic outflow from boreal fires are highly variable and range from negative to positive, irrespective of plume age. This variability has been attributed to pollution effects where the pyrogenic outflows have mixed with either local urban NOx emissions or pyrogenic emissions from the long-range transport of older plumes, thus affecting the production of O3 within the plumes. The results from this study have identified another potential cause of the variability in O3 concentrations observed in the measurements of biomass burning emissions, where evidence of stratosphere–troposphere exchange due to the pyroconvective updrafts from fires has been identified. Perturbations caused by the lofted emissions in these fire-aided convective processes may result in the intrusion of stratospheric air masses into the free troposphere and subsequent mixing of stratospheric O3 into the pyrogenic outflows causing fluctuations in observed ΔO3/ΔCO molar ratios.

Atmospheric Measurements of the Physical Evolution of Aircraft Exhaust Plumes

Drawing from a series of field measurement activities including the Alternative Aviation Fuels Experiments (AAFEX1 and AAFEX2), we present experimental measurements of particle number, size, and composition-resolved mass that describe the physical and chemical evolution of aircraft exhaust plumes on the time scale of 5 s to 2-3 min. As the plume ages, the particle number emission index initially increases by a factor of 10-50, due to gas-to-particle formation of a nucleation/growth mode, and then begins to fall with increased aging. Increasing the fuel sulfur content causes the initial increase to occur more rapidly. The contribution of the nucleation/growth mode to the overall particle number density is most pronounced at idle power and decreases with increasing engine power. Increasing fuel sulfur content, but not fuel aromatic content causes the nucleation/growth mode to dominate the particle number emissions at higher powers than for a fuel with "normal" sulfur and aromatic content. Particle size measurements indicate that the observed particle number emissions trends are due to continuing gas-to-particle conversion and coagulation growth of the nucleation/growth mode particles, processes which simultaneously increase particle mass and reduce particle number density. Measurements of nucleation/growth mode mass are consistent with the interpretation of particle number and size data and suggest that engine exit plane measurements may underestimate the total particle mass by as much as a factor of between 5 and 10.

Volatile organic compounds in Tijuana during the Cal-Mex 2010 campaign: Measurements and source apportionment

As part of the Cal-Mex 2010 air quality study, a proton transfer reaction–mass spectrometer (PTR-MS) was deployed at the San Diego–Tijuana border area to measure volatile organic compounds (VOCs) from 15 May to 30 June 2010. The major VOCs identified during the study included oxygenated VOCs (e.g., methanol, acetaldehyde, acetone, and methyl ethyl ketone) and aromatics (e.g., benzene, toluene, C8- and C9-aromatics). Biogenic VOCs (e.g., isoprene) were scarce in this region because of the lack of vegetation in this arid area. Using an U.S. EPA positive matrix factorization model, VOCs together with other trace gases (NOx, NOz and SO2) observed in this border region were attributed to four types of sources, i.e., local industrial solvent usage (58% in ppbC), gasoline vehicle exhaust (19% in ppbC), diesel vehicle exhaust (14% in ppbC), and aged plume (9% in ppbC) due to regional background and/or long-range transport. Diesel vehicle emission contributed to 87% of SO2 and 75% of NOx, and aged plume contributed to 92% of NOz. An independent conditional probability function analysis of VOCs, wind direction, and wind speed indicated that the industrial source did not show a significant tendency with wind direction. Both gasoline and diesel engine emissions were associated with air masses passing through two busy cross-border ports. Aged plumes were strongly associated with NW wind, which likely brought in aged air masses from the populated San Diego area.

Spectral absorption of biomass burning aerosol determined from retrieved single scattering albedo during ARCTAS

Abstract. Actinic flux, as well as aerosol chemical and optical properties, were measured aboard the NASA DC-8 aircraft during the ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) mission in Spring and Summer 2008. These measurements were used in a radiative transfer code to retrieve spectral (350–550 nm) aerosol single scattering albedo (SSA) for biomass burning plumes encountered on 17 April and 29 June. Retrieved SSA values were subsequently used to calculate the absorption Angstrom exponent (AAE) over the 350–500 nm range. Both plumes exhibited enhanced spectral absorption with AAE values that exceeded 1 (6.78 ± 0.38 for 17 April and 3.34 ± 0.11 for 29 June). This enhanced absorption was primarily due to organic aerosol (OA) which contributed significantly to total absorption at all wavelengths for both 17 April (57.7%) and 29 June (56.2%). OA contributions to absorption were greater at UV wavelengths than at visible wavelengths for both cases. Differences in AAE values between the two cases were attributed to differences in plume age and thus to differences in the ratio of OA and black carbon (BC) concentrations. However, notable differences between AAE values calculated for the OA (AAEOA) for 17 April (11.15 ± 0.59) and 29 June (4.94 ± 0.19) suggested differences in the plume AAE values might also be due to differences in organic aerosol composition. The 17 April OA was much more oxidized than the 29 June OA as denoted by a higher oxidation state value for 17 April (+0.16 vs. −0.32). Differences in the AAEOA, as well as the overall AAE, were thus also possibly due to oxidation of biomass burning primary organic aerosol in the 17 April plume that resulted in the formation of OA with a greater spectral-dependence of absorption.

Regional radiative impact of volcanic aerosol from the 2009 eruption of Mt. Redoubt

Abstract. High northern latitude eruptions have the potential to release volcanic aerosol into the Arctic environment, perturbing the Arctic's climate system. We present assessments of shortwave (SW), longwave (LW) and net direct aerosol radiative forcing efficiencies and atmospheric heating/cooling rates caused by volcanic aerosol from the 2009 eruption of Mt. Redoubt by performing radiative transfer modeling constrained by NASA A-Train satellite data. The optical properties of volcanic aerosol were calculated by introducing a compositionally resolved microphysical model developed for both ash and sulfates. Two compositions of volcanic aerosol were considered in order to examine a fresh, ash rich plume and an older, ash poor plume. Optical models were incorporated into a modified version of the SBDART radiative transfer model. Our results indicate that environmental conditions, such as surface albedo and solar zenith angle (SZA), can influence the sign and the magnitude of the radiative forcing at the top of the atmosphere (TOA) and at the surface and the magnitude of the forcing in the aerosol layer. We find that a fresh, thin plume (~2.5–7 km) at an AOD (550 nm) range of 0.18–0.58 and SZA = 55° over snow cools the surface and warms the TOA, but the opposite effect is seen for TOA by the same layer over ocean. The layer over snow also warms by 64 W m−2AOD−1 more than the same plume over seawater. The layer over snow at SZA = 75° warms the TOA 96 W m−2AOD−1 less than it would at SZA = 55° over snow, and there is instead warming at the surface. We also find that plume aging can alter the magnitude of the radiative forcing. An aged plume over snow at SZA = 55° would warm the TOA and layer by 146 and 143 W m−2AOD−1 less than the fresh plume, while the aging plume cools the surface 3 W m−2AOD−1 more. Comparing results for the thin plume to those for a thick plume (~3–20 km), we find that the fresh, thick plume with AOD(550 nm) = 3, over seawater, and SZA = 55° heats the upper part of the plume in the SW ~28 K day−1 more and cools in the LW by ~6.3 K day−1 more than a fresh, thin plume under the same environmental conditions. We compare our assessments with those reported for other aerosols typical to the Arctic environment (smoke from wildfires, Arctic haze, and dust) to demonstrate the importance of volcanic aerosols.

Measurement of Volatile Particulate Matter Emissions From Aircraft Engines Using a Simulated Plume Aging System

Aircraft exhaust contains nonvolatile (soot) particulate matter (PM), trace gas pollutants, and volatile PM precursor material. Nonvolatile soot particles are predominantly present at the engine exit plane, but volatile PM precursors form new particles or add mass to the existing ones as the exhaust is diluted and cooled. Accurately characterizing the volatile PM mass, number, and size distribution is challenging due to this evolving nature and the impact of local ambient conditions on the gas-to-particle conversion processes. To accurately and consistently measure the aircraft PM emissions, a dilution and aging sampling system that can condense volatile precursors to particle phase to simulate the atmospheric evolution of aircraft engine exhaust has been developed. In this paper, a field demonstration of its operation is described. The dilution/aging probe system was tested using both a combustor rig and on-wing CFM56-7 engines. During the combustor rig testing at NASA Glenn Research Center, the dilution/aging probe supported formation of both nucleation/growth mode particles and soot coatings. The results showed that by increasing residence time, the nucleation particles become larger in size, increase in total mass, and decrease in number. During the on-wing CFM56-7 engine testing at Chicago Midway Airport, the dilution/aging probe was able to form soot coatings along with nucleation mode particles, unlike conventional 1-m probe engine measurements. The number concentration of nucleation particles depended on the sample fraction and relative humidity of the dilution air. The performance of the instrument is analyzed and explained using computational microphysics simulations.

Tropical biomass burning smoke plume size, shape, reflectance, and age based on 2001–2009 MISR imagery of Borneo

Abstract. Land clearing for crops, plantations and grazing results in anthropogenic burning of tropical forests and peatlands in Indonesia, where images of fire-generated aerosol plumes have been captured by the Multi-angle Imaging SpectroRadiometer (MISR) since 2001. Here we analyze the size, shape, optical properties, and age of distinct fire-generated plumes in Borneo from 2001–2009. The local MISR overpass at 10:30 a.m. misses the afternoon peak of Borneo fire emissions, and may preferentially sample longer plumes from persistent fires burning overnight. Typically the smoke flows with the prevailing southeasterly surface winds at 3–4 m s−1, and forms ovoid plumes whose mean length, height, and cross-plume width are 41 km, 708 m, and 27% of the plume length, respectively. 50% of these plumes have length between 24 and 50 km, height between 523 and 993 m and width between 18% and 30% of plume length. Length and cross-plume width are lognormally distributed, while height follows a normal distribution. Borneo smoke plume heights are similar to previously reported plume heights, yet Borneo plumes are on average nearly three times longer than previously studied plumes. This could be due to sampling or to more persistent fires and greater fuel loads in peatlands than in other tropical forests. Plume area (median 169 km2, with 25th and 75th percentiles at 99 km2 and 304 km2, respectively) varies exponentially with length, though for most plumes a linear relation provides a good approximation. The MISR-estimated plume optical properties involve greater uncertainties than the geometric properties, and show patterns consistent with smoke aging. Optical depth increases by 15–25% in the down-plume direction, consistent with hygroscopic growth and nucleation overwhelming the effects of particle dispersion. Both particle single-scattering albedo and top-of-atmosphere reflectance peak about halfway down-plume, at values about 3% and 10% greater than at the origin, respectively. The initially oblong plumes become brighter and more circular with time, increasingly resembling smoke clouds. Wind speed does not explain a significant fraction of the variation in plume geometry. We provide a parameterization of plume shape that can help atmospheric models estimate the effects of plumes on weather, climate, and air quality. Plume age, the age of smoke furthest down-plume, is lognormally distributed with a median of 2.8 h (25th and 75th percentiles at 1.3 h and 4.0 h), different from the median ages reported in other studies. Intercomparison of our results with previous studies shows that the shape, height, optical depth, and lifetime characteristics reported for tropical biomass burning plumes on three continents are dissimilar and distinct from the same characteristics of non-tropical wildfire plumes.

Evolution of trace gases and particles emitted by a chaparral fire in California

Abstract. Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O3 to excess CO in the plume (ΔO3/ΔCO) increased from −5.13 (±1.13) × 10−3 to 10.2 (±2.16) × 10−2 in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 106 molec cm−3, consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations.

Calculation of river-seawater endmembers and differential trace metal scavenging in the Columbia River plume

A simple model is presented for calculating river and seawater mixing zone endmembers. This model allows construction of a conservative mixing line with respect to trace metals scavenged from surface waters, in the absence of direct endmember sampling. Results of the model suggest a transition from non-conservative to conservative behavior of the trace metals gallium (Ga) and zirconium (Zr) along a transect extending offshore of the Columbia River, indicating environmental controls on differential scavenging. Mechanistic explanation of observed differential scavenging is supported by wind data indicating northward transport of Columbia River plume waters, followed by southwest, offshore, transport. Columbia River plume waters transported to the southwest at the time of sample collection were therefore flanked offshore by aged plume waters returning from the north. While upwelling conditions provide nutrients during southerly transport of plume waters, northward plume transport is associated with downwelling, low nutrient conditions. Low phytoplankton abundance during periods of northward plume transport reduces trace metal scavenging, therefore dilution of river waters with ocean surface waters of comparatively low Ga and Zr concentrations results in near-conservative mixing of Ga and Zr in offshore, aged, plume waters. Results of this work suggest dynamic modification of trace metal residence time within close geographic proximity established by physical and biologic controls, dictated by local winds. Lower trace metal scavenging rates, resulting in a longer residence time, are suggested during northward transport of Columbia River plume waters, compared to higher scavenging rates, and thus shorter residence times, during southerly transport of plume waters. Gallium, demonstrating high analytical precision, reduced contamination risk, and decreased complications of upwelled sources relative to Zr, is proposed to provide identification of aged Columbia River plume waters.

Effects of aging on organic aerosol from open biomass burning smoke in aircraft and laboratory studies

Abstract. Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = −0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr−1 is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

Observations of nonmethane organic compounds during ARCTAS − Part 1: Biomass burning emissions and plume enhancements

Abstract. Mixing ratios of a large number of nonmethane organic compounds (NMOCs) were observed by the Trace Organic Gas Analyzer (TOGA) on board the NASA DC-8 as part of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaign. Many of these NMOCs were observed concurrently by one or both of two other NMOC measurement techniques on board the DC-8: proton-transfer-reaction mass spectrometry (PTR-MS) and whole air canister sampling (WAS). A comparison of these measurements to the data from TOGA indicates good agreement for the majority of co-measured NMOCs. The ARCTAS study, which included both spring and summer deployments, provided opportunities to sample a large number of biomass burning (BB) plumes with origins in Asia, California and central Canada, ranging from very recent emissions to plumes aged one week or more. For this analysis, BB smoke interceptions were grouped by flight, source region and, in some cases, time of day, generating 40 identified BB plumes for analysis. Normalized excess mixing ratios (NEMRs) to CO were determined for each of the 40 plumes for up to 19 different NMOCs or NMOC groups. Although the majority of observed NEMRs for individual NMOCs or NMOC groups were in agreement with previously-reported values, the observed NEMRs to CO for ethanol, a rarely quantified gas-phase trace gas, ranged from values similar to those previously reported, to up to an order of magnitude greater. Notably, though variable between plumes, observed NEMRs of individual light alkanes are highly correlated within BB emissions, independent of estimated plume ages. BB emissions of oxygenated NMOC were also found to be often well-correlated. Using the NCAR Master Mechanism chemical box model initialized with concentrations based on two observed scenarios, fresh Canadian BB and fresh Californian BB, decreases are predicted for the low molecular weight carbonyls (i.e. formaldehyde, acetaldehyde, acetone and methyl ethyl ketone, MEK) and alcohols (i.e. methanol and ethanol) as the plumes evolve in time, i.e. the production of these compounds is less than the chemical loss. Comparisons of the modeled NEMRs to the observed NEMRs from BB plumes estimated to be three days in age or less indicate overall good agreement.

Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

Abstract. In this paper we report chemically resolved measurements of organic aerosol (OA) and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA). The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1) aged biomass burning emissions and oxidized urban emissions, (2) oxidized urban emissions (3) oxidation products of monoterpene emissions, (4) monoterpene emissions, (5) anthropogenic emissions and (6) local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September) due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October), even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO), consistent with previous observations, while being comprised of mostly non-fossil carbon (>75%). The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1%) of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NOx enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site.

Vertical distributions of non-methane hydrocarbons and halocarbons in the lower troposphere over northeast China

Abstract Vertical distributions of air pollutants are crucial for understanding the key processes of atmospheric transport and for evaluating chemical transport models. In this paper, we present measurements of non-methane hydrocarbons (NMHCs) and halocarbons obtained from an intensive aircraft study over northeast (NE) China in summer 2007. Most compounds exhibited a typical negative profile of decreasing mixing ratios with increasing altitude, although the gradients differed with different species. Three regional plumes with enhanced VOC mixing ratios were discerned and characterized. An aged plume transported from the northern part of the densely populated North China Plain (NCP; i.e. Beijing–Tianjin area) showed relatively higher levels of HCFC-22, 1,2-dichloroethane (1,2-DCE) and toluene. In comparison, the plume originating from Korea had higher abundances of CFC-12, tetrachloroethene (C2Cl4) and methyl chloride (CH3Cl), while regional air masses from NE China contained more abundant light alkanes. By comparing these results with the earlier PEM-West B (1994) and TRACE-P (2001) aircraft measurements, continuing declining trends were derived for methyl chloroform (CH3CCl3), tetrachloromethane (CCl4) and C2Cl4 over the greater China–northwestern Pacific region, indicating the accomplishment of China in reducing these compounds under the Montreal protocol. However, the study also provided evidence for the continuing emissions of several halocarbons in China in 2007, such as CFCs (mainly from materials in stock) and HCFCs.