ALBERT

Description: A photochemical ship-plume model, which can consider the ship-plume dynamics and ship-plume chemistry, simultaneously, was developed to gain a better understanding of atmospheric impact of ship emissions. The model performance was then evaluated by a comparison with the observation data measured on a NOAA WP-3D flight during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) airborne field campaign. The simulation conditions and parameters, such as meteorological conditions, emission rates, and background gas and particulate species concentrations, were obtained directly and/or inferred indirectly from the ITCT 2K2 observation data. The model-predicted concentrations showed good agreement with the observed concentrations of five ambient species (NOx, NOy, O3, HNO3, and H2SO4) at the eight plume transects by the WP-3D flight with strong correlations around the 1:1 line (0.66≤R≤0.85). In addition, a set of tests were carried out to approximate the magnitude of the reaction probability of HNO3 onto sea-salt particles in the model-observation comparison framework. These results suggest that the reaction probability of HNO3 onto sea-salt particles may be in the order of 10−3 or smaller. The equivalent NOx lifetime throughout the "entire" plume was also estimated from ship-plume chemistry modeling. The NOx lifetimes estimated throughout the "entire ship plume" was 3.36 h. The short NOx lifetime over the entire ship plume clearly shows that the ship-plume chemistry shortens the NOx lifetime considerably. Therefore, the ship-plume chemistry model should be used to model the changes in ship-plume chemical compositions and better evaluate the atmospheric impact of ocean-going ship emissions.

Description: The shapes of raindrops play an important role in inducing polarimetric rainfall algorithms with differential reflectivity (ZDR) and specific differential phase (KDP). The shapes of raindrops have a direct impact on rainfall estimation. However, the characteristics of raindrop size distribution (DSD) are different depending on precipitation type, storm stage of development, and regional and climatological conditions. Therefore, it is necessary to provide assumptions based on raindrop shapes that reflect the rainfall characteristics of the Korean peninsula. In this study, we presented a method to find optimal polarimetric rainfall algorithms on the Korean peninsula using the 2-Dimensional Video Disdrometer (2DVD) and Bislsan S-Band dual-polarization radar. First, a new axis ratio of raindrop relations was developed for the improvement of rainfall estimation. Second, polarimetric rainfall algorithms were derived using different axis ratio relations, and estimated radar-point one-hour rain rate for the differences in polarimetric rainfall algorithms were compared with the hourly rain rate measured by gauge. In addition, radar rainfall estimation was investigated in relation to calibration bias of reflectivity and differential reflectivity. The derived raindrop axis ratio relation from the 2DVD was more oblate than existing relations in the D 〈 1.5 mm and D 〉 5.5 mm range. The R(KDP, ZDR) algorithm based on a new axis ratio relation showed the best result on DSD statistics; however, the R(Zh, ZDR) algorithm showed the best performance for radar rainfall estimation, because the rainfall events used in the analysis were mainly weak precipitation and KDP is noisy at lower rain rates ( ≤ 5 mm hr−1). Thus, the R(KDP, ZDR) algorithm is suitable for heavy rainfall and R(Zh, ZDR) algorithm is suited for light rainfall. The calibration bias of reflectivity (ZH) and differential reflectivity (ZDR) were calculated from the comparison of measured with simulated ZH and ZDR from the 2DVD. The calculated ZH and ZDR bias was used to reduce radar bias, and to produce more accurate rainfall estimation.

Description: Aged smoke from a prescribed fire (dominated by conifers) impacted Atlanta, GA on 28 February 2007 and dramatically increased hourly ambient concentrations of PM2.5 and organic carbon (OC) up to 140 and 72 μg m−3, respectively. It was estimated that over 1 million residents were exposed to the smoky air lasting from the late afternoon to midnight. To better understand the processes impacting the aging of fire plumes, a detailed chemical speciation of carbonaceous aerosols was conducted by gas chromatography/mass spectrometry (GC/MS) analysis. Ambient concentrations of many organic species (levoglucosan, resin acids, retene, n-alkanes and n-alkanoic acids) associated with wood burning emission were significantly elevated on the event day. Levoglucosan increased by a factor of 10, while hopanes, steranes, cholesterol and major polycyclic aromatic hydrocarbons (PAHs) did not show obvious increases. Strong odd over even carbon number predominance was found for n-alkanes versus even over odd predominance for n-alkanoic acids. Alteration of resin acids during transport from burning sites to monitors is suggested by the observations. Our study also suggests that large quantities of biogenic volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) were released both as products of combustion and unburned vegetation heated by the fire. Higher leaf temperature can stimulate biogenic VOC and SVOC emissions, which enhanced formation of secondary organic aerosols (SOA) in the atmosphere. This is supported by elevated ambient concentrations of secondary organic tracers (dicarboxylic acids, 2-methyltetrols, pinonic acid and pinic acid). An approximate source profile was built for the aged fire plume to help better understand evolution of wood smoke emission and for use in source impact assessment.

Description: In our previous works, it was demonstrated that the combined use of quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), which is also known as low-Z particle EPMA, and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) imaging has great potential for a detailed characterization of individual aerosol particles. In this study, extensively chemically modified (aged) individual Asian dust particles collected during an Asian dust storm event on 11 November 2002 in Korea were characterized by the combined use of low-Z particle EPMA and ATR-FTIR imaging. Overall, 109 individual particles were classified into four particle types based on their morphology, elemental concentrations, and molecular species and/or functional groups of individual particles available from the two analytical techniques: Ca-containing (38%), NaNO3-containing (30%), silicate (22%), and miscellaneous particles (10%). Among the 41 Ca-containing particles, 10, 8, and 14 particles contained nitrate, sulfate, and both, respectively, whereas only two particles contained unreacted CaCO3. Airborne amorphous calcium carbonate (ACC) particles were observed in this Asian dust sample for the first time, where their IR peaks for the insufficient symmetric environment of CO32− ions of ACC were clearly differentiated from those of crystalline CaCO3. This paper also reports the first inland field observation of CaCl2 particles probably converted from CaCO3 through the reaction with HCl(g). HCl(g) was likely released from the reaction of sea salt with NOx/HNO3, as all 33 particles of marine origin contained NaNO3 (no genuine sea salt particle was encountered). Some silicate particles with minor amounts of calcium were observed to be mixed with nitrate, sulfate, and water. Among 24 silicate particles, 10 particles are mixed with water, the presence of which could facilitate atmospheric heterogeneous reactions of silicate particles including swelling minerals, such as montmorillonite and vermiculite, and nonswelling ones, such as feldspar and quartz. This paper provides detailed information on the physicochemical characteristics of these aged individual Asia dust particles through the combined use of the two single-particle analytical techniques, and using this analytical methodology it is clearly shown that internal mixing states of the aged particles are highly complicated.

Description: A photochemical/dynamic ship-plume model, which can consider the ship-plume dynamics and ship-plume chemistry, simultaneously, was developed to gain a better understanding of atmospheric impact of ship emissions. The model performance was then evaluated by a comparison with the observation data measured on a NOAA WP-3D flight during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) airborne field campaign. The simulation conditions and parameters, such as meteorological conditions, emission rates, and background gas and particulate species concentrations, were obtained directly and/or inferred indirectly from the ITCT 2K2 observation data. The model-predicted concentrations showed good agreement with the observed concentrations of five ambient species (NOx, NOy, ozone, HNO3, and H2SO4) at the eight plume transects by the WP-3D flight with strong correlations around the 1:1 line (0.64≤R≤0.85). In addition, a set of tests were carried out to approximate the magnitude of the reaction probability of HNO3 onto sea-salt particles in the model-observation comparison framework. These results suggest that the reaction probability of HNO3 onto sea-salt particles may be in the order of 0.05–0.1. The equivalent NOx lifetime throughout the "entire plume" was also estimated from photochemical/dynamic ship-plume modeling. The NOx lifetimes estimated throughout the entire ship plume ranged from 2.64 h to 3.76 h under stable to neutral stability conditions. The short NOx lifetime over the entire ship plume clearly shows that the ship-plume chemistry shortens the NOx lifetime considerably. Therefore, the ship-plume chemistry model should be used to model the changes in ship-plume chemical compositions and better evaluate the atmospheric impact of ocean-going ship emissions.

Description: Elevated levels of formaldehyde (HCHO) along the ship corridors have been observed by satellite sensors, such as ESA/ERS-2 GOME (Global Ozone Monitoring Experiment), and were also simulated by global 3-D chemistry-transport models. In this study, three likely sources of the elevated HCHO levels in the ship plumes as well as their contributions to the elevated HCHO levels (budget) were investigated using a newly-developed ship-plume photochemical/dynamic model: (1) primary HCHO emission from ships; (2) secondary HCHO production via the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) emitted from ships; and (3) atmospheric oxidation of CH4 within the ship plumes. For this ship-plume modelling study, the ITCT 2K2 (Intercontinental Transport and Chemical Transformation 2002) ship-plume experiment, which was carried out about 100 km off the coast of California on 8 May 2002 (11:00 local standard time), was chosen as a base study case because it is the best defined in terms of (1) meteorological data, (2) in-plume chemical composition, and (3) background chemical composition. From multiple ship-plume model simulations for the ITCT 2K2 ship-plume experiment case, CH4 oxidation by elevated levels of in-plume OH radicals was found to be the main factor responsible for the elevated levels of HCHO in the ITCT 2K2 ship-plume. More than ~88% of the HCHO for the ITCT 2K2 ship-plume is produced by this atmospheric chemical process, except in the areas close to the ship stacks where the main source of the elevated HCHO levels would be primary HCHO from the ships (due to the deactivation of CH4 oxidation from the depletion of in-plume OH radicals). Because of active CH4 oxidation by OH radicals, the instantaneous chemical lifetime of CH4 (τCH4) decreased to ~0.45 yr inside the ship plume, which is in contrast to τCH4 of ~1.1 yr in the background (up to ~41% decrease) for the ITCT 2K2 ship-plume case. A variety of likely ship-plume situations at three different latitudinal locations within the global ship corridors was also studied to determine the enhancements in the HCHO levels in the marine boundary layer (MBL) influenced by ship emissions. It was found that the ship-plume HCHO levels could be 19.9–424.9 pptv higher than the background HCHO levels depending on the latitudinal locations of the ship plumes (i.e., intensity of solar radiation and temperature), MBL stability and NOx emission rates. On the other hand, NMVOC emissions from ships were not found to be a primary source of photochemical HCHO production inside ship plumes due to their rapid and individual dilution. However, the diluted NMVOCs would contribute to the HCHO productions in the background air.

Description: Thermodenuding particles can provide insights into aerosol composition and may be a way to create particles in laboratory chambers that better mimic the atmosphere. The relative volatility of secondary organic aerosol (SOA) was investigated by evaporating organics from the particles using a thermodenuder (TD) at temperatures between ∼60 and 100 °C. Volatility was influenced by the parent hydrocarbon, oxidation chemistry and relative humidity (RH). For SOA generated from ozonolysis, limonene had lower volatility than α-pinene, and OH scavengers had no influence on volatility. For photooxidation, α-pinene SOA was slightly more volatile than limonene SOA. Increasing RH also modestly increased volatility, while toluene SOA was unaffected by heating to 98 °C. For both α-pinene and limonene, the concentration of NOx and the HC / NOx ratio had no discernible effect on SOA volatility. Refractive indices for the original and denuded particles were retrieved from polar nephelometer measurements using parallel and perpendicular polarized 532 nm light. Retrievals were performed with a genetic algorithm method using Mie–Lorenz scattering theory and measured particle size distributions. Retrieved refractive indices for the SOA before thermodenuding varied between 1.35 and 1.61 depending on several factors, including parent hydrocarbon, oxidation chemistry, and SOA generation temperature. For high NOx SOA, as particles shrink, their refractive index returns to the value of the corresponding size particles before heating (limonene) or slightly higher (α-pinene). For low NOx however, the resulting refractive index is 0.05 ± 0.02 lower than the corresponding size undenuded particles. Additionally, for α-pinene SOA from ozonolysis with OH radical scavenger, resulting refractive indices were higher by about 0.03 after heating. Consistent with no change in size, refractive indices of toluene SOA were unaffected by heating. Finally, refractive index data available to date are reviewed, leading to the suggestion that the most representative values for mr at λ =532 nm for biogenic and anthropogenic SOA are 1.44 and 1.55, respectively.

Description: To examine the influence of both crop cultivation and surface air temperatures (SATs) on annual global isoprene and monoterpene emissions, which can lead to the formation of secondary organic aerosols (SOAs), we simulated, on a monthly basis, the annual emissions of volatile organic compounds (VOCs) during the period 1854–2000. The model estimates were based on historical climate data such as SATs, and downward solar radiation (DSR) reproduced with an atmospheric-ocean circulation model, as well as a time series of the global distribution of cropland (to test the hypothesis that conversion of forests into croplands lowers emissions). The simulations demonstrated that global SAT, DSR, the combination of SAT and DSR, and the expansion of cropland all affected emissions. The effect of cropland expansion (i.e., forest conversion) on annual emissions during this period was larger for isoprene (~7% reduction on a global scale) than for monoterpenes (~2% reduction), mainly because of the reduction in broadleaf evergreen forests (BEFs) in Southeast Asia, which have the highest and most constant emissions of isoprene and where both temperature and radiation are high all year round. The reduction in the Amazon region and in parts of Africa, which are other primary sources of annual global isoprene emissions, but where the conversion of BEF to cropland has been much smaller than in Southeast Asia, was less remarkable, probably because the broadleaf deciduous forests and C4 grasslands in these areas have lower and seasonal emissions; hence, their conversion has less effect. On the other hand, the difference in the emission factors (ε) between cropland and the other vegetation types was much lower for monoterpenes than for isoprene, although the ε for cropland was generally the lowest for both compounds. Thus, the expansion of cropland also contributed to the reduction in monoterpene emissions to some degree, but had less effect. A ~5% increase in emissions due to rising SAT was more than offset by the decrease in isoprene emissions and a concurrent ~2% reduction caused by a decrease in DSR. Overall, annual global isoprene emissions in 2000 were lower than in 1854 by 13 TgC yr−1, whereas annual global monoterpene emissions were higher by 2.3 TgC yr−1.

Description: To show how remote-sensing products can be used to classify the entire CONUS domain into "geographical regions" and "chemical regimes", we analyzed the results of simulation from the Community Multiscale Air Quality (CMAQ) model version 4.7.1 over the Conterminous United States (CONUS) for August 2009. In addition, we observe how these classifications capture the weekly cycles of ground-level nitrogen oxide (NOx) and ozone (O3) at US EPA Air Quality System (AQS) sites. We use the Advanced Very High Resolution Radiometer (AVHRR) land use dominant categories and the Global Ozone Monitoring Experiment-2 (GOME-2) HCHO/NO2 column density ratios to allocate geographical regions (i.e., "urban", "forest", and "other" regions) and chemical regimes (i.e., "NOx-saturated", "NOx-sensitive", and "mixed" regimes). We also show that CMAQ simulations using GOME-2 satellite-adjusted NOx emissions mitigate the discrepancy between the weekly cycles of NOx from AQS observations and that from CMAQ simulation results. We found geographical regions and chemical regimes do not show a one-to-one correspondence: the averaged HCHO / NO2 ratios for AVHRR "urban" and "forest" regions are 2.1 and 4.0, which correspond to GOME-2 "mixed" and "NOx-sensitive" regimes, respectively. Both AQS-observed and CMAQ-simulated weekly cycles of NOx show high concentrations on weekdays and low concentrations on weekends, but with one- or two-day shifts of weekly high peaks in the simulated results, which eventually introduces the shifts in simulated weekly-low O3 concentration. In addition, whereas the high weekend O3 anomaly is clearly observable at sites over the GOME-2 NOx-saturated regime in both AQS and CMAQ, the weekend effect is not captured at sites over the AVHRR urban region because of the chemical characteristics of the urban sites (≈GOME-2 mixed regime). In addition, the weekend effect from AQS is more clearly discernible at sites above the GOME-2 NOx-saturated regime than at other sites above the CMAQ NOx-saturated regime, suggesting that the GOME-2-based chemical regime classification is more accurate than CMAQ-based chemical classification. Furthermore, the CMAQ simulations using the GOME-2-derived NOx emissions adjustment (decreasing from 462 Gg N to 426 Gg N over the US for August 2009) show large reductions of simulated NOx concentrations (particularly over the urban, or NOx-saturated, regime), and mitigates the large discrepancies between the absolute amount and the weekly pattern of NOx concentrations of the EPA AQS and those of the baseline CMAQ.

Description: Previous controversial studies on the hygroscopic behavior of NaNO3 aerosols and our frequent observation of crystalline NaNO3-containing ambient aerosol particles prompted this extensive hygroscopic study on NaNO3 aerosol particles. In this work, the hygroscopic behavior of individual NaNO3 particles of 2.5–4.0 μm in diameter is investigated on a single-particle basis using an optical microscopy technique. Quite different hygroscopic behaviors between particles generated by the nebulization of NaNO3 solution and powdery particles were observed; i.e., most of generated particles continuously grew and shrank during humidifying and dehydration processes, respectively, and yet all the individual powdery particles had reproducible deliquescence and efflorescence relative humidities (DRHs and ERHs). The different behaviors of the two NaNO3 systems are due to the different nucleation mechanisms. Our hygroscopic studies of NaNO3 particles generated from aqueous NaNO3 solutions indicate that they nucleate via homogeneous nucleation, but the time scale for the nucleation to occur is too long to be atmospherically relevant. And thus no efflorescence of the particles has been observed in the laboratory measurements. However, when chemical species acting as heterogeneous nuclei are present, then efflorescence occurs which can explain the observation of ambient crystalline NaNO3 particles. It is imperative to work with heterogeneous nucleation systems which are more relevant to the real world.