ALBERT

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: 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.

Description: Despite recent debates on erosion-enhanced sinks of CO2 and contrasting findings on the biodegradation of recalcitrant organic materials in large rivers, little attention has been paid to the export and transformations of particulate organic carbon (POC) and dissolved organic C (DOC) in mountainous headwater watersheds under monsoon climates. To comparatively evaluate the significance of heavy monsoon rainfalls for the magnitude and environmental implications of storm-enhanced export of POC and DOC, the relationships between storm magnitude and C export were examined in a mountainous, forested headwater stream in the Haean Basin, South Korea, during 50 storm events over the 4 year monitoring period. We also compared biodegradation and disinfection byproduct (DBP) formation potentials of the DOC and POC exported during an extreme rainfall event. Event mean concentrations and export of POC increased nonlinearly above thresholds of precipitation and discharge, significantly exceeding the increases of DOC. The export of POC during a few storm events with a total rainfall above 200 mm per event exceeded the annual organic C export during dry years. During the large storm event (209 mm), concentrations of total trihalomethanes formed by POC-derived dissolved components changed synchronously with POC concentrations, exhibiting lower levels than those formed by DOC. During a 30 day incubation at 25 °C, both DOC and POC exported during peak flow initially exhibited rapid biodegradation of labile components, whereas POC-derived materials increased continuously not only DOC concentrations, but also fulvic- and humic-like fluorescent components. These results highlight the significance of extreme rainfall events as "hot moments" for POC export and also suggest that storm pulses of POC can provide potential sources of labile DOC components that can rapidly biodegrade and form DBPs in headwater streams, contrasting with other studies assuming mountainous rivers as a passive conduit of organic C.

Description: The National Air Quality Forecast Capability (NAQFC) project provides the US with operational and experimental real-time ozone predictions using two different versions of the three-dimensional Community Multi-scale Air Quality (CMAQ) modeling system. Routine evaluation using near-real-time AIRNow ozone measurements through 2011 showed better performance of the operational ozone predictions. In this work, quality-controlled and -assured Air Quality System (AQS) ozone and nitrogen dioxide (NO2) observations are used to evaluate the experimental predictions in 2010. It is found that both ozone and NO2 are overestimated over the contiguous US (CONUS), with annual biases of +5.6 and +5.1 ppbv, respectively. The annual root mean square errors (RMSEs) are 15.4 ppbv for ozone and 13.4 ppbv for NO2. For both species the overpredictions are most pronounced in the summer. The locations of the AQS monitoring sites are also utilized to stratify comparisons by the degree of urbanization. Comparisons for six predefined US regions show the highest annual biases for ozone predictions in Southeast (+10.5 ppbv) and for NO2 in the Lower Middle (+8.1 ppbv) and Pacific Coast (+7.1 ppbv) regions. The spatial distributions of the NO2 biases in August show distinctively high values in the Los Angeles, Houston, and New Orleans areas. In addition to the standard statistics metrics, daily maximum eight-hour ozone categorical statistics are calculated using the current US ambient air quality standard (75 ppbv) and another lower threshold (70 ppbv). Using the 75 ppbv standard, the hit rate and proportion of correct over CONUS for the entire year are 0.64 and 0.96, respectively. Summertime biases show distinctive weekly patterns for ozone and NO2. Diurnal comparisons show that ozone overestimation is most severe in the morning, from 07:00 to 10:00 local time. For NO2, the morning predictions agree with the AQS observations reasonably well, but nighttime concentrations are overpredicted by around 100%.

Description: The importance of evaluating models through paleoclimate simulations is becoming more recognized in efforts to improve climate projection. To evaluate an integrated Earth System Model, MIROC-ESM, we performed simulations in time-slice experiments for the mid-Holocene (6000 yr before present, 6 ka) and preindustrial (1850 AD, 0 ka) periods under the protocol of the Coupled Model Intercomparison Project 5/Paleoclimate Modelling Intercomparison Project 3. We first give an overview of the simulated global climates by comparing with simulations using a previous version of the MIROC model (MIROC3), which is an atmosphere–ocean coupled general circulation model. We then comprehensively discuss various aspects of climate change with 6 ka forcing and how the differences in the models can affect the results. We also discuss the representation of the precipitation enhancement at 6 ka over northern Africa. The precipitation enhancement at 6 ka over northern Africa according to MIROC-ESM does not differ greatly from that obtained with MIROC3, which means that newly developed components such as dynamic vegetation and improvements in the atmospheric processes do not have significant impacts on the representation of the 6 ka monsoon change suggested by proxy records. Although there is no drastic difference between the African monsoon representations of the two models, there are small but significant differences in the precipitation enhancement over the Sahara in early summer, which can be related to the representation of the sea surface temperature rather than the vegetation coupling in MIROC-ESM. Because the oceanic parts of the two models are identical, the difference in the sea surface temperature change is ultimately attributed to the difference in the atmospheric and/or land modules, and possibly the difference in the representation of low-level clouds.

Description: The importance of evaluating models using paleoclimate simulations is becoming more recognized in efforts to improve climate projection. To evaluate an integrated Earth System Model, MIROC-ESM, we performed simulations in time-slice experiments for the mid-Holocene (6000 yr before present, 6 ka) and preindustrial (1850 AD) times under the protocol of the Coupled Model Intercomparison Project 5/Paleoclimate Modelling Intercomparison Project 3. We first overview the simulated global climates by comparing with simulations using a previous version of the MIROC model (MIROC3), which is an atmosphere-ocean coupled general circulation model, and then comprehensively discuss various aspects of climate change with 6 ka forcing. We also discuss the 6 ka African monsoon activity. The 6 ka precipitation change over northern Africa according to MIROC-ESM does not differ dramatically from that obtained with MIROC3, which means that newly developed components such as dynamic vegetation and improvements in the atmospheric processes do not have significant impacts on representing the 6 ka monsoon change suggested by proxy records. Although there is no drastic difference in the African monsoon representation between the two models, there are small but significant differences in the precipitation enhancement in MIROC-ESM, which can be related to the representation of the sea surface temperature rather than the vegetation coupling, at least in MIROC-ESM.