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Using boundary layer equilibrium to reduce uncertainties in transport models and CO2 flux inversions

This paper reexamines evidence for systematic errors in atmospheric transport models, in terms of the diagnostics used to infer vertical mixing rates from models and observations. Different diagnostics support different conclusions about transport model errors that could imply either stronger or weaker northern terrestrial carbon sinks. Conventional mixing diagnostics are compared to analyzed vertical mixing rates using data from the US Southern Great Plains Atmospheric Radiation Measurement Climate Research Facility, the CarbonTracker data assimilation system based on Transport Model version 5 (TM5), and atmospheric reanalyses. The results demonstrate that diagnostics based on boundary layer depth and vertical concentration gradients do not always indicate the vertical mixing strength. Vertical mixing rates are anti-correlated with boundary layer depth at some sites, diminishing in summer when the boundary layer is deepest. Boundary layer equilibrium concepts predict an inverse proportionality between CO2 vertical gradients and vertical mixing strength, such that previously reported discrepancies between observations and models most likely reflect overestimated as opposed to underestimated vertical mixing. However, errors in seasonal concentration gradients can also result from errors in modeled surface fluxes. This study proposes using the timescale for approach to boundary layer equilibrium to diagnose vertical mixing independently of seasonal surface fluxes, with applications to observations and model simulations of CO2 or other conserved boundary layer tracers with surface sources and sinks. Results indicate that frequently cited discrepancies between observations and inverse estimates do not provide sufficient proof of systematic errors in atmospheric transport models. Some previously hypothesized transport model biases, if found and corrected, could cause inverse estimates to further diverge from carbon inventory estimates of terrestrial sinks.
Studies of propane flame soot acting as heterogeneous ice nuclei in conjunction with single particle soot photometer measurements

The ice nucleation efficiency of propane flame soot particles with and without a sulphuric acid coating was investigated using the aerosol and cloud chamber facility AIDA (Aerosol Interaction and Dynamics in the Atmosphere). The test soot for cloud formation simulations was produced using a propane flame Combustion Aerosol Standard generator (CAST, Jing-CAST Technologies). The organic carbon content (OC) of the test soot was altered in a reproducible fashion by changing the fuel/air mixture of the generator. The soot content of ice nuclei was subsequently investigated using a combination of a pumped counterflow virtual impactor (PCVI) to separate and evaporate the ice crystals, and a DMT single particle soot photometer (SP2) to examine the mixing state of the BC containing ice residuals. Ice nucleation was found to be most efficient for uncoated soot of low organic carbon content (~5 % organic carbon content) where deposition freezing occurred at an ice saturation ratio Sice ~ 1.22 at a temperature T = 226.6 K with 25 % of the test soot becoming active as ice nuclei. Propane flame soot of higher organic carbon content (~30 % and ~70 % organic carbon content) showed significantly lower ice nucleation efficiency (an activated fraction of the order of a few percent in the experiments) than the low organic carbon content soot, with water saturation being required for freezing to occur. Ice nucleation occurred over the range Sice = 1.22–1.70, and T = 223.2–226.6 K. Analysis of the SP2 data showed that the 5 % organic carbon content soot had an undetectable OC coating whereas the 30 % organic carbon content soot had a thicker or less volatile OC coating. The application of a sulphuric acid coating to the flame soot shifted the threshold of the onset of freezing towards that of the homogeneous freezing of sulphuric acid; for the minimum OC flame soot this inhibited nucleation since the onset of freezing occurred at colder temperatures and required a greater ice saturation ratio; for the medium and maximum OC flame soot, the addition of a sulphuric acid significantly reduced the freezing threshold.
The size-dependent charge fraction of sub-3-nm particles as a key diagnostic of competitive nucleation mechanisms under atmospheric conditions

A clear physical understanding of atmospheric particle nucleation mechanisms is critical in assessing the influences of aerosols on climate and climate variability. Currently, several mechanisms have been proposed and are being employed to interpret field observations of nucleation events. Roughly speaking, the two most likely candidates are neutral cluster nucleation (NCN) and ion-mediated nucleation (IMN). Detailed nucleation event data has been obtained in boreal forests. In one set of analyses of these measurements, NCN was suggested as the dominant formation mode, while in another, it was IMN. Information on the electrical charge distribution carried by the nucleating clusters is one key for identifying the relative contributions of neutral and ion-mediated processes under various conditions. Fortunately, ground-breaking measurements of the charged states or fractions of ambient nanometer-sized particles soon after undergoing nucleation are now available to help resolve the main pathways. In the present study, the size-dependent "apparent" formation rates and fractions of charged and neutral particles in a boreal forest setting are simulated with a detailed kinetic model. We show that the predicted "apparent" formation rates of charged and neutral particles at 2 nm for eight representative case study days agree well with the corresponding values based on observations. In the simulations, the "apparent" contribution of ion-based nucleation increases by up to ~one order of magnitude as the size of "sampled" particles is decreased from 2 nm to ~1.5 nm. These results suggest that most of the neutral particles sampled in the field at sizes around 2 nm are in reality initially formed on ionic cores that are neutralized before the particles grow to this size. Thus, although the apparent rate of formation of neutral 2-nm particles might seem to be dominated by a neutral clustering process, in fact those particles may be largely the result of an ion-induced nucleation mechanism. This point is clarified when the formation rates of smaller particles (e.g., ~1.5 nm) are explicitly analyzed (noting that measurements at these smaller sizes are not yet available), indicating that IMN dominates NCN processes under typical circumstances in the boreal forest cases investigated.
Effect of the exclusion of crustal ions (Ca2+, Mg 2+, and K+) in estimating water content of PM2.5 at polluted and clean areas

Effect of the exclusion of crustal ions (Ca2+, Mg2+, and K+) in estimating water content of PM2.5 is investigated using a gas/aerosol equilibrium model, SCAPE 2 (Simulating Composition of Atmospheric Particles at Equilibrium 2), (Kim et al., 1993; Kim and Seinfeld, 1995; Meng et al., 1998), for the particles collected at polluted city, Seoul, and clean background offshore, Gosan, Korea. Measurement data show higher concentration of all inorganic species at Seoul, up to 5 times higher in average equivalent concentration especially for volatile species. At both sites there were sufficient equivalent fractions of t-NH3 (total ammonia = NH3+NH4+ to neutralize acidic species such as t-H2SO4 (total sulfuric acid = H2SO4+SO42−), t-HNO3 (total nitric acid = HNO3+NO3−) and t-HCl (total hydrochloric acid = HCl+Cl−). t-NH3 and t-HNO3 were higher at Seoul while t-H2SO4 was higher at Gosan. With respect to the estimated water content differences between with and without crustal ions, all the samples are classified into 3 cases; increased, decreased, and constant water content. We identified that change in inorganic composition contributes to increase of water content for aqueous aerosols. And those inorganic compositions vary differently according to ambient atmospheric composition. Meanwhile, aerosol phase shifting from the aqueous to solid phase is the main contributor to decrease of water content and binary salt composition change in the solid phase appears as no change of water content.
Formation of hydroxyl radical from San Joaquin Valley particles extracted in a cell-free surrogate lung fluid

Previous studies have suggested that the adverse health effects from ambient particulate matter (PM) are linked to the formation of reactive oxygen species (ROS) by PM in cardiopulmonary tissues. While hydroxyl radical (•OH) is the most reactive of the ROS species, there are few quantitative studies of •OH generation from PM. Here we report on •OH formation from PM collected at an urban (Fresno) and rural (Westside) site in the San Joaquin Valley (SJV) of California. We quantified •OH in PM extracts using a cell-free, phosphate-buffered saline (PBS) solution with or without 50 μM ascorbate (Asc). The results show that generally the urban Fresno PM generates much more •OH than the rural Westside PM. The presence of Asc at a physiologically relevant concentration in the extraction solution greatly enhances •OH formation from all the samples. Fine PM (PM2.5) generally makes more •OH than the corresponding coarse PM (PMcf, i.e. with diameters of 2.5 to 10 μm) normalized by air volume collected, while the coarse PM typically generates more •OH normalized by PM mass. •OH production by SJV PM is reduced on average by (97 ± 6) % when the transition metal chelator desferoxamine (DSF) is added to the extraction solution, indicating a dominant role of transition metals. By measuring calibration curves of •OH generation from copper and iron, and quantifying copper and iron concentrations in our particle extracts, we find that PBS-soluble copper is primarily responsible for •OH production by the SJV PM, while iron often makes a significant contribution. Extrapolating our results to expected burdens of PM-derived •OH in human lung lining fluid suggests that typical daily PM exposures in the San Joaquin Valley are unlikely to result in a high amount of pulmonary •OH, although high PM events could produce much higher levels of •OH, which might lead to cytotoxicity.
Overshooting of clean tropospheric air in the tropical lower stratosphere as seen by the CALIPSO lidar

The evolution of aerosols in the tropical upper troposphere/lower stratosphere between June 2006 and October 2009 is examined using the observations of the space borne CALIOP lidar aboard the CALIPSO satellite. Superimposed on several volcanic plumes and soot from an extreme biomass-burning event in 2009, the measurements reveal the existence of fast-cleansing episodes in the lower stratosphere to altitudes as high as 20 km. The cleansing of the layer, which extends from 14 to 20 km, takes place within 1 to 4 months during the southern tropics convective season that transports aerosol-poor tropospheric air into the lower stratosphere. In contrast, the convective season of the Northern Hemisphere summer shows an increase in the particle load at the tropopause consistent with a lofting of air rich with aerosols. These aerosols can consist of surface-derived material such as mineral dust and soot as well as liquid sulfate and organic particles. The flux of tropospheric air during the Southern Hemisphere convective season derived from CALIOP observations is shown to be 5 times at 16 km and 20 times at 19 km larger, respectively, than that associated with flux caused by slow ascent through radiative heating. These results suggest that convective overshooting is a major contributor to troposphere-to-stratosphere transport with concomitant implications for the Tropical Tropopause Layer top height, the humidity, the photochemistry and the thermal structure of the layer.
Correlation of black carbon aerosol and carbon monoxide in the high-altitude environment of Mt. Huang in Eastern China

Understanding the relationship between black carbon (BC) and carbon monoxide (CO) will help improve BC emission inventories and the evaluation of global/regional climate forcing effects. In the present work, the BC (PM1) mass concentration and CO mixing ratio were continuously measured at a high-altitude background station on the summit of Mt. Huang (30.16° N, 118.26° E, 1840 m a.s.l.). Annual mean BC mass concentration was 1004.5 ± 895.5 ng m−3 with maxima in spring and autumn, and annual mean CO mixing ratio was 424.1 ± 159.2 ppbv. A large increase of CO was observed in the cold season, implying the contribution from the large-scale domestic coal/biofuel combustion for heating. The BC-CO relationship was found to show different seasonal features but strong positive correlation (R>0.8). In Mt. Huang area, the ΔBC/ΔCO ratio showed unimodal diurnal variations and had a maximum during the day (09:00–17:00 LST) and minimum at night (21:00–04:00 LST) in all seasons, indicating the impact of planetary boundary layer and the intrusion of clean air masses from the high troposphere. Back trajectory cluster analysis showed that the ΔBC/ΔCO ratio of plumes from the Eastern China (Jiangsu, Zhejiang provinces and Shanghai) was 8.8 ± 0.9 ng m−3 ppbv−1. Transportation and industry were deemed as controlling factors of the BC-CO relationship in this region. The ΔBC/ΔCO ratios for air masses from Northern China (Anhui, Henan, Shanxi and Shandong provinces) and southern China (Jiangxi, Fujian and Hunan provinces) were quite similar with mean values of 6.5 ± 0.4 and 6.5 ± 0.2 ng m−3 ppbv−1 respectively. The case studies combined with satellite observations demonstrated that the ΔBC/ΔCO ratio for biomass burning (BB) plumes were 10.3 ± 0.3 and 11.6 ± 0.5ng m−3 ppbv−1, significantly higher than those during non-BB impacted periods. The loss of BC during transport was also investigated on the basis of the ΔBC/ΔCO-RH (relative humidity) relationship along air mass pathways. The results showed that BC particles from Eastern China area was much more easily removed from atmosphere than other inland regions due to the higher RH along transport pathway, implying the importance of chemical compositions and mixing states on BC residence time in the atmosphere.
Atmospheric ammonia measurements in Houston, TX using an external-cavity quantum cascade laser-based sensor

In order to improve the current understanding of the dynamics of ammonia (NH3) in a major industrial and urban area, intensive measurements of atmospheric NH3 were conducted in Houston during two sampling periods (12 February 2010–1 March 2010 and 5 August 2010–25 September 2010). The measurements were performed with a 10.4-μm external cavity quantum cascade laser (EC-QCL)-based sensor employing conventional photo-acoustic spectroscopy. The mixing ratio of NH3 ranged from 0.1 to 8.7 ppb with a mean of 2.4 ± 1.2 ppb in winter and ranged from 0.2 to 27.1 ppb with a mean of 3.1 ± 2.9 ppb in summer. The larger levels in summer probably are due to higher ambient temperature. A notable morning increase and a mid-day decrease were observed in the diurnal profile of NH3 mixing ratios. Motor vehicles were found to be major contributors to the elevated levels during morning rush hours in winter. However, changes in vehicular catalytic converter performance and other local or regional emission sources from different wind directions governed the behavior of NH3 during morning rush hours in summer. There was a large amount of variability, particularly in summer, with several episodes of elevated NH3 mixing ratios that could be linked to industrial facilities. A considerable discrepancy in NH3 mixing ratios existed between weekdays and weekends. This study suggests that NH3 mixing ratios in Houston occasionally exceeded previous modeling predictions when sporadic and substantial enhancements occurred, potentially causing profound effects on particulate matter formation and local air quality.
Modelling atmospheric OH-reactivity in a boreal forest ecosystem

We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined as well as the vertical OH-reactivity profile. We have used SOSA; a one dimensional vertical chemistry-transport model (Boy et al., 2011a) together with measurements from Hyytiälä, SMEAR II station, Southern Finland, conducted in August 2008. Model simulations only account for ~30–50% of the total measured OH sink, and in our opinion, the reason for missing OH-reactivity is due to unmeasured unknown BVOCs, and limitations in our knowledge of atmospheric chemistry including uncertainties in rate constants. Furthermore, we found that the OH-reactivity correlates with both organic and inorganic compounds and increases during summer. The summertime canopy level OH-reactivity peaks during night and the vertical OH-reactivity decreases with height.
A comprehensive numerical study of aerosol-cloud-precipitation interactions in marine stratocumulus

Three-dimensional large-eddy simulations (LES) with detailed bin-resolved microphysics are performed to explore the diurnal variation of marine stratocumulus (MSc) clouds under clean and polluted conditions. The sensitivity of the aerosol-cloud-precipitation interactions to variation of sea surface temperature, free tropospheric humidity, large-scale divergence rate, and wind speed is assessed. The comprehensive set of simulations corroborates previous studies that (1) with moderate/heavy drizzle, an increase in aerosol leads to an increase in cloud thickness; and (2) with non/light drizzle, an increase in aerosol results in a thinner cloud, due to the pronounced effect on entrainment. It is shown that for higher SST, stronger large-scale divergence, drier free troposphere, or lower wind speed, the cloud thins and precipitation decreases. The sign and magnitude of the Twomey effect, droplet dispersion effect, cloud thickness effect, and cloud optical depth susceptibility to aerosol perturbations (i.e., change in cloud optical depth to change in aerosol number concentration) are evaluated by LES experiments and compared with analytical formulations. The Twomey effect emerges as dominant in total cloud optical depth susceptibility to aerosol perturbations. The dispersion effect, that of aerosol perturbations on the cloud droplet size spectrum, is positive (i.e., increase in aerosol leads to spectral narrowing) and accounts for 3% to 10% of the total cloud optical depth susceptibility at nighttime, with greater influence in heavier drizzling clouds. The cloud thickness effect is negative (i.e., increase in aerosol leads to thinner cloud) for non/light drizzling cloud and positive for a moderate/heavy drizzling clouds; the cloud thickness effect contributes 5% to 22% of the nighttime total cloud susceptibility. Overall, the total cloud optical depth susceptibility ranges from ~0.28 to 0.53 at night; an increase in aerosol concentration enhances cloud optical depth, especially with heavier precipitation and in a more pristine environment. During the daytime, the range of magnitude for each effect is more variable owing to cloud thinning and decoupling. The good agreement between LES experiments and analytical formulations suggests that the latter may be useful in evaluations of the total cloud susceptibility. The ratio of the magnitude of the cloud thickness effect to that of the Twomey effect depends on cloud base height and cloud thickness in unperturbed (clean) clouds.