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Insights into a historic severe haze event in Shanghai: synoptic situation, boundary layer and pollutants

A historic haze event, characterized by lengthy, large-scale and severe pollution, occurred in the Yangtze River Delta (YRD) of China from 1 to 10 December 2013. This haze event significantly influenced air quality throughout the region, especially in urban areas. Aerosol physical, chemical and optical properties were measured in Shanghai. Sometimes the 1 h average particle concentration (e.g., PM2.5) exceeded 600 µg m−3. Inorganic water-soluble ions in particles, trace gases and aerosol optical coefficients had a similar tendency to increase evidently from clear to hazy episodes. A combination of various factors contributed to the formation and evolution of the haze event, among which meteorological conditions, local anthropogenic emissions and pollutants are the major factors. High pressure system, calm surface wind and subsidence airflow were responsible for the decrease of planetary boundary layer (PBL) and the accumulation of pollutants. Atmospheric visibility correlated strongly with relative humidity (RH), particle number in size of 600–1400 nm other than particulate water-soluble species and particle mass (PM2.5). The particle hygroscopicity plays an important role in atmospheric visibility reduction. The results are somewhat helpful to forecast and eliminate regional atmospheric pollution in China.
Adjusting particle-size distributions to account for aggregation in tephra-deposit model forecasts

Volcanic ash transport and dispersion (VATD) models are used to forecast tephra deposition during volcanic eruptions. Model accuracy is limited by the fact that fine-ash aggregates (clumps into clusters), thus altering patterns of deposition. In most models this is accounted for by ad hoc changes to model input, representing fine ash as aggregates with density ρagg, and a log-normal size distribution with median μagg and standard deviation σagg. Optimal values may vary between eruptions. To test the variance, we used the Ash3d tephra model to simulate four deposits: 18 May 1980 Mount St. Helens; 16–17 September 1992 Crater Peak (Mount Spurr); 17 June 1996 Ruapehu; and 23 March 2009 Mount Redoubt. In 192 simulations, we systematically varied μagg and σagg, holding ρagg constant at 600 kg m−3. We evaluated the fit using three indices that compare modeled versus measured (1) mass load at sample locations; (2) mass load versus distance along the dispersal axis; and (3) isomass area. For all deposits, under these inputs, the best-fit value of μagg ranged narrowly between ∼  2.3 and 2.7φ (0.20–0.15 mm), despite large variations in erupted mass (0.25–50 Tg), plume height (8.5–25 km), mass fraction of fine ( <  0.063 mm) ash (3–59 %), atmospheric temperature, and water content between these eruptions. This close agreement suggests that aggregation may be treated as a discrete process that is insensitive to eruptive style or magnitude. This result offers the potential for a simple, computationally efficient parameterization scheme for use in operational model forecasts. Further research may indicate whether this narrow range also reflects physical constraints on processes in the evolving cloud.
Theoretical analysis of mixing in liquid clouds – Part 3: Inhomogeneous mixing

An idealized diffusion–evaporation model of time-dependent mixing between a cloud volume and a droplet-free volume is analyzed. The initial droplet size distribution (DSD) in the cloud volume is assumed to be monodisperse. It is shown that evolution of the microphysical variables and the final equilibrium state are unambiguously determined by two non-dimensional parameters. The first one is the potential evaporation parameter R, proportional to the ratio of the saturation deficit to the liquid water content in the cloud volume, that determines whether the equilibrium state is reached at 100 % relative humidity, or is characterized by a complete evaporation of cloud droplets. The second parameter Da is the Damkölher number equal to the ratio of the characteristic mixing time to the phase relaxation time. Parameters R and Da determine the type of mixing. The results are analyzed within a wide range of values of R and Da. It is shown that there is no pure homogeneous mixing, since the first mixing stage is always inhomogeneous. The mixing type can change during the mixing process. Any mixing type leads to formation of a tail of small droplets in DSD and, therefore, to DSD broadening that depends on Da. At large Da, the final DSD dispersion can be as large as 0.2. The total duration of mixing varies from several to 100 phase relaxation time periods, depending on R and Da. The definitions of homogeneous and inhomogeneous types of mixing are reconsidered and clarified, enabling a more precise delimitation between them. The paper also compares the results obtained with those based on the classic mixing concepts. >
Theoretical investigation of mixing in warm clouds – Part 2: Homogeneous mixing

Evolution of monodisperse and polydisperse droplet size distributions (DSD) during homogeneous mixing is analyzed. Time-dependent universal analytical expressions for supersaturation and liquid water content are derived. For an initial monodisperse DSD, these quantities are shown to depend on a sole non-dimensional parameter. The evolution of moments and moment-related functions in the course of homogeneous evaporation of polydisperse DSD is analyzed using a parcel model. It is shown that the classic conceptual scheme, according to which homogeneous mixing leads to a decrease in droplet mass at constant droplet concentration, is valid only in cases of monodisperse or initially very narrow polydisperse DSD. In cases of wide polydisperse DSD, mixing and successive evaporation lead to a decrease of both mass and concentration, so the characteristic droplet sizes remain nearly constant. As this feature is typically associated with inhomogeneous mixing, we conclude that in cases of an initially wide DSD at cloud top, homogeneous mixing is nearly indistinguishable from inhomogeneous mixing.
Multiple new-particle growth pathways observed at the US DOE Southern Great Plains field site

New-particle formation (NPF) is a significant source of aerosol particles into the atmosphere. However, these particles are initially too small to have climatic importance and must grow, primarily through net uptake of low-volatility species, from diameters ∼  1 to 30–100 nm in order to potentially impact climate. There are currently uncertainties in the physical and chemical processes associated with the growth of these freshly formed particles that lead to uncertainties in aerosol-climate modeling. Four main pathways for new-particle growth have been identified: condensation of sulfuric-acid vapor (and associated bases when available), condensation of organic vapors, uptake of organic acids through acid–base chemistry in the particle phase, and accretion of organic molecules in the particle phase to create a lower-volatility compound that then contributes to the aerosol mass. The relative importance of each pathway is uncertain and is the focus of this work. The 2013 New Particle Formation Study (NPFS) measurement campaign took place at the DOE Southern Great Plains (SGP) facility in Lamont, Oklahoma, during spring 2013. Measured gas- and particle-phase compositions during these new-particle growth events suggest three distinct growth pathways: (1) growth by primarily organics, (2) growth by primarily sulfuric acid and ammonia, and (3) growth by primarily sulfuric acid and associated bases and organics. To supplement the measurements, we used the particle growth model MABNAG (Model for Acid–Base chemistry in NAnoparticle Growth) to gain further insight into the growth processes on these 3 days at SGP. MABNAG simulates growth from (1) sulfuric-acid condensation (and subsequent salt formation with ammonia or amines), (2) near-irreversible condensation from nonreactive extremely low-volatility organic compounds (ELVOCs), and (3) organic-acid condensation and subsequent salt formation with ammonia or amines. MABNAG is able to corroborate the observed differing growth pathways, while also predicting that ELVOCs contribute more to growth than organic salt formation. However, most MABNAG model simulations tend to underpredict the observed growth rates between 10 and 20 nm in diameter; this underprediction may come from neglecting the contributions to growth from semi-to-low-volatility species or accretion reactions. Our results suggest that in addition to sulfuric acid, ELVOCs are also very important for growth in this rural setting. We discuss the limitations of our study that arise from not accounting for semi- and low-volatility organics, as well as nitrogen-containing species beyond ammonia and amines in the model. Quantitatively understanding the overall budget, evolution, and thermodynamic properties of lower-volatility organics in the atmosphere will be essential for improving global aerosol models.
Influence of seed aerosol surface area and oxidation rate on vapor wall deposition and SOA mass yields: a case study with α-pinene ozonolysis

Laboratory chambers, invaluable in atmospheric chemistry and aerosol formation studies, are subject to particle and vapor wall deposition, processes that need to be accounted for in order to accurately determine secondary organic aerosol (SOA) mass yields. Although particle wall deposition is reasonably well understood and usually accounted for, vapor wall deposition is less so. The effects of vapor wall deposition on SOA mass yields in chamber experiments can be constrained experimentally by increasing the seed aerosol surface area to promote the preferential condensation of SOA-forming vapors onto seed aerosol. Here, we study the influence of seed aerosol surface area and oxidation rate on SOA formation in α-pinene ozonolysis. The observations are analyzed using a coupled vapor–particle dynamics model to interpret the roles of gas–particle partitioning (quasi-equilibrium vs. kinetically limited SOA growth) and α-pinene oxidation rate in influencing vapor wall deposition. We find that the SOA growth rate and mass yields are independent of seed surface area within the range of seed surface area concentrations used in this study. This behavior arises when the condensation of SOA-forming vapors is dominated by quasi-equilibrium growth. Faster α-pinene oxidation rates and higher SOA mass yields are observed at increasing O3 concentrations for the same initial α-pinene concentration. When the α-pinene oxidation rate increases relative to vapor wall deposition, rapidly produced SOA-forming oxidation products condense more readily onto seed aerosol particles, resulting in higher SOA mass yields. Our results indicate that the extent to which vapor wall deposition affects SOA mass yields depends on the particular volatility organic compound system and can be mitigated through the use of excess oxidant concentrations.
Theoretical study of mixing in liquid clouds – Part 1: Classical concepts

The present study considers final stages of in-cloud mixing in the framework of classical concept of homogeneous and extreme inhomogeneous mixing. Simple analytical relationships between basic microphysical parameters were obtained for homogeneous and extreme inhomogeneous mixing based on the adiabatic consideration. It was demonstrated that during homogeneous mixing the functional relationships between the moments of the droplets size distribution hold only during the primary stage of mixing. Subsequent random mixing between already mixed parcels and undiluted cloud parcels breaks these relationships. However, during extreme inhomogeneous mixing the functional relationships between the microphysical parameters hold both for primary and subsequent mixing. The obtained relationships can be used to identify the type of mixing from in situ observations. The effectiveness of the developed method was demonstrated using in situ data collected in convective clouds. It was found that for the specific set of in situ measurements the interaction between cloudy and entrained environments was dominated by extreme inhomogeneous mixing.
Tropospheric ozone seasonal and long-term variability as seen by lidar and surface measurements at the JPL-Table Mountain Facility, California

A combined surface and tropospheric ozone climatology and interannual variability study was performed for the first time using co-located ozone photometer measurements (2013–2015) and tropospheric ozone differential absorption lidar measurements (2000–2015) at the Jet Propulsion Laboratory Table Mountain Facility (TMF; elev. 2285 m), in California. The surface time series were investigated both in terms of seasonal and diurnal variability. The observed surface ozone is typical of high-elevation remote sites, with small amplitude of the seasonal and diurnal cycles, and high ozone values, compared to neighboring lower altitude stations representative of urban boundary layer conditions. The ozone mixing ratio ranges from 45 ppbv in the winter morning hours to 65 ppbv in the spring and summer afternoon hours. At the time of the lidar measurements (early night), the seasonal cycle observed at the surface is similar to that observed by lidar between 3.5 and 9 km. Above 9 km, the local tropopause height variation with time and season impacts significantly the ozone lidar observations. The frequent tropopause folds found in the vicinity of TMF (27 % of the time, mostly in winter and spring) produce a dual-peak vertical structure in ozone within the fold layer, characterized by higher-than-average values in the bottom half of the fold (12–14 km), and lower-than-averaged values in the top half of the fold (14–18 km). This structure is consistent with the expected origin of the air parcels within the fold, i.e., mid-latitude stratospheric air folding down below the upper tropospheric sub-tropical air. The influence of the tropopause folds extends down to 5 km, increasing the ozone content in the troposphere. No significant signature of interannual variability could be observed on the 2000–2015 de-seasonalized lidar time series, with only a statistically non-significant positive anomaly during the years 2003–2007. Our trend analysis reveals however an overall statistically significant positive trend of 0.3 ppbv year−1 (0.6 %) in the free troposphere (7–10 km) for the period 2000–2015. A classification of the air parcels sampled by lidar was made at 1 km intervals between 5 and 14 km altitude, using 12-day backward trajectories (HYSPLIT, Hybrid Single Particle Lagrangian Integrated Trajectory Model). Our classification revealed the influence of the Pacific Ocean, with air parcels of low ozone content (43–60 ppbv below 9 km), and significant influence of the stratosphere leading to ozone values of 57–83 ppbv down to 8–9 km. In summer, enhanced ozone values (76 ppbv at 9 km) were found in air parcels originating from Central America, probably due to the enhanced thunderstorm activity during the North American Monsoon. Influence from Asia was observed throughout the year, with more frequent episodes during spring, associated with ozone values from 53 to 63 ppbv at 9 km.
Speciation of OH reactivity above the canopy of an isoprene-dominated forest

Measurements of OH reactivity, the inverse lifetime of the OH radical, can provide a top–down estimate of the total amount of reactive carbon in an air mass. Using a comprehensive measurement suite, we examine the measured and modeled OH reactivity above an isoprene-dominated forest in the southeast United States during the 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign. Measured and modeled species account for the vast majority of average daytime reactivity (80–95 %) and a smaller portion of nighttime and early morning reactivity (68–80 %). The largest contribution to total reactivity consistently comes from primary biogenic emissions, with isoprene contributing ∼  60 % in the afternoon, and ∼  30–40 % at night and monoterpenes contributing ∼  15–25 % at night. By comparing total reactivity to the reactivity stemming from isoprene alone, we find that ∼  20 % of the discrepancy is temporally related to isoprene reactivity, and an additional constant ∼  1 s−1 offset accounts for the remaining portion. The model typically overestimates measured OVOC concentrations, indicating that unmeasured oxidation products are unlikely to influence measured OH reactivity. Instead, we suggest that unmeasured primary emissions may influence the OH reactivity at this site.
Estimation of the advection effects induced by surface heterogeneities in the surface energy budget

The effect of terrain heterogeneities in one-point measurements is a continuous subject of discussion. Here we focus on the order of magnitude of the advection term in the equation of the evolution of temperature as generated by documented terrain heterogeneities and we estimate its importance as a term in the surface energy budget (SEB), for which the turbulent fluxes are computed using the eddy-correlation method. The heterogeneities are estimated from satellite and model fields for scales near 1 km or broader, while the smaller scales are estimated through direct measurements with remotely piloted aircraft and thermal cameras and also by high-resolution modelling. The variability of the surface temperature fields is not found to decrease clearly with increasing resolution, and consequently the advection term becomes more important as the scales become finer. The advection term provides non-significant values to the SEB at scales larger than a few kilometres. In contrast, surface heterogeneities at the metre scale yield large values of the advection, which are probably only significant in the first centimetres above the ground. The motions that seem to contribute significantly to the advection term in the SEB equation in our case are roughly those around the hectometre scales.