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A chamber study of the influence of boreal BVOC emissions and sulfuric acid on nanoparticle formation rates at ambient concentrations

Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Jülich plant–atmosphere simulation chamber with instrumentation for the detection of sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulfuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.
High-resolution ammonia emissions inventories in China from 1980 to 2012

Ammonia (NH3) can interact in the atmosphere with other trace chemical species, which can lead to detrimental environmental consequences, such as the formation of fine particulates and ultimately global climate change. China is a major agricultural country, and livestock numbers and nitrogen fertilizer use have increased drastically since 1978, following the rapid economic and industrial development experienced by the country. In this study, comprehensive NH3 emissions inventories were compiled for China for 1980–2012. In a previous study, we parameterized emissions factors (EFs) considering ambient temperature, soil acidity, and the method and rate of fertilizer application. In this study, we refined these EFs by adding the effects of wind speed and new data from field experiments of NH3 flux in cropland in northern China. We found that total NH3 emissions in China increased from 5.9 to 11.1 Tg from 1980 to 1996, and then decreased to 9.7 Tg in 2012. The two major contributors were livestock manure and synthetic fertilizer application, which contributed 80–90 % of the total emissions. Emissions from livestock manure rose from 2.86 Tg (1980) to 6.16 Tg (2005), and then decreased to 5.0 Tg (2012); beef cattle were the largest source followed by laying hens and pigs. The remarkable downward trend in livestock emissions that occurred in 2007 was attributed to a decrease in the numbers of various livestock animals, including beef cattle, goats, and sheep. Meanwhile, emissions from synthetic fertilizer ranged from 2.1 Tg (1980) to 4.7 Tg (1996), and then declined to 2.8 Tg (2012). Urea and ammonium bicarbonate (ABC) dominated this category of emissions, and a decline in ABC application led to the decrease in emissions that took place from the mid-1990s onwards. High emissions were concentrated in eastern and southwestern China. Seasonally, peak NH3 emissions occurred in spring and summer. The inventories had a monthly temporal resolution and a spatial resolution of 1000 m, and thus are suitable for global and regional air-quality modeling.
On the progress of the 2015–2016 El Niño event

It has been recently reported that the current 2015–2016 El Niño could become "one of the strongest on record". To further explore this claim, we performed the new analysis described in detail in Varotsos et al. (2015) that allows the detection of precursory signals of the strong El Niño events by using a recently developed non-linear dynamics tool. In this context, the analysis of the Southern Oscillation Index time series for the period 1876–2015 shows that the running 2015–2016 El Niño would be rather a "moderate to strong" or even a "strong" event and not “one of the strongest on record", as that of 1997–1998.
Volatility of organic aerosol and its components in the megacity of Paris

Using a mass transfer model and the volatility basis set, we estimate the volatility distribution for the organic aerosol (OA) components during summer and winter in Paris, France as part of the collaborative project MEGAPOLI. The concentrations of the OA components as a function of temperature were measured combining data from a thermodenuder and an aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. The hydrocarbon-like organic aerosol (HOA) had similar volatility distributions for the summer and winter campaigns with half of the material in the saturation concentration bin of 10 µg m−3 and another 35–40 % consisting of low and extremely low volatility organic compounds (LVOCs with effective saturation concentrations C* of 10−3–0.1 µg m−3 and ELVOCs C* less or equal than 10−4 µg m−3, respectively). The winter cooking OA (COA) was more than an order of magnitude less volatile than the summer COA. The low-volatility oxygenated OA (LV-OOA) factor detected in the summer had the lowest volatility of all the derived factors and consisted almost exclusively of ELVOCs. The volatility for the semi-volatile oxygenated OA (SV-OOA) was significantly higher than that of the LV-OOA, containing both semi-volatile organic components (SVOCs with C* in the 1–100 µg m−3 range) and LVOCs. The oxygenated OA (OOA) factor in winter consisted of SVOCs (45 %), LVOCs (25 %) and ELVOCs (30 %). The volatility of marine OA (MOA) was higher than that of the other factors containing around 60 % SVOCs. The biomass burning OA (BBOA) factor contained components with a wide range of volatilities with significant contributions from both SVOCs (50 %) and LVOCs (30 %). Finally, combining the bulk average O : C ratios and volatility distributions of the various factors, our results are placed into the two-dimensional volatility basis set (2D-VBS) framework. The OA factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O : C of the OA components.
Speciation of 127I and 129I in atmospheric aerosols at Risø, Denmark: insight into sources of iodine isotopes and their species transformations

Speciation analysis of iodine in aerosols is a very useful approach for understanding geochemical cycling of iodine in the atmosphere. In this study, overall iodine species, including water-soluble iodine species (iodide, iodate and water-soluble organic iodine), NaOH-soluble iodine, and insoluble iodine have been determined for 129I and 127I in the aerosols collected at Risø, Denmark, during March and May 2011 (shortly after the Fukushima nuclear accident) and in December 2014. The measured concentrations of total iodine are in the range of 1.04–2.48 ng m−3 for 127I and (11.3–97.0)  ×  105 atoms m−3 for 129I, corresponding to 129I ∕ 127I atomic ratios of (17.8–86.8)  ×  10−8. The contribution of Fukushima-derived 129I (peak value of 6.3  ×  104 atoms m−3) is estimated to be negligible (less than 6 %) compared to the total 129I concentration in northern Europe. The concentrations and species of 129I and 127I in the aerosols are found to be strongly related to their sources and atmospheric pathways. Aerosols that were transported over the contaminated seas contained higher concentrations of 129I than aerosols transported over the European continent. The high 129I concentrations of the marine aerosols are attributed to secondary emission of marine discharged 129I in the contaminated seawater in the North Sea, North Atlantic Ocean, English Channel, Kattegat, etc., rather than direct gaseous release from the European nuclear reprocessing plants (NRPs). Water-soluble iodine was found to be a minor fraction to the total iodine for both 127I (7.8–13.7 %) and 129I (6.5–14.1 %) in ocean-derived aerosols, but accounted for 20.2–30.3 % for 127I and 25.6–29.5 % for 129I in land-derived aerosols. Iodide was the predominant form of water-soluble iodine, accounting for more than 97 % of the water-soluble iodine. NaOH-soluble iodine seems to be independent of the sources of aerosols. The significant proportion of 129I and 127I found in NaOH-soluble fractions is likely bound with organic substances. In contrast to water-soluble iodine, the sources of air masses exerted distinct influences on insoluble iodine for both 129I and 127I, with higher values for marine air masses and lower values for terrestrial air masses.
Utilization of O4 slant column density to derive aerosol layer height from a space-borne UV–visible hyperspectral sensor: sensitivity and case study

The sensitivities of oxygen-dimer (O4) slant column densities (SCDs) to changes in aerosol layer height are investigated using the simulated radiances by a radiative transfer model, the linearized pseudo-spherical vector discrete ordinate radiative transfer (VLIDORT), and the differential optical absorption spectroscopy (DOAS) technique. The sensitivities of the O4 index (O4I), which is defined as dividing O4 SCD by 1040 molecules2 cm−5, to aerosol types and optical properties are also evaluated and compared. Among the O4 absorption bands at 340, 360, 380, and 477 nm, the O4 absorption band at 477 nm is found to be the most suitable to retrieve the aerosol effective height. However, the O4I at 477 nm is significantly influenced not only by the aerosol layer effective height but also by aerosol vertical profiles, optical properties including single scattering albedo (SSA), aerosol optical depth (AOD), particle size, and surface albedo. Overall, the error of the retrieved aerosol effective height is estimated to be 1276, 846, and 739 m for dust, non-absorbing, and absorbing aerosol, respectively, assuming knowledge on the aerosol vertical distribution shape. Using radiance data from the Ozone Monitoring Instrument (OMI), a new algorithm is developed to derive the aerosol effective height over East Asia after the determination of the aerosol type and AOD from the MODerate resolution Imaging Spectroradiometer (MODIS). About 80 % of retrieved aerosol effective heights are within the error range of 1 km compared to those obtained from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) measurements on thick aerosol layer cases.
Secondary formation of nitrated phenols: insights from observations during the Uintah Basin Winter Ozone Study (UBWOS) 2014

We describe the results from online measurements of nitrated phenols using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with acetate as reagent ion in an oil and gas production region in January and February of 2014. Strong diurnal profiles were observed for nitrated phenols, with concentration maxima at night. Based on known markers (CH4, NOx, CO2), primary emissions of nitrated phenols were not important in this study. A box model was used to simulate secondary formation of phenol, nitrophenol (NP), and dinitrophenols (DNP). The box model results indicate that oxidation of aromatics in the gas phase can explain the observed concentrations of NP and DNP in this study. Photolysis was the most efficient loss pathway for NP in the gas phase. We show that aqueous-phase reactions and heterogeneous reactions were minor sources of nitrated phenols in our study. This study demonstrates that the emergence of new ToF-CIMS (including PTR-TOF) techniques allows for the measurement of intermediate oxygenates at low levels and these measurements improve our understanding on the evolution of primary VOCs in the atmosphere.
Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimental data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, Ntot, and the heterogeneous ice nucleation rate coefficient, Jhet(T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of Jhet is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. The model simulations allow for a quantitative experimental uncertainty analysis for parameters Ntot, T, RH, and the ISA variability. The implications of our results for experimental analysis and interpretation of the immersion freezing process are discussed.
Properties of young contrails – a parametrisation based on large-eddy simulations

Contrail–cirrus is probably the largest climate forcing from aviation. The evolution of contrail–cirrus and its radiative impact depends not only on a multitude of atmospheric parameters, but also on the geometric and microphysical properties of the young contrails evolving into contrail–cirrus. The early evolution of contrails (t <  5 min) is dominated by an interplay of ice microphysics and wake vortex dynamics. Young contrails may undergo a fast vertical expansion due to a descent of the wake vortices and may lose a substantial fraction of their ice crystals due to adiabatic heating. The geometric depth H and total ice crystal number N of young contrails are highly variable and depend on many environmental and aircraft parameters. Both properties, H and N, affect the later properties of the evolving contrail–cirrus, as they control the extent of shear-induced spreading and sedimentation losses. In this study, we provide parametrisations of H and N after 5 min taking into account the effects of temperature, relative humidity, thermal stratification and aircraft type (mass, wing span, fuel burn). The parametrisations rely on a large data set of recent large-eddy simulations of young contrails. They are suited to be incorporated in larger-scale models in order to refine the present-day contrail initialisations by considering the processes that strongly affect the contrail evolution during the vortex phase.
On the vertical distribution of smoke in the Amazonian atmosphere during the dry season

Lidar observations of smoke aerosols have been analysed from six flights of the Facility for Airborne Atmospheric Measurements BAe-146 research aircraft over Brazil during the biomass burning season (September 2012). A large aerosol optical depth (AOD) was observed, typically ranging 0.4–0.9, along with a typical aerosol extinction coefficient of 100–400 Mm−1. The data highlight the persistent and widespread nature of the Amazonian haze, which had a consistent vertical structure, observed over a large distance ( ∼ 2200 km) during a period of 14 days. Aerosols were found near the surface; but the larger aerosol load was typically found in elevated layers that extended from 1–1.5 to 4–6 km. The measurements have been compared to model predictions with the Met Office Unified Model (MetUM) and the ECMWF-MACC model. The MetUM generally reproduced the vertical structure of the Amazonian haze observed with the lidar. The ECMWF-MACC model was also able to reproduce the general features of smoke plumes albeit with a small overestimation of the AOD. The models did not always capture localised features such as (i) smoke plumes originating from individual fires, and (ii) aerosols in the vicinity of clouds. In both these circumstances, peak extinction coefficients of the order of 1000–1500 Mm−1 and AODs as large as 1–1.8 were encountered, but these features were either underestimated or not captured in the model predictions. Smoke injection heights derived from the Global Fire Assimilation System (GFAS) for the region are compatible with the general height of the aerosol layers.