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Particle formation rates are usually measured at sizes larger than the critical size at which nucleation occurs. Due to loss of particles during their growth to the detection threshold, the measured formation rate is often substantially lower than the nucleation rate. For this reason a correction needs to be applied in order to determine the nucleation rate from the measured formation rate. Analytical formulae for the correction factor are provided in the literature. However, these methods were derived for atmospheric nucleation measurements and therefore need to be adjusted in order to be applied to chamber nucleation studies. Here we propose an alternative, numerical method that allows precise nucleation rates to be determined in arbitrary experimental environments. The method requires knowledge of the particle size distribution above detection threshold, the particle growth rate, and the particle loss rates as a function of particle size. The effect of self-coagulation, i.e., cluster–cluster collisions, is taken into account in the method.
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Cloud glaciation is critically important for the global radiation budget (albedo) and for initiation of precipitation. But the freezing of pure water droplets requires cooling to temperatures as low as 235 K. Freezing at higher temperatures requires the presence of an ice nucleator, which serves as a template for arranging water molecules in an ice-like manner. It is often assumed that these ice nucleators have to be insoluble particles. We point out that also free macromolecules which are dissolved in water can efficiently induce ice nucleation: the size of such ice nucleating macromolecules (INMs) is in the range of nanometers, corresponding to the size of the critical ice embryo. As the latter is temperature-dependent, we see a correlation between the size of INMs and the ice nucleation temperature as predicted by classical nucleation theory. Different types of INMs have been found in a wide range of biological species and comprise a variety of chemical structures including proteins, saccharides, and lipids. Our investigation of the fungal species <i>Acremonium implicatum</i>, <i>Isaria farinosa</i>, and <i>Mortierella alpina</i> shows that their ice nucleation activity is caused by proteinaceous water-soluble INMs. We combine these new results and literature data on INMs from fungi, bacteria, and pollen with theoretical calculations to develop a chemical interpretation of ice nucleation and water-soluble INMs. This has atmospheric implications since many of these INMs can be released by fragmentation of the carrier cell and subsequently may be distributed independently. Up to now, this process has not been accounted for in atmospheric models.
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A green light sensor has been developed at KNMI to measure actinic flux profiles using an ozonesonde balloon. In total, 63 launches with ascending and descending profiles were performed between 2006 and 2010. The measured uncalibrated actinic flux profiles are analysed using the Doubling–Adding KNMI (DAK) radiative transfer model. Values of the cloud optical thickness (COT) along the flight track were taken from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) Cloud Physical Properties (CPP) product. The impact of clouds on the actinic flux profile is evaluated on the basis of the cloud modification factor (CMF) at the cloud top and cloud base, which is the ratio between the actinic fluxes for cloudy and clear-sky scenes. The impact of clouds on the actinic flux is clearly detected: the largest enhancement occurs at the cloud top due to multiple scattering. The actinic flux decreases almost linearly from cloud top to cloud base. Above the cloud top the actinic flux also increases compared to clear-sky scenes. We find that clouds can increase the actinic flux to 2.3 times the clear-sky value at cloud top and decrease it to about 0.05 at cloud base. The relationship between CMF and COT agrees well with DAK simulations, except for a few outliers. Good agreement is found between the DAK-simulated actinic flux profiles and the observations for single-layer clouds in fully overcast scenes. The instrument is suitable for operational balloon measurements because of its simplicity and low cost. It is worth further developing the instrument and launching it together with atmospheric chemistry composition sensors.
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Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain an abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactors (MOUDIs). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second-longest freeway tunnel (12.9 km) in Asia. This endeavor aims to characterize the chemical constituents and size distributions, as well as fingerprinting ratios of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups – namely, tailpipe emissions (Zn, Pb, and V in fine mode), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb) – of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM<sub>1–10</sub>). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios – including Fe / Cu (14), Ba / Cu (1.05), Sb / Cu (0.16), Sn / Cu (0.10), and Ga / Cu (0.03) – served as fingerprints for wear debris. However, the data set collected in this work is useful for further studies on traffic emission inventory and human health effects of traffic-related PM.
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This paper describes the atmospheric modeling that underlies the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) science analysis, including its meteorological and atmospheric transport components (polar variant of the Weather Research and Forecasting (WRF) and Stochastic Time Inverted Lagrangian Transport (STILT) models), and provides WRF validation for May–October 2012 and March–November 2013 – the first 2 years of the aircraft field campaign. A triply nested computational domain for WRF was chosen so that the innermost domain with 3.3 km grid spacing encompasses the entire mainland of Alaska and enables the substantial orography of the state to be represented by the underlying high-resolution topographic input field. Summary statistics of the WRF model performance on the 3.3 km grid indicate good overall agreement with quality-controlled surface and radiosonde observations. Two-meter temperatures are generally too cold by approximately 1.4 K in 2012 and 1.1 K in 2013, while 2 m dewpoint temperatures are too low (dry) by 0.2 K in 2012 and too high (moist) by 0.6 K in 2013. Wind speeds are biased too low by 0.2 m s<sup>−1</sup> in 2012 and 0.3 m s<sup>−1</sup> in 2013. Model representation of upper level variables is very good. These measures are comparable to model performance metrics of similar model configurations found in the literature. The high quality of these fine-resolution WRF meteorological fields inspires confidence in their use to drive STILT for the purpose of computing surface influences ("footprints") at commensurably increased resolution. Indeed, footprints generated on a 0.1° grid show increased spatial detail compared with those on the more common 0.5° grid, better allowing for convolution with flux models for carbon dioxide and methane across the heterogeneous Alaskan landscape. Ozone deposition rates computed using STILT footprints indicate good agreement with observations and exhibit realistic seasonal variability, further indicating that WRF-STILT footprints are of high quality and will support accurate estimates of CO<sub>2</sub> and CH<sub>4</sub> surface–atmosphere fluxes using CARVE observations.
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This study presents the difference between oxidised organic compounds formed by α-pinene oxidation under various conditions in the CLOUD environmental chamber: (1) pure ozonolysis (in the presence of hydrogen as hydroxyl radical (OH) scavenger) and (2) OH oxidation (initiated by nitrous acid (HONO) photolysis by ultraviolet light) in the absence of ozone. <br><br> We discuss results from three Atmospheric Pressure interface Time-of-Flight (APi-TOF) mass spectrometers measuring simultaneously the composition of naturally charged as well as neutral species (via chemical ionisation with nitrate). Natural chemical ionisation takes place in the CLOUD chamber and organic oxidised compounds form clusters with nitrate, bisulfate, bisulfate/sulfuric acid clusters, ammonium, and dimethylaminium, or get protonated. The results from this study show that this process is selective for various oxidised organic compounds with low molar mass and ions, so that in order to obtain a comprehensive picture of the elemental composition of oxidation products and their clustering behaviour, several instruments must be used. We compare oxidation products containing 10 and 20 carbon atoms and show that highly oxidised organic compounds are formed in the early stages of the oxidation.
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In the present work, three different techniques to separate ice-nucleating particles (INPs) as well as ice particle residuals (IPRs) from non-ice-active particles are compared. The Ice Selective Inlet (ISI) and the Ice Counterflow Virtual Impactor (Ice-CVI) sample ice particles from mixed-phase clouds and allow after evaporation in the instrument for the analysis of the residuals. The Fast Ice Nucleus Chamber (FINCH) coupled with the Ice Nuclei Pumped Counterflow Virtual Impactor (IN-PCVI) provides ice-activating conditions to aerosol particles and extracts the activated particles for analysis. The instruments were run during a joint field campaign which took place in January and February 2013 at the High Alpine Research Station Jungfraujoch (Switzerland). INPs and IPRs were analyzed offline by scanning electron microscopy and energy-dispersive X-ray microanalysis to determine their size, chemical composition and mixing state. Online analysis of the size and chemical composition of INP activated in FINCH was performed by laser ablation mass spectrometry. With all three INP/IPR separation techniques high abundances (median 20–70%) of instrumental contamination artifacts were observed (ISI: Si-O spheres, probably calibration aerosol; Ice-CVI: Al-O particles; FINCH + IN-PCVI: steel particles). After removal of the instrumental contamination particles, silicates, Ca-rich particles, carbonaceous material and metal oxides were the major INP/IPR particle types obtained by all three techniques. In addition, considerable amounts (median abundance mostly a few percent) of soluble material (e.g., sea salt, sulfates) were observed. As these soluble particles are often not expected to act as INP/IPR, we consider them as potential measurement artifacts. Minor types of INP/IPR include soot and Pb-bearing particles. The Pb-bearing particles are mainly present as an internal mixture with other particle types. Most samples showed a maximum of the INP/IPR size distribution at 200–400 nm in geometric diameter. In a few cases, a second supermicron maximum was identified. Soot/carbonaceous material and metal oxides were present mainly in the sub-micrometer range. Silicates and Ca-rich particles were mainly found with diameters above 1 μm (using ISI and FINCH), in contrast to the Ice-CVI which also sampled many submicron particles of both groups. Due to changing meteorological conditions, the INP/IPR composition was highly variable if different samples were compared. Thus, the observed discrepancies between the different separation techniques may partly result from the non-parallel sampling. The differences of the particle group relative number abundance as well as the mixing state of INP/IPR clearly demonstrate the need of further studies to better understand the influence of the separation techniques on the INP/IPR chemical composition. Also, it must be concluded that the abundance of contamination artifacts in the separated INP and IPR is generally large and should be corrected for, emphasizing the need for the accompanying chemical measurements. Thus, further work is needed to allow for routine operation of the three separation techniques investigated.
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This study presents an original method to evaluate key parameters for the estimation of the direct radiative effect (DRE) of aerosol above clouds: the absorption of the the cloud albedo. It is based on multi-angle total and polarized radiances both provided by the A-train satellite instrument POLDER – Polarization and Directionality of Earth Reflectances. The sensitivities brought by each kind of measurements are used in a complementary way. Polarization mostly translates scattering processes and is thus used to estimate scattering aerosol optical thickness and aerosol size. On the other hand, total radiances, together with the scattering properties of aerosols, are used to evaluate the absorption optical thickness of aerosols and cloud optical thickness. The retrieval of aerosol and clouds properties (i.e., aerosol and cloud optical thickness, aerosol single scattering albedo and Ångström exponent) is restricted to homogeneous and optically thick clouds (cloud optical thickness larger than 3). In addition, a procedure has been developed to process the shortwave DRE of aerosols above clouds. Three case studies have been selected: a case of absorbing biomass burning aerosols above clouds over the southeast Atlantic Ocean, a Siberian biomass burning event and a layer of Saharan dust above clouds off the northwest coast of Africa. Besides these case studies, both algorithms have been applied to the southeast Atlantic Ocean and the results have been averaged during August 2006. The mean DRE is found to be 33.5 W m<sup>−2</sup> (warming). Finally, the effect of the heterogeneity of clouds has been investigated and reveals that it affects mostly the retrieval of the cloud optical thickness and not greatly the aerosols properties. The homogenous cloud assumption used in both the properties retrieval and the DRE processing leads to a slight underestimation of the DRE.
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While global stratospheric O<sub>3</sub> has begun to recover, there are localized regions where O<sub>3</sub> has decreased since 1991. Specifically, we use measurements from the Halogen Occultation Experiment (HALOE) for the period 1991–2005 and the NASA Aura Microwave Limb Sounder (MLS) for the period 2004–2013 to demonstrate a significant decrease in O<sub>3</sub> near ~ 10 hPa in the tropics. O<sub>3</sub> in this region is very sensitive to variations in NO<sub><i>y</i></sub>, and the observed decrease can be understood as a spatially localized, yet long-term increase in NO<sub><i>y</i></sub>. In turn, using data from MLS and from the Atmospheric Chemistry Experiment (ACE), we show that the NO<sub><i>y</i></sub> variations are caused by decreases in N<sub>2</sub>O which are likely linked to long-term variations in dynamics. To illustrate how variations in dynamics can affect N<sub>2</sub>O and O<sub>3</sub>, we show that by decreasing the upwelling in the tropics, more of the N<sub>2</sub>O can photodissociate with a concomitant increase in NO<sub><i>y</i></sub> production (via N<sub>2</sub>O + O(<sup>1</sup>D) → 2NO) at 10 hPa. Ultimately, this can cause an O<sub>3</sub> decrease of the observed magnitude.
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Teflon chambers are ubiquitous in studies of atmospheric chemistry. Secondary organic aerosol (SOA) formation can be underestimated, owing to deposition of SOA-forming vapors to the chamber wall. We present here an experimental protocol and a model framework to constrain the vapor–wall interactions in Teflon chambers. We measured the wall deposition rates of 25 oxidized organic compounds generated from the photooxidation of isoprene, toluene, α-pinene, and dodecane in two chambers that had been extensively used and in two new unused chambers. We found that the extent of prior use of the chamber did not significantly affect the sorption behavior of the Teflon films. Among the 25 compounds studied, the maximum wall deposition rate is exhibited by the most highly oxygenated and least volatile compounds. By optimizing the model output to the observed vapor decay profiles, we identified that the dominant parameter governing the extent of wall deposition of a compound is its wall accommodation coefficient (α<sub>w<I>i</I></sub>), which can be correlated through its volatility with the number of carbons and oxygens in the molecule. By doing so, the wall-induced deposition rate of intermediate/semi-volatile organic vapors can be reasonably predicted based on their molecular constituency. The extent to which vapor wall deposition impacts measured SOA yields depends on the competition between uptake of organic vapors by suspended particles and the chamber wall. The timescale associated with vapor wall deposition can vary from minutes to hours depending on the value of α<sub>w,<I>i</I></sub>. For volatile and intermediate volatility organic compounds (small α<sub>w,<I>i</I></sub>), gas-particle partitioning will dominate wall deposition for typical particle number concentrations in chamber experiments. For compounds characterized by relatively large α<sub>w,<I>i</I></sub>, vapor transport to particles is suppressed by competition with the chamber wall even with perfect particle accommodation.
