scholarly journals A light-driven burst of hydroxyl radicals dominates oxidation chemistry in newly activated cloud droplets

2019 ◽  
Vol 5 (5) ◽  
pp. eaav7689 ◽  
Author(s):  
Suzanne E. Paulson ◽  
Peter J. Gallimore ◽  
Xiaobi M. Kuang ◽  
Jie Rou Chen ◽  
Markus Kalberer ◽  
...  

Aerosol particles and their interactions with clouds are one of the most uncertain aspects of the climate system. Aerosol processing by clouds contributes to this uncertainty, altering size distributions, chemical composition, and radiative properties. Many changes are limited by the availability of hydroxyl radicals in the droplets. We suggest an unrecognized potentially substantial source of OH formation in cloud droplets. During the first few minutes following cloud droplet formation, the material in aerosols produces a near-UV light–dependent burst of hydroxyl radicals, resulting in concentrations of 0.1 to 3.5 micromolar aqueous OH ([OH]aq). The source of this burst is previously unrecognized chemistry between iron(II) and peracids. The contribution of the “OH burst” to total OH in droplets varies widely, but it ranges up to a factor of 5 larger than previously known sources. Thus, this new process will substantially enhance the impact of clouds on aerosol properties.

2006 ◽  
Vol 6 (6) ◽  
pp. 1627-1634 ◽  
Author(s):  
S. Romakkaniemi ◽  
H. Kokkola ◽  
K. E. J. Lehtinen ◽  
A. Laaksonen

Abstract. In this paper we present simulations of the effect of nitric acid (HNO3) on cloud processing of aerosol particles. Sulfuric acid (H2SO4) production and incloud coagulation are both affected by condensed nitric acid as nitric acid increases the number of cloud droplets, which will lead to smaller mean size and higher total surface area of droplets. As a result of increased cloud droplet number concentration (CDNC), the incloud coagulation rate is enhanced by a factor of 1–1.3, so that the number of interstitial particles reduces faster. In addition, sulfuric acid production occurs in smaller particles and so the cloud processed aerosol size distribution is dependent on the HNO3 concentration. This affects both radiative properties of aerosol particles and the formation of cloud droplets during a sequence of cloud formation-evaporation events. It is shown that although the condensation of HNO3 increases the number of cloud droplets during the single updraft, it is possible that presence of HNO3 can actually decrease the cloud droplet number concentration after several cloud cycles when also H2SO4 production is taken into account.


2004 ◽  
Vol 4 (5) ◽  
pp. 1255-1263 ◽  
Author(s):  
B. Mayer ◽  
M. Schröder ◽  
R. Preusker ◽  
L. Schüller

Abstract. Cloud single scattering properties are mainly determined by the effective radius of the droplet size distribution. There are only few exceptions where the shape of the size distribution affects the optical properties, in particular the rainbow and the glory directions of the scattering phase function. Using observations by the Compact Airborne Spectrographic Imager (CASI) in 180° backscatter geometry, we found that high angular resolution aircraft observations of the glory provide unique new information which is not available from traditional remote sensing techniques: Using only one single wavelength, 753nm, we were able to determine not only optical thickness and effective radius, but also the width of the size distribution at cloud top. Applying this novel technique to the ACE-2 CLOUDYCOLUMN experiment, we found that the size distributions were much narrower than usually assumed in radiation calculations which is in agreement with in-situ observations during this campaign. While the shape of the size distribution has only little relevance for the radiative properties of clouds, it is extremely important for understanding their formation and evolution.


2013 ◽  
Vol 13 (2) ◽  
pp. 5477-5507
Author(s):  
J. Tonttila ◽  
P. Räisänen ◽  
H. Järvinen

Abstract. A new method for parameterizing the subgrid variations of vertical velocity and cloud droplet number concentration (CDNC) is presented for GCMs. These parameterizations build on top of existing parameterizations that create stochastic subgrid cloud columns inside the GCM grid-cells, which can be employed by the Monte Carlo independent column approximation approach for radiative transfer. The new model version adds a description for vertical velocity in individual subgrid columns, which can be used to compute cloud activation and the subgrid distribution of the number of cloud droplets explicitly. This provides a consistent way for simulating the cloud radiative effects with two-moment cloud microphysical properties defined in subgrid-scale. The primary impact of the new parameterizations is to decrease the CDNC over polluted continents, while over the oceans the impact is smaller. This promotes changes in the global distribution of the cloud radiative effects and might thus have implications on model estimation of the indirect radiative effect of aerosols.


2021 ◽  
Author(s):  
Fabian Mahrt ◽  
Yuanzhou Huang ◽  
Shaun Xu ◽  
Manabu Shiraiwa ◽  
Andreas Zuend ◽  
...  

<p>Aerosol particles are ubiquitous in the atmosphere and play an important role for air quality and Earth’s climate. Primary organic aerosol (POA), secondary organic aerosol (SOA), and secondary inorganic aerosol (SIA) constitute a significant mass fraction of these particles. POA, SOA, and SIA can become internally mixed within the same particle though different processes such as coagulation, gas–particle partitioning. To predict the role of these internally mixed particles in climate and air quality information on their phase behaviour is needed, i.e. information on the number and type of phases present within these particles. As an example, a particle with a single homogeneous liquid phase can have different radiative properties, reaction rates, uptake kinetics, and potential to change cloud microphysical properties by activating into a cloud droplet, compared to a particle with multiple liquid or solid phases.</p><p>In the current study we used Nile red, a solvatochromic dye, and fluorescence microscopy in order to determine the phase behaviour of POA+SOA+SIA particles. Squalane was used as a proxy of POA, ammonium sulfate was used as SIA and 1 of 23 different oxidized organic molecules were used as proxies of SOA. We demonstrate that three liquid phases often coexist within individual particles. We find that the phase behaviour strongly depends on the oxygen-to-carbon ratio of the SOA proxies. Experiments with SOA generated by dark ozonolysis of α-pinene in an environmental chamber are consistent with these observations. We also used thermodynamic and kinetic modelling to investigate the atmospheric implications of our experimental results.</p>


2020 ◽  
Author(s):  
Alexis Dépée ◽  
Pascal Lemaitre ◽  
Thomas Gelain ◽  
Marie Monier ◽  
Andrea Flossmann

Abstract. A new In-Cloud Aerosol Scavenging Experiment (In-CASE) has been conceived to measure the collection efficiency (CE) of submicron aerosol particles by cloud droplets. In this setup, droplets fall at their terminal velocity through a one-meter-high chamber in a laminar flow containing aerosol particles. At the bottom of the In-CASE's chamber, the droplet train is separated from the aerosol particle flow – droplets are collected in an impaction cup whereas aerosol particles are deposited on a High Efficiency Particulate Air (HEPA) filter. The collected droplets and the filter are then analysed by fluorescence spectrometry since the aerosol particles are atomised from a sodium fluorescein salt solution (C20H10Na2O5). In-CASE fully controls all the parameters which affect the CE – the droplets and aerosol particles size distributions are monodispersed, the electric charges of droplets and aerosol particles are controlled, while the relative humidity is indirectly set via the chamber's temperature. This novel In-CASE setup is presented here as well as the first measurements obtained to study the impact of relative humidity on CE. For this purpose, droplets and particles are electrically neutralised. A droplet radius of 49.6 ± 1.3 μm has been considered for six particle dry radii between 50 and 250 nm and three relative humidity levels of 71.1 ± 1.3, 82.4 ± 1.4 and 93.5 ± 0.9 %. These new CE measurements have been compared to the Wang et al. (1978) and the extended model of Dépée et al. (2019) where thermophoresis and diffusiophoresis are implemented. Both models adequately describe the relative humidity influence on the measured CE.


2020 ◽  
Vol 117 (29) ◽  
pp. 16831-16838
Author(s):  
Prasanth Prabhakaran ◽  
Abu Sayeed Md Shawon ◽  
Gregory Kinney ◽  
Subin Thomas ◽  
Will Cantrell ◽  
...  

Aerosol indirect effects are one of the leading contributors to cloud radiative properties relevant to climate. Aerosol particles become cloud droplets when the ambient relative humidity (saturation ratio) exceeds a critical value, which depends on the particle size and chemical composition. In the traditional formulation of this problem, only average, uniform saturation ratios are considered. Using experiments and theory, we examine the effects of fluctuations, produced by turbulence. Our measurements, from a multiphase, turbulent cloud chamber, show a clear transition from a regime in which the mean saturation ratio dominates to one in which the fluctuations determine cloud properties. The laboratory measurements demonstrate cloud formation in mean-subsaturated conditions (i.e., relative humidity <100%) in the fluctuation-dominant activation regime. The theoretical framework developed to interpret these measurements predicts a transition from a mean- to a fluctuation-dominated regime, based on the relative values of the mean and standard deviation of the environmental saturation ratio and the critical saturation ratio at which aerosol particles activate or become droplets. The theory is similar to the concept of stochastic condensation and can be used in the context of the atmosphere to explore the conditions under which droplet activation is driven by fluctuations as opposed to mean supersaturation. It provides a basis for future development of cloud droplet activation parameterizations that go beyond the internally homogeneous parcel calculations that have been used in the past.


2011 ◽  
Vol 50 (4) ◽  
pp. 895-915 ◽  
Author(s):  
A. Protat ◽  
G. M. McFarquhar ◽  
J. Um ◽  
J. Delanoë

AbstractBest estimates of the bulk microphysical and radiative properties (ice water content, visible extinction, effective radius, and total concentration) are derived for three case studies of tropical ice clouds sampled during the Tropical Warm Pool International Cloud Experiment (TWP-ICE). Two case studies are aged cirrus clouds produced by deep convection (the so-called 27/01 and 29/01 cases), and the third (“02/02”) is a fresh anvil produced by deep convective activity over the Tiwi Islands. Using crystal images obtained by a Cloud Particle Imager (CPI), it is observed that small ice particles (with maximum dimension D < 50–100 μm) were predominantly quasi spherical, with the degree of nonsphericity increasing rapidly in the 50 < D < 100-μm range. For D > 100 μm, the aged cirrus clouds were predominantly characterized by bullet rosettes and aggregates of bullet rosettes, plates, and columns. In contrast, the fresh anvil had more frequent occurrences of plates, columns, aggregates of plates, and occasionally capped columns. The impact of shattering of large ice crystals on probe tips and the overall quality of the TWP-ICE in situ microphysical measurements are assessed. It is suggested that shattering has a relatively small impact on the CPI and cloud droplet probe (CDP) TWP-ICE data and a large impact on the Cloud Aerosol Spectrometer data, as already documented by others. It is also shown that the CPI size distributions must be multiplied by a factor of 4 to match those of the cloud imaging probe (CIP) for maximum dimension larger than 100 μm (taken as a reference). A technique [named Best Estimate of Area and Density (BEAD)] to minimize errors associated with the density (ρ)–D and projected area (A)–D assumptions in bulk microphysics calculation is introduced and applied to the TWP-ICE data. The method makes direct use of the frequency of occurrence of each particle habit as classified from the CPI data and prescribed ρ–D and A–D relationships from the literature. This approach produces ice water content (IWC) estimates that are virtually unbiased relative to bulk measures obtained from a counterflow spectrometer and impactor (CSI) probe. In contrast, the use of ρ–D and A–D relationships for single habits does produce large biases relative to the CSI observations: from −50% for bullet rosettes to +70%–80% for aggregates. The so-called width, length, area, and perimeter (WLAP) technique, which also makes use of individual CPI images, is found to produce positively biased IWCs (by 40% or so), and has a standard deviation of the errors similar to the BEAD technique. The impact of the large variability of the size distributions measured by different probe combinations on the bulk microphysical properties is characterized. The mean fractional differences with respect to the CSI measurements are small for the CPI + CIP, CPI, and CDP + CIP combinations (2.2%, −0.8%, and −1.1%, respectively), with standard deviations of the fractional differences ranging from 7% to 9%. This result provides an independent validation of the CPI scaling factor. The fractional differences produced between the CPI + CIP, CPI, and CDP + CIP combinations for extinction, effective radius, and total concentration are 33%, 10%–20%, and 90%, respectively, with relatively small standard deviations of 5%–8%. The fractional difference on total concentration varies greatly over the concentration range though, with values being larger than a factor of 2 for total concentrations smaller than 40 L−1, but reducing to 10%–20% for concentrations larger than 100 L−1. Therefore, caution should be exercised when using total concentrations smaller than 60–80 L−1 as references for radar–lidar retrieval evaluation.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Bernadette Rosati ◽  
Sigurd Christiansen ◽  
Anders Dinesen ◽  
Pontus Roldin ◽  
Andreas Massling ◽  
...  

AbstractSea spray aerosol (SSA) contributes significantly to natural aerosol particle concentrations globally, in marine areas even dominantly. The potential changes of the omnipresent inorganic fraction of SSA due to atmospheric ageing is largely unexplored. In the atmosphere, SSA may exist as aqueous phase solution droplets or as dried solid or amorphous particles. We demonstrate that ageing of liquid NaCl and artificial sea salt aerosol by exposure to ozone and UV light leads to a substantial decrease in hygroscopicity and cloud activation potential of the dried particles of the same size. The results point towards surface reactions on the liquid aerosols that are more crucial for small particles and the formation of salt structures with water bound within the dried aerosols, termed hydrates. Our findings suggest an increased formation of hydrate forming salts during ageing and the presence of hydrates in dried SSA. Field observations indicate a reduced hygroscopic growth factor of sub-micrometre SSA in the marine atmosphere compared to fresh laboratory generated NaCl or sea salt of the same dry size, which is typically attributed to organic matter or sulphates. Aged inorganic sea salt offers an additional explanation for such a measured reduced hygroscopic growth factor and cloud activation potential.


2012 ◽  
Vol 12 (10) ◽  
pp. 27111-27172
Author(s):  
J. L. Petters ◽  
H. Jiang ◽  
G. Feingold ◽  
D. L. Rossiter ◽  
D. Khelif ◽  
...  

Abstract. The impact of changes in aerosol and cloud droplet concentration (Na and Nd) on the radiative forcing of stratocumulus-topped boundary layers (STBLs) has been widely studied. How these impacts compare to those due to variations in meteorological context has not been investigated in a systematic fashion. In this study we examine the impact of observed variations in meteorological context and aerosol state on daytime, non-drizzling stratiform evolution, and determine how resulting changes in cloud properties compare. We perturb aerosol and meteorological properties within an observationally-constrained LES and determine the cloud response, focusing on changes in liquid water path (LWP), bulk optical depth (τ) and cloud radiative forcing (CRF). We find that realistic variations in meteorological context (i.e. jump properties) can elicit responses in τ and shortwave (SW) CRF that are on the same order of magnitude as, and at times larger than, those responses found due to similar changes in aerosol state (i.e Nd). Further, we find that one hour differences in the timing of SW radiative heating can lead to substantial changes in LWP and τ. Our results suggest that, for observational studies of aerosol influences on the radiative properties of stratiform clouds, consistency in meteorological context (the cloud top jump properties in particular) and time of observations from day-to-day must be carefully considered.


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