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Unusually large wind shears across the inversion in the stratocumulus-topped marine boundary layer (MBL) were frequently observed during VOCALS-REx. To investigate the impact of wind shear on the MBL turbulence structure, a large-eddy simulation (LES) model is used to simulate the strongly sheared MBL observed from Twin-Otter RF 18 on 13 November 2008. The LES simulated turbulence statistics agree in general with those derived from the measurements, with the MBL exhibiting a decoupled structure characterized by an enhanced entrainment and a turbulence intensity minimum just below the clouds. Sensitivity simulations show that the shear forcing tends to reduce the dynamic stability of the inversion, characterized by the bulk (or gradient) Richardson number. This decrease enhances the entrainment mixing, leading to reduced cloud water. Consequently, the turbulence intensity in the MBL is significantly weakened by the intense wind shear. The inversion thickens considerably and the MBL top separates from the cloud top, creating a finite cloud-free sublayer of 10–50 m thickness within the inversion, depending on the Richardson number. The weakened inversion tends to enhance the turbulence buoyant consumption and simultaneously lead to a reduced buoyant production in the cloud layer due to less radiative cooling. These effects may result in a decoupling process that creates the different heating/moistening rates between the cloud and subcloud layer, leading to a two-layered structure in the strongly sheared stratocumulus-topped MBL.
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This study introduces an observation-based dust identification approach and applies it to reconstruct long-term dust climatology in the western United States. Long-term dust climatology is important for quantifying the effects of atmospheric aerosols on regional and global climate. Although many routine aerosol monitoring networks exist, it is often difficult to obtain dust records from these networks, because these monitors are either deployed far away from dust active regions (most likely collocated with dense population) or contaminated by anthropogenic sources and other natural sources, such as wildfires and vegetation detritus. Here we propose an approach to identify local dust events relying solely on aerosol mass and composition from general-purpose aerosol measurements. Through analyzing the chemical and physical characteristics of aerosol observations during satellite-detected dust episodes, we select five indicators to be used to identify local dust records: (1) high PM<sub>10</sub> concentrations; (2) low PM<sub>2.5</sub>/PM<sub>10</sub> ratio; (3) higher concentrations and percentage of crustal elements; (4) lower percentage of anthropogenic pollutants; and (5) low enrichment factors of anthropogenic elements. After establishing these identification criteria, we conduct hierarchical cluster analysis for all validated aerosol measurement data over 68 IMPROVE sites in the western United States. A total of 182 local dust events were identified over 30 of the 68 locations from 2000 to 2007. These locations are either close to the four US Deserts, namely the Great Basin Desert, the Mojave Desert, the Sonoran Desert, and the Chihuahuan Desert, or in the high wind power region (Colorado). During the eight-year study period, the total number of dust events displays an interesting four-year activity cycle (one in 2000–2003 and the other in 2004–2007). The years of 2003, 2002 and 2007 are the three most active dust periods, with 46, 31 and 24 recorded dust events, respectively, while the years of 2000, 2004 and 2005 are the calmest periods, all with single digit dust records. Among these deserts, the Chihuahuan Desert (59 cases) and the Sonoran Desert (62 cases) are by far the most active source regions. In general, the Chihuahuan Desert dominates dust activities in the first half of the eight-year period while the Sonoran Desert in the second half. The monthly frequency of dust events shows a peak from March to July and a second peak in autumn from September to November. The large quantity of dust events occurring in summertime also suggests the prevailing impact of windblown dust across the year. This seasonal variation is consistent with previous model simulations over the United States.
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The Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) aboard the Canadian satellite SCISAT (launched in August 2003) was designed to investigate the composition of the upper troposphere, stratosphere, and mesosphere. ACE-FTS utilizes solar occultation to measure temperature and pressure as well as vertical profiles of over thirty chemical species including O<sub>3</sub>, H<sub>2</sub>O, CH<sub>4</sub>, N<sub>2</sub>O, CO, NO, NO<sub>2</sub>, N<sub>2</sub>O<sub>5</sub>, HNO<sub>3</sub>, HCl, ClONO<sub>2</sub>, CCl<sub>3</sub>F, CCl<sub>2</sub>F<sub>2</sub>, and HF. Global coverage for each species is obtained approximately over a three month period and measurements are made with a vertical resolution of typically 3–4 km. A quality-controlled climatology has been created for each of these 14 baseline species, where individual profiles are averaged over the period of February 2004 to February 2009. Measurements used are from the ACE-FTS version 2.2 data set including updates for O<sub>3</sub> and N<sub>2</sub>O<sub>5</sub>. The climatological fields are provided on a monthly and three-monthly basis (DJF, MAM, JJA, SON) at 5 degree latitude and equivalent latitude spacing and on 28 pressure surfaces (26 of which are defined by the Stratospheric Processes And their Role in Climate (SPARC) Chemistry-Climate Model Validation Activity). The ACE-FTS climatological data set is available through the ACE website.
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A degradation mechanism for β-caryophyllene has recently been released as part of version 3.2 of the Master Chemical Mechanism (MCM v3.2), describing the gas phase oxidation initiated by reaction with ozone, OH radicals and NO<sub>3</sub> radicals. A detailed overview of the construction methodology is given, within the context of reported experimental and theoretical mechanistic appraisals. The performance of the mechanism has been evaluated in chamber simulations in which the gas phase chemistry was coupled to a representation of the gas-to-aerosol partitioning of 280 multi-functional oxidation products. This evaluation exercise considered data from a number of chamber studies of either the ozonolysis of β-caryophyllene, or the photo-oxidation of β-caryophyllene/NO<sub>x</sub> mixtures, in which detailed product distributions have been reported. This includes the results of a series of photo-oxidation experiments performed in the University of Manchester aerosol chamber, also reported here, in which a comprehensive characterization of the temporal evolution of the organic product distribution in the gas phase was carried out, using Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), in conjunction with measurements of NO<sub>x</sub>, O<sub>3</sub> and SOA mass loading. The CIR-TOF-MS measurements allowed approximately 45 time-resolved product ion signals to be detected, which were assigned on the basis of the simulated temporal profiles of the more abundant MCM v3.2 species, and their probable fragmentation patterns. The evaluation studies demonstrate that the MCM v3.2 mechanism provides an acceptable description of β-caryophyllene degradation under the chamber conditions considered, with the temporal evolution of the observables identified above generally being recreated within the uncertainty bounds of key parameters within the mechanism. The studies have highlighted a number of areas of uncertainty or discrepancy, where further investigation would be valuable to help interpret the results of chamber studies and improve detailed mechanistic understanding. These particularly include: (i) quantification of the yield and stability of the secondary ozonide (denoted BCSOZ in MCM v3.2), formed from β-caryophyllene ozonolysis, and elucidation of the details of its further oxidation, including whether the products retain the "ozonide" functionality; (ii) investigation of the impact of NO<sub>x</sub> on the β-caryophyllene ozonolysis mechanism, in particular its effect on the formation of β-caryophyllinic acid (denoted C137CO2H in MCM v3.2), and elucidation of its formation mechanism; (iii) routine independent identification of β-caryophyllinic acid, and its potentially significant isomer β-nocaryophyllonic acid (denoted C131CO2H in MCM v3.2); (iv) more precise quantification of the primary yield of OH (and other radicals) from β-caryophyllene ozonolysis; (v) quantification of the yields of the first-generation hydroxy nitrates (denoted BCANO3, BCBNO3 and BCCNO3 in MCM v3.2) from the OH-initiated chemistry in the presence of NO<sub>x</sub>; and (vi) further studies in general to improve the identification and quantification of products formed from both ozonolysis and photo-oxidation, including confirmation of the simulated formation of multifunctional species containing hydroperoxide groups, and their important contribution to SOA under NO<sub>x</sub>-free conditions.
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We examined the reaction of N<sub>2</sub>O<sub>5</sub> on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS). The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO<sub>2</sub>) and/or molecular bromine (Br<sub>2</sub>). The relative yield of ClNO<sub>2</sub> and Br<sub>2</sub> depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br<sub>2</sub> was the dominant product otherwise ClNO<sub>2</sub> was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.
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Thermal structure associated with deep convective clouds is investigated using Global Positioning System (GPS) radio occultation measurements. GPS data are insensitive to the presence of clouds, and provide high vertical resolution and high accuracy measurements to identify associated temperature behavior. Deep convective systems are identified using International Satellite Cloud Climatology Project (ISCCP) satellite data, and cloud tops are accurately measured using Cloud-Aerosol Lidar with Orthogonal Polarization (CALIPSO) lidar observations; we focus on 53 cases of near-coincident GPS occultations with CALIPSO profiles over deep convection. Results show a sharp spike in GPS bending angle highly correlated to the top of the clouds, corresponding to anomalously cold temperatures within the clouds. Above the clouds the temperatures return to background conditions, and there is a strong inversion at cloud top. For cloud tops below 14 km, the temperature lapse rate within the cloud often approaches a moist adiabat, consistent with rapid undiluted ascent within the convective systems.
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We study the interactions between atmospheric boundary layer (ABL) dynamics and atmospheric chemistry using a mixed-layer model coupled to chemical reaction schemes. Guided by both atmospheric and chemical measurements obtained during the DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign (2008), numerical experiments are performed to study the role of ABL dynamics and the accuracy of chemical schemes with different complexity: the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) and a reduced mechanism of this chemical system. Both schemes produce satisfactory results, indicating that the reduced scheme is capable of reproducing the O<sub>3</sub>-NO<sub>x</sub>-VOC-HO<sub>x</sub> diurnal cycle during conditions characterized by a low NO<sub>x</sub> regime and small O<sub>3</sub> tendencies (less than 1 ppb per hour). By focusing on the budget equations of chemical species in the mixed-layer model, we show that for species like O<sub>3</sub>, NO and NO<sub>2</sub>, the influence of entrainment and boundary layer growth is of the same order as chemical production/loss. This indicates that an accurate representation of ABL processes is crucial in understanding the diel cycle of chemical species. By comparing the time scales of chemical reactive species with the mixing time scale of turbulence, we propose a classification based on the Damköhler number to further determine the importance of dynamics on chemistry during field campaigns. Our findings advocate an integrated approach, simultaneously solving the ABL dynamics and chemical reactions, in order to obtain a better understanding of chemical pathways and processes and the interpretation of the results obtained during measurement campaigns.
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Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO<sub>2</sub> through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in <sup>34</sup>S and we find an enrichment factor (δ<sup>34</sup>S) of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of <sup>33</sup>S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO<sub>2</sub> by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.
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A new parameter model for α-pinene secondary organic aerosol (SOA) is presented, based on simulations with the detailed model BOREAM (Biogenic hydrocarbon Oxidation and Related Aerosol formation Model). The parameterisation takes into account the influence of temperature, type of oxidant, NO<sub>x</sub>-regime, photochemical ageing and water uptake, and is suitable for use in global chemistry transport models. BOREAM is validated against recent photooxidation smog chamber experiments, for which it reproduces SOA yields to within a factor of 2 in most cases. In the simple chemical mechanism of the parameter model, oxidation of α-pinene generates peroxy radicals, which, upon reaction with NO or HO<sub>2</sub>, yield products corresponding to high or low-NO<sub>x</sub> conditions, respectively. The model parameters – i.e. the temperature-dependent stoichiometric coefficients and partitioning coefficients of 10 semi-volatile products – are obtained from simulations with BOREAM, including a prescribed diurnal cycle for the radiation, oxidant and emission levels, as well as a deposition sink for the particulate and gaseous products. The effects of photooxidative ageing are implicitly included in the parameterisation, since it is based on near-equilibrium SOA concentrations, obtained through simulations of a two-week period. In order to mimic the full BOREAM model results both during SOA build-up and when SOA has reached an equilibrium concentration, the revolatilisation of condensable products due to photochemical processes is taken into account through a fitted pseudo-photolysis reaction of the lumped semi-volatile products. Modelled SOA mass yields are about ten times higher in low-NO<sub>x</sub> than in high-NO<sub>x</sub> conditions, with yields of more than 50% in the low-NO<sub>x</sub> OH-initiated oxidation of α-pinene, considerably more than in previous parameterisations based on smog chamber experiments. Sensitivity calculations indicate that discrepancies between the full model and the parameterisation due to variations in assumed oxidant levels are limited, but that changes in the radiation levels can lead to larger deviations. Photolysis of species in the particulate phase is found to strongly reduce SOA yields in the full model. Simulations of ambient conditions at 17 different sites (using oxidant, radiation and meteorological data from a global chemistry-transport model) show that overall, the parameterisation displays only little bias (2%) compared with the full model, whereas averaged relative deviations amount to about 11%. Water uptake is parameterised using fitted activity coefficients, resulting in a good agreement with the full model.
