Time dependent chemistry in dense molecular clouds. I - Grain surface reactions, gas/grain interactions and infrared spectroscopy

NASA Technical Reports Server (NTRS)

Dhendecourt, L. B.; Allamandola, L. J.; Greenberg, J. M.

1985-01-01

For the fist time, a time-dependent model is described which includes the role of grains in the production of molecules in dense clouds including ion-molecule gas phase chemistry. The approach provides information regarding the coupling between the two phases. Although the coupling between the two chemistries is extremely strong, the two domains maintain their own identities. While H2O, CH4, and NH3 are made efficiently, with a high production rate on grains and released back to the gas phase, the gas phase is essentially responsible for the formation of CO, a very stable molecule which may or may not react on grains with atomic oxygen and may or may not form CO2.

The molecular composition of dense interstellar clouds

NASA Technical Reports Server (NTRS)

Allen, M.; Robinson, G. W.

1977-01-01

Presented in this paper is an ab initio chemical model for dense interstellar clouds that incorporates 598 grain surface reactions, with small grains providing the reaction area. Gas-phase molecules are depleted through collisions with grains. The abundances of 372 chemical species are calculated as a function of time and are found to be of sufficient magnitude to explain most observations. Peak abundances are achieved on time scales of the order of 100,000 to 1 million years, depending on cloud density and kinetic temperature. The reaction rates for ion-molecule chemistry are approximately the same, indicating that surface and gas-phase chemistry may be coupled in certain regions. The composition of grain mantles is shown to be a function of grain radius. In certain grain-size ranges, large molecules containing two or more heavy atoms are more predominant than lighter 'ices' - H2O, NH3, and CH4. It is possible that absorption due to these large molecules in the mantle may contribute to the observed 3-micron band in astronomical spectra.

Static Chemistry in Disks or Clouds

NASA Astrophysics Data System (ADS)

Semenov, D.; Wiebe, D.

2006-11-01

This FORTRAN77 code can be used to model static, time-dependent chemistry in ISM and circumstellar disks. Current version is based on the OSU'06 gas-grain astrochemical network with all updates to the reaction rates, and includes surface chemistry from Hasegawa & Herbst (1993) and Hasegawa, Herbst, and Leung (1992). Surface chemistry can be modeled either with the standard rate equation approach or modified rate equation approach (useful in disks). Gas-grain interactions include sticking of neutral molecules to grains, dissociative recombination of ions on grains as well as thermal, UV, X-ray, and CRP-induced desorption of frozen species. An advanced X-ray chemistry and 3 grain sizes with power-law size distribution are also included. An deuterium extension to this chemical model is available.

Interstellar Antifreeze: Ethylene Glycol

NASA Technical Reports Server (NTRS)

Hollis, J. M.; Lovas, F. J.; Jewell, P. R.; Coudert, L. H.

2002-01-01

Interstellar ethylene glycol (HOCH2CH2,OH) has been detected in emission toward the Galactic center source Sagittarius B2(N-LMH) by means of several millimeter-wave rotational torsional transitions of its lowest energy conformer. The types and kinds of molecules found to date in interstellar clouds suggest a chemistry that favors aldehydes and their corresponding reduced alcohols-e.g., formaldehyde (H2CO)/methanol (CH3OH), acetaldehyde (CH3CHO)/ethanol (CH3CH2OH). Similarly, ethylene glycol is the reduced alcohol of glycolaldehyde (CH2OHCHO), which has also been detected toward Sgr B2(N-LMH). While there is no consensus as to how any such large complex molecules are formed in the interstellar clouds, atomic hydrogen (H) and carbon monoxide (CO) could form formaldehyde on grain surfaces, but such surface chemistry beyond that point is uncertain. However, laboratory experiments have shown that the gas-phase reaction of atomic hydrogen (H) and solid-phase CO at 10-20 K can produce formaldehyde and methanol and that alcohols and other complex molecules can be synthesized from cometary ice analogs when subject to ionizing radiation at 15 K. Thus, the presence of aldehyde/ reduced alcohol pairs in interstellar clouds implies that such molecules are a product of a low-temperature chemistry on grain surfaces or in grain ice mantles. This work suggests that aldehydes and their corresponding reduced alcohols provide unique observational constraints on the formation of complex interstellar molecules.

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

PubMed

Li, Tao; Wang, Yan; Mao, Huiting; Wang, Shuxiao; Talbot, Robert W; Zhou, Ying; Wang, Zhe; Nie, Xiaoling; Qie, Guanghao

2018-05-01

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L -1 , respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( N d ) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients K ad (5.9-362.7 L g -1 ) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Chemistry and dynamics of the Arctic winter 2015/2016: Simulations with the Chemistry-Climate Model EMAC

NASA Astrophysics Data System (ADS)

Khosrawi, Farahnaz; Kirner, Ole; Sinnhuber, Bjoern-Martin; Ruhnke, Roland; Hoepfner, Michael; Woiwode, Wolfgang; Oelhaf, Hermann; Santee, Michelle L.; Manney, Gloria L.; Froidevaux, Lucien; Murtagh, Donal; Braesicke, Peter

2016-04-01

Model simulations of the Arctic winter 2015/2016 were performed with the atmospheric chemistry-climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC) for the POLSTRACC (Polar Stratosphere in a Changing Climate) project. The POLSTRACC project is a HALO mission (High Altitude and LOng Range Research Aircraft) that aims to investigate the structure, composition and evolution of the Arctic Upper Troposphere Lower Stratosphere (UTLS) in a changing climate. Especially, the chemical and physical processes involved in Arctic stratospheric ozone depletion, transport and mixing processes in the UTLS at high latitudes, polar stratospheric clouds as well as cirrus clouds are investigated. The model simulations were performed with a resolution of T42L90, corresponding to a quadratic Gaussian grid of approximately 2.8°× 2.8° degrees in latitude and longitude, and 90 vertical layers from the surface up to 0.01 hPa (approx. 80 km). A Newtonian relaxation technique of the prognostic variables temperature, vorticity, divergence and surface pressure towards ECMWF data was applied above the boundary layer and below 10 hPa, in order to nudge the model dynamics towards the observed meteorology. During the Arctic winter 2015/2016 a stable vortex formed in early December, with a cold pool where temperatures reached below the Nitric Acid Trihydrate (NAT) existence temperature of 195 K, thus allowing Polar Stratospheric Clouds (PSCs) to form. The early winter has been exceptionally cold and satellite observations indicate that sedimenting PSC particles have lead to denitrification as well as dehydration of stratospheric layers. In this presentation an overview of the chemistry and dynamics of the Arctic winter 2015/2016 as simulated with EMAC will be given and comparisons to satellite observations such as e.g. Aura/MLS and Odin/SMR will be shown.

Grain Surface Chemistry and the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.

2006-01-01

Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

Evaluation of the cloud fields in the UK Met Office HadGEM3-UKCA model using the CCCM satellite data product to advance our understanding of the influence of clouds on tropospheric composition and chemistry

NASA Astrophysics Data System (ADS)

Varma, S.; Voulgarakis, A.; Liu, H.; Crawford, J. H.

2016-12-01

What drives the variability of trace gases and aerosols in the troposphere is not well understood, as is the role of clouds in modulating this variability via radiative, transport, deposition, and lightning effects that are associated with them. Such uncertainties are expected to be of particular importance in the tropical troposphere, a region that receives significant surface emissions and moisture via deep convection and upwelling, and experiences large amounts of lightning production of nitrogen oxides (NOx). Accurately simulating tropospheric composition and its variability is of utmost importance as both could have a significant effect on the region's temperature and circulation, as well as on surface climate and the amount of UV radiation in the troposphere. In this presentation, we will examine the key cloud processes which are expected to have an influence on tropospheric composition with a specific focus on their roles in modifying solar radiation and photolysis rates of trace gases through the backscattering of shortwave radiation. We will pay particular attention to the UT/LS which is less well understood and where clouds could have a significant impact due to backscattering. We will also utilize CCCM (a unique 3-D cloud data product merged from multiple A-Train satellites (CERES, CloudSat, CALIPSO, and MODIS) developed at the NASA Langley Research Center to evaluate the cloud fields and their vertical distribution in the HadGEM3-UKCA model and to adjust the cloud fields where appropriate. This evaluation will initially involve the comparison of effective cloud optical depth (ECOD) as calculated from CCCM and HadGEM3-UKCA using the approximate random overlap approximation followed by the application of 3-D scaling factors to the model's ECOD. We will then examine the impacts of the cloud field adjustment on tropospheric chemistry, with a focus on oxidants in the UT/LS.

Quantifying errors in surface ozone predictions associated with clouds over the CONUS: a WRF-Chem modeling study using satellite cloud retrievals

NASA Astrophysics Data System (ADS)

Ryu, Young-Hee; Hodzic, Alma; Barre, Jerome; Descombes, Gael; Minnis, Patrick

2018-05-01

Clouds play a key role in radiation and hence O3 photochemistry by modulating photolysis rates and light-dependent emissions of biogenic volatile organic compounds (BVOCs). It is not well known, however, how much error in O3 predictions can be directly attributed to error in cloud predictions. This study applies the Weather Research and Forecasting with Chemistry (WRF-Chem) model at 12 km horizontal resolution with the Morrison microphysics and Grell 3-D cumulus parameterization to quantify uncertainties in summertime surface O3 predictions associated with cloudiness over the contiguous United States (CONUS). All model simulations are driven by reanalysis of atmospheric data and reinitialized every 2 days. In sensitivity simulations, cloud fields used for photochemistry are corrected based on satellite cloud retrievals. The results show that WRF-Chem predicts about 55 % of clouds in the right locations and generally underpredicts cloud optical depths. These errors in cloud predictions can lead to up to 60 ppb of overestimation in hourly surface O3 concentrations on some days. The average difference in summertime surface O3 concentrations derived from the modeled clouds and satellite clouds ranges from 1 to 5 ppb for maximum daily 8 h average O3 (MDA8 O3) over the CONUS. This represents up to ˜ 40 % of the total MDA8 O3 bias under cloudy conditions in the tested model version. Surface O3 concentrations are sensitive to cloud errors mainly through the calculation of photolysis rates (for ˜ 80 %), and to a lesser extent to light-dependent BVOC emissions. The sensitivity of surface O3 concentrations to satellite-based cloud corrections is about 2 times larger in VOC-limited than NOx-limited regimes. Our results suggest that the benefits of accurate predictions of cloudiness would be significant in VOC-limited regions, which are typical of urban areas.

Molecular Composition and Chemistry of Isolated Dense Cores

NASA Astrophysics Data System (ADS)

Cook, Amanda; Boogert, A.

2009-01-01

The composition of molecular clouds and the envelopes and disks surrounding low mass protostars within them is still poorly known. There is little doubt that a large fraction of the molecules is frozen on grains, but the abundance of several crucial species (e.g. ammonia, methanol, ions) in the ices is still uncertain. In addition, prominent spectral features discovered decades ago are still not securely identified (e.g. the 6.85-micron absorption band). Gas phase and grain surface chemistry play pivotal roles in molecule formation, but numerous other processes could have significant impacts as well: shocks, thermal heating, irradiation of ices by ultraviolet photons and cosmic rays. Complex species could be formed this way, profoundly influencing cloud, disk and planetary/cometary chemistry. We have obtained Spitzer/IRS spectra of an unprecedented sample of sight-lines tracing 25 dense isolated cores. These cores physically differ from the large, cluster-forming molecular clouds (e.g. Ophiuchus, Perseus) that are commonly studied: they are less turbulent, colder, less dense, and likely longer lived. These IRS spectra of isolated cores thus provide unique information on ice formation and destruction mechanisms. Toward the same cores, we observed 33 highly extincted background stars as well, tracing the quiescent cloud medium against which the ices around protostars can be contrasted.

Implementation of warm-cloud processes in a source-oriented WRF/Chem model to study the effect of aerosol mixing state on fog formation in the Central Valley of California

NASA Astrophysics Data System (ADS)

Lee, H.-H.; Chen, S.-H.; Kleeman, M. J.; Zhang, H.; DeNero, S. P.; Joe, D. K.

2015-11-01

The source-oriented Weather Research and Forecasting chemistry model (SOWC) was modified to include warm cloud processes and applied to investigate how aerosol mixing states influence fog formation and optical properties in the atmosphere. SOWC tracks a 6-dimensional chemical variable (X, Z, Y, Size Bins, Source Types, Species) through an explicit simulation of atmospheric chemistry and physics. A source-oriented cloud condensation nuclei module was implemented into the SOWC model to simulate warm clouds using the modified two-moment Purdue Lin microphysics scheme. The Goddard shortwave and longwave radiation schemes were modified to interact with source-oriented aerosols and cloud droplets so that aerosol direct and indirect effects could be studied. The enhanced SOWC model was applied to study a fog event that occurred on 17 January 2011, in the Central Valley of California. Tule fog occurred because an atmospheric river effectively advected high moisture into the Central Valley and nighttime drainage flow brought cold air from mountains into the valley. The SOWC model produced reasonable liquid water path, spatial distribution and duration of fog events. The inclusion of aerosol-radiation interaction only slightly modified simulation results since cloud optical thickness dominated the radiation budget in fog events. The source-oriented mixture representation of particles reduced cloud droplet number relative to the internal mixture approach that artificially coats hydrophobic particles with hygroscopic components. The fraction of aerosols activating into CCN at a supersaturation of 0.5 % in the Central Valley decreased from 94 % in the internal mixture model to 80 % in the source-oriented model. This increased surface energy flux by 3-5 W m-2 and surface temperature by as much as 0.25 K in the daytime.

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.

PubMed

Finlayson-Pitts, Barbara J

2009-09-28

While particles have significant deleterious impacts on human health, visibility and climate, quantitative understanding of their formation, composition and fates remains problematic. Indeed, in many cases, even qualitative understanding is lacking. One area of particular uncertainty is the nature of particle surfaces and how this determines interactions with gases in the atmosphere, including water, which is important for cloud formation and properties. The focus in this Perspective article is on some chemistry relevant to airborne particles and especially to reactions occurring on their surfaces. The intent is not to provide a comprehensive review, but rather to highlight a few selected examples of interface chemistry involving inorganic and organic species that may be important in the lower atmosphere. This includes sea salt chemistry, nitrate and nitrite ion photochemistry, organics on surfaces and heterogeneous reactions of oxides of nitrogen on proxies for airborne mineral dust and boundary layer surfaces. Emphasis is on the molecular level understanding that can only be gained by fully integrating experiment and theory to elucidate these complex systems.

Accounting for Heterogeneous-Phase Chemistry in Air Quality Models - Research Needs and Applications

EPA Science Inventory

Understanding the extent to which heterogeneous chemical reactions affect the burden and distribution of atmospheric pollutants is important because heterogeneous surfaces are ubiquitous throughout our environment. They include materials such as aerosol particles, clouds and fog,...

Overview of the DACCIWA ground-based field campaign in southern West Africa

NASA Astrophysics Data System (ADS)

Lohou, Fabienne; Kalthoff, Norbert; Brooks, Barbara; Jegede, Gbenga; Adler, Bianca; Ajao, Adewale; Ayoola, Muritala; Babić, Karmen; Bessardon, Geoffrey; Delon, Claire; Dione, Cheikh; Handwerker, Jan; Jambert, Corinne; Kohler, Martin; Lothon, Marie; Pedruzo-Bagazgoitia, Xabier; Smith, Victoria; Sunmonu, Lukman; Wieser, Andreas; Derrien, Solène

2017-04-01

During June and July 2016, a ground-based field campaign took place in southern West Africa within the framework of the Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) project. In the investigated region, extended low-level stratus clouds form very frequently during night-time and persist long into the following day influencing the diurnal cycle of the atmospheric boundary layer and, hence, the regional climate. The motivation for the measurements was to identify the meteorological controls on the whole process chain from the formation of nocturnal stratus clouds, via the daytime transition to convective clouds and the formation of deep precipitating clouds. During the measurement period, extensive remote sensing and in-situ measurements were performed at three supersites in Kumasi (Ghana), Savè (Benin) and Ile-Ife (Nigeria). The gathered observations included the energy-balance components at the Earth's surface, the mean and turbulent conditions in the nocturnal and daytime ABL as well as the de- and entrainment processes between the ABL and the free troposphere. The meteorological measurements were supplemented by aerosol and air-chemistry observations. We will give an overview of the conducted measurements including instrument availability and strategy during intensive observation periods.

The Arctic Summer Cloud Ocean Study (ASCOS): overview and experimental design

NASA Astrophysics Data System (ADS)

Tjernström, M.; Leck, C.; Birch, C. E.; Bottenheim, J. W.; Brooks, B. J.; Brooks, I. M.; Bäcklin, L.; Chang, R. Y.-W.; de Leeuw, G.; Di Liberto, L.; de la Rosa, S.; Granath, E.; Graus, M.; Hansel, A.; Heintzenberg, J.; Held, A.; Hind, A.; Johnston, P.; Knulst, J.; Martin, M.; Matrai, P. A.; Mauritsen, T.; Müller, M.; Norris, S. J.; Orellana, M. V.; Orsini, D. A.; Paatero, J.; Persson, P. O. G.; Gao, Q.; Rauschenberg, C.; Ristovski, Z.; Sedlar, J.; Shupe, M. D.; Sierau, B.; Sirevaag, A.; Sjogren, S.; Stetzer, O.; Swietlicki, E.; Szczodrak, M.; Vaattovaara, P.; Wahlberg, N.; Westberg, M.; Wheeler, C. R.

2014-03-01

The climate in the Arctic is changing faster than anywhere else on earth. Poorly understood feedback processes relating to Arctic clouds and aerosol-cloud interactions contribute to a poor understanding of the present changes in the Arctic climate system, and also to a large spread in projections of future climate in the Arctic. The problem is exacerbated by the paucity of research-quality observations in the central Arctic. Improved formulations in climate models require such observations, which can only come from measurements in situ in this difficult-to-reach region with logistically demanding environmental conditions. The Arctic Summer Cloud Ocean Study (ASCOS) was the most extensive central Arctic Ocean expedition with an atmospheric focus during the International Polar Year (IPY) 2007-2008. ASCOS focused on the study of the formation and life cycle of low-level Arctic clouds. ASCOS departed from Longyearbyen on Svalbard on 2 August and returned on 9 September 2008. In transit into and out of the pack ice, four short research stations were undertaken in the Fram Strait: two in open water and two in the marginal ice zone. After traversing the pack ice northward, an ice camp was set up on 12 August at 87°21' N, 01°29' W and remained in operation through 1 September, drifting with the ice. During this time, extensive measurements were taken of atmospheric gas and particle chemistry and physics, mesoscale and boundary-layer meteorology, marine biology and chemistry, and upper ocean physics. ASCOS provides a unique interdisciplinary data set for development and testing of new hypotheses on cloud processes, their interactions with the sea ice and ocean and associated physical, chemical, and biological processes and interactions. For example, the first-ever quantitative observation of bubbles in Arctic leads, combined with the unique discovery of marine organic material, polymer gels with an origin in the ocean, inside cloud droplets suggests the possibility of primary marine organically derived cloud condensation nuclei in Arctic stratocumulus clouds. Direct observations of surface fluxes of aerosols could, however, not explain observed variability in aerosol concentrations, and the balance between local and remote aerosols sources remains open. Lack of cloud condensation nuclei (CCN) was at times a controlling factor in low-level cloud formation, and hence for the impact of clouds on the surface energy budget. ASCOS provided detailed measurements of the surface energy balance from late summer melt into the initial autumn freeze-up, and documented the effects of clouds and storms on the surface energy balance during this transition. In addition to such process-level studies, the unique, independent ASCOS data set can and is being used for validation of satellite retrievals, operational models, and reanalysis data sets.

Investigation of Polar Stratospheric Cloud Solid Particle Formation Mechanisms Using ILAS and AVHRR Observations in the Arctic

NASA Technical Reports Server (NTRS)

Irie, H.; Pagan, K. L.; Tabazadeh, A.; Legg, M. J.; Sugita, T.

2004-01-01

Satellite observations of denitrification and ice clouds in the Arctic lower stratosphere in February 1997 are used with Lagrangian microphysical box model calculations to evaluate nucleation mechanisms of solid polar stratospheric cloud (PSC) particles. The occurrences of ice clouds are not correlated in time and space with the locations of back trajectories of denitrified air masses, indicating that ice particle surfaces are not always a prerequisite for the formation of solid PSCs that lead to denitrification. In contrast, the model calculations incorporating a pseudoheterogeneous freezing process occurring at the vapor-liquid interface can quantitatively explain most of the observed denitrification when the nucleation activation free energy for nitric acid dihydrate formation is raised by only approx.10% relative to the current published values. Once nucleated, the conversion of nitric acid dihydrate to the stable trihydrate phase brings the computed levels of denitrification closer to the measurements. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and SblctureC: loud physics and chemistry; 0340 Atmospheric Composition and Structure: Middle atmosphere-composition and chemistry

The Effects of Grain Size and Temperature Distributions on the Formation of Interstellar Ice Mantles

NASA Astrophysics Data System (ADS)

Pauly, Tyler; Garrod, Robin T.

2016-02-01

Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry of dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual grain-size population. We find that the temperature difference plays a significant role in determining the total bulk ice composition across the grain-size distribution, while the effects of geometrical differences between size populations appear marginal. We also consider collapse from a diffuse to a dark cloud, allowing dust temperatures to fall. Under the initial diffuse conditions, small grains are too warm to promote grain-mantle build-up, with most ices forming on the mid-sized grains. As collapse proceeds, the more abundant, smallest grains cool and become the dominant ice carriers; the large population of small grains means that this ice is distributed across many grains, with perhaps no more than 40 monolayers of ice each (versus several hundred assuming a single grain size). This effect may be important for the subsequent processing and desorption of the ice during the hot-core phase of star formation, exposing a significant proportion of the ice to the gas phase, increasing the importance of ice-surface chemistry and surface-gas interactions.

Following the Interstellar History of Carbon: From the Interiors of Stars to the Surfaces of Planets.

PubMed

Ziurys, L M; Halfen, D T; Geppert, W; Aikawa, Y

2016-12-01

The chemical history of carbon is traced from its origin in stellar nucleosynthesis to its delivery to planet surfaces. The molecular carriers of this element are examined at each stage in the cycling of interstellar organic material and their eventual incorporation into solar system bodies. The connection between the various interstellar carbon reservoirs is also examined. Carbon has two stellar sources: supernova explosions and mass loss from evolved stars. In the latter case, the carbon is dredged up from the interior and then ejected into a circumstellar envelope, where a rich and unusual C-based chemistry occurs. This molecular material is eventually released into the general interstellar medium through planetary nebulae. It is first incorporated into diffuse clouds, where carbon is found in polyatomic molecules such as H 2 CO, HCN, HNC, c-C 3 H 2 , and even C 60 + . These objects then collapse into dense clouds, the sites of star and planet formation. Such clouds foster an active organic chemistry, producing compounds with a wide range of functional groups with both gas-phase and surface mechanisms. As stars and planets form, the chemical composition is altered by increasing stellar radiation, as well as possibly by reactions in the presolar nebula. Some molecular, carbon-rich material remains pristine, however, encapsulated in comets, meteorites, and interplanetary dust particles, and is delivered to planet surfaces. Key Words: Carbon isotopes-Prebiotic evolution-Interstellar molecules-Comets-Meteorites. Astrobiology 16, 997-1012.

The Arctic Summer Cloud-Ocean Study (ASCOS): overview and experimental design

NASA Astrophysics Data System (ADS)

Tjernström, M.; Leck, C.; Birch, C. E.; Brooks, B. J.; Brooks, I. M.; Bäcklin, L.; Chang, R. Y.-W.; Granath, E.; Graus, M.; Hansel, A.; Heintzenberg, J.; Held, A.; Hind, A.; de la Rosa, S.; Johnston, P.; Knulst, J.; de Leeuw, G.; Di Liberto, L.; Martin, M.; Matrai, P. A.; Mauritsen, T.; Müller, M.; Norris, S. J.; Orellana, M. V.; Orsini, D. A.; Paatero, J.; Persson, P. O. G.; Gao, Q.; Rauschenberg, C.; Ristovski, Z.; Sedlar, J.; Shupe, M. D.; Sierau, B.; Sirevaag, A.; Sjogren, S.; Stetzer, O.; Swietlicki, E.; Szczodrak, M.; Vaattovaara, P.; Wahlberg, N.; Westberg, M.; Wheeler, C. R.

2013-05-01

The climate in the Arctic is changing faster than anywhere else on Earth. Poorly understood feedback processes relating to Arctic clouds and aerosol-cloud interactions contribute to a poor understanding of the present changes in the Arctic climate system, and also to a large spread in projections of future climate in the Arctic. The problem is exacerbated by the paucity of research-quality observations in the central Arctic. Improved formulations in climate models require such observations, which can only come from measurements in-situ in this difficult to reach region with logistically demanding environmental conditions. The Arctic Summer Cloud-Ocean Study (ASCOS) was the most extensive central Arctic Ocean expedition with an atmospheric focus during the International Polar Year (IPY) 2007-2008. ASCOS focused on the study of the formation and life cycle of low-level Arctic clouds. ASCOS departed from Longyearbyen on Svalbard on 2 August and returned on 9 September 2008. In transit into and out of the pack ice, four short research stations were undertaken in the Fram Strait; two in open water and two in the marginal ice zone. After traversing the pack-ice northward an ice camp was set up on 12 August at 87°21' N 01°29' W and remained in operation through 1 September, drifting with the ice. During this time extensive measurements were taken of atmospheric gas and particle chemistry and physics, mesoscale and boundary-layer meteorology, marine biology and chemistry, and upper ocean physics. ASCOS provides a unique interdisciplinary data set for development and testing of new hypotheses on cloud processes, their interactions with the sea ice and ocean and associated physical, chemical, and biological processes and interactions. For example, the first ever quantitative observation of bubbles in Arctic leads, combined with the unique discovery of marine organic material, polymer gels with an origin in the ocean, inside cloud droplets suggest the possibility of primary marine organically derived cloud condensation nuclei in Arctic stratocumulus clouds. Direct observations of surface fluxes of aerosols could, however, not explain observed variability in aerosol concentrations and the balance between local and remote aerosols sources remains open. Lack of CCN was at times a controlling factor in low-level cloud formation, and hence for the impact of clouds on the surface energy budget. ASCOS provided detailed measurements of the surface energy balance from late summer melt into the initial autumn freeze-up, and documented the effects of clouds and storms on the surface energy balance during this transition. In addition to such process-level studies, the unique, independent ASCOS data set can and is being used for validation of satellite retrievals, operational models, and reanalysis data sets.

Impacts of aerosol-cloud interactions on past and future changes in tropospheric composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Unger, N.; Menon, S.; Shindell, D. T.

2009-02-02

The development of effective emissions control policies that are beneficial to both climate and air quality requires a detailed understanding of all the feedbacks in the atmospheric composition and climate system. We perform sensitivity studies with a global atmospheric composition-climate model to assess the impact of aerosols on tropospheric chemistry through their modification on clouds, aerosol-cloud interactions (ACI). The model includes coupling between both tropospheric gas-phase and aerosol chemistry and aerosols and liquid-phase clouds. We investigate past impacts from preindustrial (PI) to present day (PD) and future impacts from PD to 2050 (for the moderate IPCC A1B scenario) that embracemore » a wide spectrum of precursor emission changes and consequential ACI. The aerosol indirect effect (AIE) is estimated to be -2.0 Wm{sup -2} for PD-PI and -0.6 Wm{sup -2} for 2050-PD, at the high end of current estimates. Inclusion of ACI substantially impacts changes in global mean methane lifetime across both time periods, enhancing the past and future increases by 10% and 30%, respectively. In regions where pollution emissions increase, inclusion of ACI leads to 20% enhancements in in-cloud sulfate production and {approx}10% enhancements in sulfate wet deposition that is displaced away from the immediate source regions. The enhanced in-cloud sulfate formation leads to larger increases in surface sulfate across polluted regions ({approx}10-30%). Nitric acid wet deposition is dampened by 15-20% across the industrialized regions due to ACI allowing additional re-release of reactive nitrogen that contributes to 1-2 ppbv increases in surface ozone in outflow regions. Our model findings indicate that ACI must be considered in studies of methane trends and projections of future changes to particulate matter air quality.« less

Green Bank Telescope OH Observations of Smith's Cloud: Evidence Of A Lack Of Chemistry

NASA Astrophysics Data System (ADS)

Minter, Anthony

2017-03-01

Smith's Cloud is a large few × 106 Solar Mass cloud which will impact the Milk Way disk in about 35 Million Years (Lockman et al., 2008). Green Bank Telescope OH observations indicate that there are no molecules present in Smith's Cloud, and thus there is no active ongoing chemistry in Smith's Cloud.

Implementation of warm-cloud processes in a source-oriented WRF/Chem model to study the effect of aerosol mixing state on fog formation in the Central Valley of California

NASA Astrophysics Data System (ADS)

Lee, Hsiang-He; Chen, Shu-Hua; Kleeman, Michael J.; Zhang, Hongliang; DeNero, Steven P.; Joe, David K.

2016-07-01

The source-oriented Weather Research and Forecasting chemistry model (SOWC) was modified to include warm cloud processes and was applied to investigate how aerosol mixing states influence fog formation and optical properties in the atmosphere. SOWC tracks a 6-D chemical variable (X, Z, Y, size bins, source types, species) through an explicit simulation of atmospheric chemistry and physics. A source-oriented cloud condensation nuclei module was implemented into the SOWC model to simulate warm clouds using the modified two-moment Purdue Lin microphysics scheme. The Goddard shortwave and long-wave radiation schemes were modified to interact with source-oriented aerosols and cloud droplets so that aerosol direct and indirect effects could be studied. The enhanced SOWC model was applied to study a fog event that occurred on 17 January 2011, in the Central Valley of California. Tule fog occurred because an atmospheric river effectively advected high moisture into the Central Valley and nighttime drainage flow brought cold air from mountains into the valley. The SOWC model produced reasonable liquid water path, spatial distribution and duration of fog events. The inclusion of aerosol-radiation interaction only slightly modified simulation results since cloud optical thickness dominated the radiation budget in fog events. The source-oriented mixture representation of particles reduced cloud droplet number relative to the internal mixture approach that artificially coats hydrophobic particles with hygroscopic components. The fraction of aerosols activating into cloud condensation nuclei (CCN) at a supersaturation of 0.5 % in the Central Valley decreased from 94 % in the internal mixture model to 80 % in the source-oriented model. This increased surface energy flux by 3-5 W m-2 and surface temperature by as much as 0.25 K in the daytime.

Aircraft-based investigation of Dynamics-Aerosol-Chemistry-Cloud Interactions in Southern West Africa

NASA Astrophysics Data System (ADS)

Flamant, Cyrille

2017-04-01

The EU-funded project DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa, http://www.dacciwa.eu) is investigating the relationship between weather, climate and air pollution in southern West Africa. The air over the coastal region of West Africa is a unique mixture of natural and anthropogenic gases, liquids and particles, emitted in an environment, in which multi-layer cloud decks frequently form. These exert a large influence on the local weather and climate, mainly due to their impact on radiation, the surface energy balance and thus the diurnal cycle of the atmospheric boundary layer. The main objective for the aircraft detachment was to build robust statistics of cloud properties in southern West Africa in different chemical landscapes to investigate the physical processes involved in their life cycle in such a complex chemical environment. As part of the DACCIWA field campaigns, three European aircraft (the German DLR Falcon 20, the French SAFIRE ATR 42 and the British BAS Twin Otter) conducted a total of 50 research flights across Ivory Coast, Ghana, Togo, and Benin from 27 June to 16 July 2016 for a total of 155 flight hours, including hours sponsored through 3 EUFAR projects. The aircraft were used in different ways based on their strengths, but all three had comparable instrumentation with the the capability to do gas-phase chemistry, aerosol and clouds, thereby generating a rich dataset of atmospheric conditions across the region. Eight types of flight objectives were conducted to achieve the goals of the DACCIWA: (i) Stratus clouds, (ii) Land-sea breeze clouds, (iii) Mid-level clouds, (iv) Biogenic emission, (v) City emissions, (vi) Flaring and ship emissions, (vii) Dust and biomass burning aerosols, and (viii) air-sea interactions. An overview of the DACCIWA aircraft campaign as well as first highlights from the airborne observations will be presented.

Insights into H2 formation in space from ab initio molecular dynamics

PubMed Central

Casolo, Simone; Tantardini, Gian Franco; Martinazzo, Rocco

2013-01-01

Hydrogen formation is a key process for the physics and the chemistry of interstellar clouds. Molecular hydrogen is believed to form on the carbonaceous surface of dust grains, and several mechanisms have been invoked to explain its abundance in different regions of space, from cold interstellar clouds to warm photon-dominated regions. Here, we investigate direct (Eley–Rideal) recombination including lattice dynamics, surface corrugation, and competing H-dimers formation by means of ab initio molecular dynamics. We find that Eley–Rideal reaction dominates at energies relevant for the interstellar medium and alone may explain observations if the possibility of facile sticking at special sites (edges, point defects, etc.) on the surface of the dust grains is taken into account. PMID:23572584

Composition, structure and chemistry of interstellar dust

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.; Allamandola, Louis J.

1986-01-01

The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.

Comprehensive evaluation of multi-year real-time air quality forecasting using an online-coupled meteorology-chemistry model over southeastern United States

NASA Astrophysics Data System (ADS)

Zhang, Yang; Hong, Chaopeng; Yahya, Khairunnisa; Li, Qi; Zhang, Qiang; He, Kebin

2016-08-01

An online-coupled meteorology-chemistry model, WRF/Chem-MADRID, has been deployed for real time air quality forecast (RT-AQF) in southeastern U.S. since 2009. A comprehensive evaluation of multi-year RT-AQF shows overall good performance for temperature and relative humidity at 2-m (T2, RH2), downward surface shortwave radiation (SWDOWN) and longwave radiation (LWDOWN), and cloud fraction (CF), ozone (O3) and fine particles (PM2.5) at surface, tropospheric ozone residuals (TOR) in O3 seasons (May-September), and column NO2 in winters (December-February). Moderate-to-large biases exist in wind speed at 10-m (WS10), precipitation (Precip), cloud optical depth (COT), ammonium (NH4+), sulfate (SO42-), and nitrate (NO3-) from the IMPROVE and SEARCH networks, organic carbon (OC) at IMPROVE, and elemental carbon (EC) and OC at SEARCH, aerosol optical depth (AOD) and column carbon monoxide (CO), sulfur dioxide (SO2), and formaldehyde (HCHO) in both O3 and winter seasons, column nitrogen dioxide (NO2) in O3 seasons, and TOR in winters. These biases indicate uncertainties in the boundary layer and cloud process treatments (e.g., surface roughness, microphysics cumulus parameterization), emissions (e.g., O3 and PM precursors, biogenic, mobile, and wildfire emissions), upper boundary conditions for all major gases and PM2.5 species, and chemistry and aerosol treatments (e.g., winter photochemistry, aerosol thermodynamics). The model shows overall good skills in reproducing the observed multi-year trends and inter-seasonal variability in meteorological and radiative variables such as T2, WS10, Precip, SWDOWN, and LWDOWN, and relatively well in reproducing the observed trends in surface O3 and PM2.5, but relatively poor in reproducing the observed column abundances of CO, NO2, SO2, HCHO, TOR, and AOD. The sensitivity simulations using satellite-constrained boundary conditions for O3 and CO show substantial improvement for both spatial distribution and domain-mean performance statistics. The model's forecasting skills for air quality can be further enhanced through improving model inputs (e.g., anthropogenic emissions for urban areas and upper boundary conditions of chemical species), meteorological forecasts (e.g., WS10, Precip) and meteorologically-dependent emissions (e.g., biogenic and wildfire emissions), and model physics and chemical treatments (e.g., gas-phase chemistry in winter conditions, cloud processes and their interactions with radiation and aerosol).

Solid propellant exhausted aluminum oxide and hydrogen chloride - Environmental considerations

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Winstead, E. L.; Purgold, G. C.; Edahl, R. A.

1993-01-01

Measurements of gaseous hydrogen chloride (HCl) and particulate aluminum oxide (Al2O3) were made during penetrations of five Space Shuttle exhaust clouds and one static ground test firing of a shuttle booster. Instrumented aircraft were used to penetrate exhaust clouds and to measure and/or collect samples of exhaust for subsequent analyses. The focus was on the primary solid rocket motor exhaust products, HCl and Al2O3, from the Space Shuttle's solid boosters. Time-dependent behavior of HCl was determined for the exhaust clouds. Composition, morphology, surface chemistry, and particle size distributions were determined for the exhausted Al2O3. Results determined for the exhaust cloud from the static test firing were complicated by having large amounts of entrained alkaline ground debris (soil) in the lofted cloud. The entrained debris may have contributed to neutralization of in-cloud HCl.

Investigating expanded chemistry in CMAQ clouds

EPA Science Inventory

Clouds and fogs significantly impact the amount, composition, and spatial distribution of gas and particulate atmospheric species, not least of which through the chemistry that occurs in cloud droplets.ﾠ Atmospheric sulfate is an important component of fine aerosol mass an...

The sensitivity of tropospheric chemistry to cloud interactions

NASA Technical Reports Server (NTRS)

Jonson, Jan E.; Isaksen, Ivar S. A.

1994-01-01

Clouds, although only occupying a relatively small fraction of the troposphere volume, can have a substantial impact on the chemistry of the troposphere. In newly formed clouds, or in clouds with air rapidly flowing through, the chemistry is expected to be far more active than in aged clouds with stagnant air. Thus, frequent cycling of air through shortlived clouds, i.e. cumulus clouds, is likely to be a much more efficient media for altering the composition of the atmosphere than an extensive cloud cover i.e. frontal cloud systems. The impact of clouds is tested out in a 2-D channel model encircling the globe in a latitudinal belt from 30 to 60 deg N. The model contains a detailed gas phase chemistry. In addition physiochemical interactions between the gas and aqueous phases are included. For species as H2O2, CH2O, O3, and SO2, Henry's law equilibria are assumed, whereas HNO3 and H2SO4 are regarded as completed dissolved in the aqueous phase. Absorption of HO2 and OH is assumed to be mass-transport limited. The chemistry of the aqueous phase is characterized by rapid cycling of odd hydrogen, (H2O2, HO2, and OH). O2(-) (produced through dissociation of HO2) reacting with dissolved O3 is a major source of OH in the aqueous phase. This reaction can be a significant sink for O3 in the troposphere. In the interstitial cloud air, odd hydrogen is depleted, whereas NO(x) remains in the gas phase, thus reducing ozone production due to the reaction between NO and HO2. Our calculations give markedly lower ozone levels when cloud interactions are included. This may in part explain the overpredictions of ozone levels often experienced in models neglecting cloud chemical interactions. In the present study, the existence of clouds, cloud types, and their lifetimes are modeled as pseudo random variables. Such pseudo random sequences are in reality deterministic and may, given the same starting values, be reproduced. The effects of cloud interactions on the overall chemistry of the troposphere are discussed. In particular, tests are performed to determine the sensitivity of cloud frequencies and cloud types.

Storm clouds on Saturn: Lightning-induced chemistry and associated materials consistent with Cassini/VIMS spectra

USGS Publications Warehouse

Baines, K.H.; Delitsky, M.L.; Momary, T.W.; Brown, R.H.; Buratti, B.J.; Clark, R.N.; Nicholson, P.D.

2009-01-01

Thunderstorm activity on Saturn is associated with optically detectable clouds that are atypically dark throughout the near-infrared. As observed by Cassini/VIMS, these clouds are ~20% less reflective than typical neighboring clouds throughout the spectral range from 0.8 ??m to at least 4.1 ??m. We propose that active thunderstorms originating in the 10-20 bar water-condensation region vertically transport dark materials at depth to the ~1 bar level where they can be observed. These materials in part may be produced by chemical processes associated with lightning, likely within the water clouds near the ~10 bar freezing level of water, as detected by the electrostatic discharge of lightning flashes observed by Cassini/RPWS (e.g., Fischer et al. 2008, Space Sci. Rev., 137, 271-285). We review lightning-induced pyrolytic chemistry involving a variety of Saturnian constituents, including hydrogen, methane, ammonia, hydrogen sulfide, phosphine, and water. We find that the lack of absorption in the 1-2 ??m spectral region by lightning-generated sulfuric and phosphorous condensates renders these constituents as minor players in determining the color of the dark storm clouds. Relatively small particulates of elemental carbon, formed by lightning-induced dissociation of methane and subsequently upwelled from depth - perhaps embedded within and on the surface of spectrally bright condensates such as ammonium hydrosulfide or ammonia - may be a dominant optical material within the dark thunderstorm-related clouds of Saturn. ?? 2009 Elsevier Ltd. All rights reserved.

Using the C3M Satellite Data Product to Evaluate and Constrain the Cloud Fields in the HadGEM3-UKCA Model with an Aim to Enhance Understanding of the Effects of Clouds on Atmospheric Composition via Photolysis

NASA Astrophysics Data System (ADS)

Varma, S.; Voulgarakis, A.; Liu, H.; Crawford, J. H.; Zhang, B.

2017-12-01

What drives the variability of trace gases in the troposphere is not well understood, as is the role of clouds in modulating this variability via radiative, transport, deposition, heterogeneous chemistry, and lightning effects that are associated with them. Accurately simulating tropospheric composition and its variability is of utmost importance as both could have a significant effect on the region's temperature and circulation, as well as on surface climate and the amount of UV radiation in the troposphere. In this presentation, we will examine how clouds can influence tropospheric and lower stratospheric composition through modifying solar radiation leading to changes in the local actinic flux and subsequently to photolysis, a key driver of chemistry. We will utilize C3M (a unique 3-D cloud data product merged from multiple A-Train satellites (CERES, CloudSat, CALIPSO, and MODIS) developed at the NASA Langley Research Center to evaluate the cloud fields and their vertical distribution in the HadGEM3-UKCA model developed by the Natural Environment Research Council (NERC, UK) and the Met Office. This evaluation will involve 1) comparing the effective cloud optical depth (ECOD) as calculated from C3M and the model using the approximate random overlap method, 2) applying 3-D scaling factors from C3M to the model's ECOD and analyzing the changes this makes to the model's cloud fields, and 3) running the scaled model and analyzing the impacts of this cloud field adjustment on the model's estimates of photolysis rates and key tropospheric oxidants such as ozone and OH.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pauly, Tyler; Garrod, Robin T., E-mail: tap74@cornell.edu

Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry of dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual grain-size population. We find that the temperature difference plays amore » significant role in determining the total bulk ice composition across the grain-size distribution, while the effects of geometrical differences between size populations appear marginal. We also consider collapse from a diffuse to a dark cloud, allowing dust temperatures to fall. Under the initial diffuse conditions, small grains are too warm to promote grain-mantle build-up, with most ices forming on the mid-sized grains. As collapse proceeds, the more abundant, smallest grains cool and become the dominant ice carriers; the large population of small grains means that this ice is distributed across many grains, with perhaps no more than 40 monolayers of ice each (versus several hundred assuming a single grain size). This effect may be important for the subsequent processing and desorption of the ice during the hot-core phase of star formation, exposing a significant proportion of the ice to the gas phase, increasing the importance of ice-surface chemistry and surface–gas interactions.« less

Ice Chemistry in Starless Molecular Cores

NASA Astrophysics Data System (ADS)

Kalvāns, J.

2015-06-01

Starless molecular cores are natural laboratories for interstellar molecular chemistry research. The chemistry of ices in such objects was investigated with a three-phase (gas, surface, and mantle) model. We considered the center part of five starless cores, with their physical conditions derived from observations. The ice chemistry of oxygen, nitrogen, sulfur, and complex organic molecules (COMs) was analyzed. We found that an ice-depth dimension, measured, e.g., in monolayers, is essential for modeling of chemistry in interstellar ices. Particularly, the H2O:CO:CO2:N2:NH3 ice abundance ratio regulates the production and destruction of minor species. It is suggested that photodesorption during the core-collapse period is responsible for the high abundance of interstellar H2O2 and O2H and other species synthesized on the surface. The calculated abundances of COMs in ice were compared to observed gas-phase values. Smaller activation barriers for CO and H2CO hydrogenation may help explain the production of a number of COMs. The observed abundance of methyl formate HCOOCH3 could be reproduced with a 1 kyr, 20 K temperature spike. Possible desorption mechanisms, relevant for COMs, are gas turbulence (ice exposure to interstellar photons) or a weak shock within the cloud core (grain collisions). To reproduce the observed COM abundances with the present 0D model, 1%-10% of ice mass needs to be sublimated. We estimate that the lifetime for starless cores likely does not exceed 1 Myr. Taurus cores are likely to be younger than their counterparts in most other clouds.

A new chemistry option in WRF-Chem v. 3.4 for the simulation of direct and indirect aerosol effects using VBS: evaluation against IMPACT-EUCAARI data

NASA Astrophysics Data System (ADS)

Tuccella, P.; Curci, G.; Grell, G. A.; Visconti, G.; Crumeyrolle, S.; Schwarzenboeck, A.; Mensah, A. A.

2015-09-01

A parameterization for secondary organic aerosol (SOA) production based on the volatility basis set (VBS) approach has been coupled with microphysics and radiative schemes in the Weather Research and Forecasting model with Chemistry (WRF-Chem) model. The new chemistry option called "RACM-MADE-VBS-AQCHEM" was evaluated on a cloud resolving scale against ground-based and aircraft measurements collected during the IMPACT-EUCAARI (Intensive Cloud Aerosol Measurement Campaign - European Integrated project on Aerosol Cloud Climate and Air quality interaction) campaign, and complemented with satellite data from MODIS. The day-to-day variability and the diurnal cycle of ozone (O3) and nitrogen oxides (NOx) at the surface are captured by the model. Surface aerosol mass concentrations of sulfate (SO4), nitrate (NO3), ammonium (NH4), and organic matter (OM) are simulated with correlations larger than 0.55. WRF-Chem captures the vertical profile of the aerosol mass concentration in both the planetary boundary layer (PBL) and free troposphere (FT) as a function of the synoptic condition, but the model does not capture the full range of the measured concentrations. Predicted OM concentration is at the lower end of the observed mass concentrations. The bias may be attributable to the missing aqueous chemistry processes of organic compounds and to uncertainties in meteorological fields. A key role could be played by assumptions on the VBS approach such as the SOA formation pathways, oxidation rate, and dry deposition velocity of organic condensable vapours. Another source of error in simulating SOA is the uncertainties in the anthropogenic emissions of primary organic carbon. Aerosol particle number concentration (condensation nuclei, CN) is overestimated by a factor of 1.4 and 1.7 within the PBL and FT, respectively. Model bias is most likely attributable to the uncertainties of primary particle emissions (mostly in the PBL) and to the nucleation rate. Simulated cloud condensation nuclei (CCN) are also overestimated, but the bias is more contained with respect to that of CN. The CCN efficiency, which is a characterization of the ability of aerosol particles to nucleate cloud droplets, is underestimated by a factor of 1.5 and 3.8 in the PBL and FT, respectively. The comparison with MODIS data shows that the model overestimates the aerosol optical thickness (AOT). The domain averages (for 1 day) are 0.38 ± 0.12 and 0.42 ± 0.10 for MODIS and WRF-Chem data, respectively. The droplet effective radius (Re) in liquid-phase clouds is underestimated by a factor of 1.5; the cloud liquid water path (LWP) is overestimated by a factor of 1.1-1.6. The consequence is the overestimation of average liquid cloud optical thickness (COT) from a few percent up to 42 %. The predicted cloud water path (CWP) in all phases displays a bias in the range +41-80 %, whereas the bias of COT is about 15 %. In sensitivity tests where we excluded SOA, the skills of the model in reproducing the observed patterns and average values of the microphysical and optical properties of liquid and all phase clouds decreases. Moreover, the run without SOA (NOSOA) shows convective clouds with an enhanced content of liquid and frozen hydrometers, and stronger updrafts and downdrafts. Considering that the previous version of WRF-Chem coupled with a modal aerosol module predicted very low SOA content (secondary organic aerosol model (SORGAM) mechanism) the new proposed option may lead to a better characterization of aerosol-cloud feedbacks.

DC3 Data and Information Page

Atmospheric Science Data Center

2015-03-16

Deep Convective Clouds and Chemistry (DC3) Data and Information The Deep Convective Clouds and Chemistry ( DC3 ) field campaign is investigating the impact of deep, ... processes, on upper tropospheric (UT) composition and chemistry. The primary science objectives are:   To quantify and ...

Water and complex organic chemistry in the cold dark cloud Barnard 5: Observations and Models

NASA Astrophysics Data System (ADS)

Wirström, Eva; Charnley, Steven B.; Taquet, Vianney; Persson, Carina M.

2015-08-01

Studies of complex organic molecule (COM) formation have traditionally been focused on hot cores in regions of massive star formation, where chemistry is driven by the elevated temperatures - evaporating ices and allowing for endothermic reactions in the gas-phase. As more sensitive instruments have become available, the types of objects known to harbour COMs like acetaldehyde (CH3CHO), dimethyl ether (CH3OCH3), methyl formate (CH3OCHO), and ketene (CH2CO) have expanded to include low mass protostars and, recently, even pre-stellar cores. We here report on the first in a new category of objects harbouring COMs: the cold dark cloud Barnard 5 where non-thermal ice desorption induce complex organic chemistry entirely unrelated to local star-formation.Methanol, which only forms efficiently on the surfaces of dust grains, provide evidence of efficient non-thermal desorption of ices in the form of prominent emission peaks offset from protostellar activity and high density tracers in cold molecular clouds. A study with Herschel targeting such methanol emission peaks resulted in the first ever detection of gas-phase water offset from protostellar activity in a dark cloud, at the so called methanol hotspot in Barnard 5.To model the effect a transient injection of ices into the gas-phase has on the chemistry of a cold, dark cloud we have included gas-grain interactions in an existing gas-phase chemical model and connected it to a chemical reaction network updated and expanded to include the formation and destruction paths of the most common COMs. Results from this model will be presented.Ground-based follow-up studies toward the methanol hotspot in B5 have resulted in the detection of a number of COMs, including CH2CO, CH3CHO, CH3OCH3, and CH3OCHO, as well as deuterated methanol (CH2DOH). Observations have also confirmed that COM emission is extended and not localised to a core structure. The implications of these observational and theoretical studies of B5 will be discussed in the context of the gas-grain interaction in dark clouds and its relation to the chemistry of the earliest phases of low-mass star formation.

Coupled Photochemical and Condensation Model for the Venus Atmosphere

NASA Astrophysics Data System (ADS)

Bierson, Carver; Zhang, Xi; Mendonca, Joao; Liang, Mao-Chang

2017-10-01

Ground based and Venus Express observations have provided a wealth of information on the vertical and latitudinal distribution of many chemical species in the Venus atmosphere [1,2]. Previous 1D models have focused on the chemistry of either the lower [3] or middle atmosphere [4,5]. Photochemical models focusing on the sulfur gas chemistry have also been independent from models of the sulfuric acid haze and cloud formation [6,7]. In recent years sulfur-bearing particles have become important candidates for the observed SO2 inversion above 80 km [5]. To test this hypothesis it is import to create a self-consistent model that includes photochemistry, transport, and cloud condensation.In this work we extend the domain of the 1D chemistry model of Zhang et al. (2012) [5] to encompass the region between the surface to 110 km. This model includes a simple sulfuric acid condensation scheme with gravitational settling. It simultaneously solves for the chemistry and condensation allowing for self-consistent cloud formation. We compare the resulting chemical distributions to observations at all altitudes. We have also validated our model cloud mass against pioneer Venus observations [8]. This updated full atmosphere chemistry model is also being applied in our 2D solver (altitude and altitude). With this 2D model we can model how the latitudinal distribution of chemical species depends on the meridional circulation. This allows us to use the existing chemical observations to place constraints on Venus GCMs [9-11].References: [1] Arney et al., JGR:Planets, 2014 [2] Vandaele et al., Icarus 2017 (pt. 1 & 2) [3] Krasnopolsky, Icarus, 2007 [4] Krasnopolsky, Icarus, 2012 [5] Zhang et al., Icarus 2012 [6] Gao et al., Icarus, 2014 [7] Krasnopolsky, Icarus, 2015 [8] Knollenberg and Hunten, JGR:Space Physics, 1980 [9] Lee et al., JGR:Planets, 2007 [10] Lebonnois et al., Towards Understanding the Climate of Venus, 2013 [11] Mendoncca and Read, Planetary and Space Science, 2016

Diffuse cloud chemistry. [in interstellar matter

NASA Technical Reports Server (NTRS)

Van Dishoeck, Ewine F.; Black, John H.

1988-01-01

The current status of models of diffuse interstellar clouds is reviewed. A detailed comparison of recent gas-phase steady-state models shows that both the physical conditions and the molecular abundances in diffuse clouds are still not fully understood. Alternative mechanisms are discussed and observational tests which may discriminate between the various models are suggested. Recent developments regarding the velocity structure of diffuse clouds are mentioned. Similarities and differences between the chemistries in diffuse clouds and those in translucent and high latitude clouds are pointed out.

Cloud processing of gases and aerosols in the Community Multiscale Air Quality (CMAQ) model: Impacts of extended chemistry

EPA Science Inventory

Clouds and fogs can significantly impact the concentration and distribution of atmospheric gases and aerosols through chemistry, scavenging, and transport. This presentation summarizes the representation of cloud processes in the Community Multiscale Air Quality (CMAQ) modeling ...

Cloud Resolving Modeling

NASA Technical Reports Server (NTRS)

Tao, Wei-Kuo

2007-01-01

One of the most promising methods to test the representation of cloud processes used in climate models is to use observations together with cloud-resolving models (CRMs). CRMs use more sophisticated and realistic representations of cloud microphysical processes, and they can reasonably well resolve the time evolution, structure, and life cycles of clouds and cloud systems (with sizes ranging from about 2-200 km). CRMs also allow for explicit interaction between clouds, outgoing longwave (cooling) and incoming solar (heating) radiation, and ocean and land surface processes. Observations are required to initialize CRMs and to validate their results. This paper provides a brief discussion and review of the main characteristics of CRMs as well as some of their major applications. These include the use of CRMs to improve our understanding of: (1) convective organization, (2) cloud temperature and water vapor budgets, and convective momentum transport, (3) diurnal variation of precipitation processes, (4) radiative-convective quasi-equilibrium states, (5) cloud-chemistry interaction, (6) aerosol-precipitation interaction, and (7) improving moist processes in large-scale models. In addition, current and future developments and applications of CRMs will be presented.

New framework for extending cloud chemistry in the Community Multiscale Air Quality (CMAQ) modeling

EPA Science Inventory

Clouds and fogs significantly impact the amount, composition, and spatial distribution of gas and particulate atmospheric species, not least of which through the chemistry that occurs in cloud droplets. Atmospheric sulfate is an important component of fine aerosol mass and in an...

On the Formation of Interstellar Water Ice: Constraints from a Search for Hydrogen Peroxide Ice in Molecular Clouds

NASA Technical Reports Server (NTRS)

Smith, R. G.; Charnely, S. B.; Pendleton, Y. J.; Wright, C. M.; Maldoni, M. M.; Robinson, G.

2011-01-01

Recent surface chemistry experiments have shown that the hydrogenation of molecular oxygen on interstellar dust grains is a plausible formation mechanism, via hydrogen peroxide (H2O2), for the production of water (H2O) ice mantles in the dense interstellar medium. Theoretical chemistry models also predict the formation of a significant abundance of H2O2 ice in grain mantles by this route. At their upper limits, the predicted and experimental abundances are sufficiently high that H2O2 should be detectable in molecular cloud ice spectra. To investigate this further, laboratory spectra have been obtained for H2O2/H2O ice films between 2.5 and 200 micron, from 10 to 180 K, containing 3%, 30%, and 97% H2O2 ice. Integrated absorbances for all the absorption features in low-temperature H2O2 ice have been derived from these spectra. For identifying H2O2 ice, the key results are the presence of unique features near 3.5, 7.0, and 11.3 micron. Comparing the laboratory spectra with the spectra of a group of 24 protostars and field stars, all of which have strong H2O ice absorption bands, no absorption features are found that can definitely be identified with H2O2 ice. In the absence of definite H2O2 features, the H2O2 abundance is constrained by its possible contribution to the weak absorption feature near 3.47 micron found on the long-wavelength wing of the 3 micron H2O ice band. This gives an average upper limit for H2O2, as a percentage of H2O, of 9% +/- 4%. This is a strong constraint on parameters for surface chemistry experiments and dense cloud chemistry models.

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Ehrenfreund, P.; Kuan, Y. J.

2001-01-01

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Ozone destruction through heterogeneous chemistry following the eruption of El Chichon

NASA Technical Reports Server (NTRS)

Hofmann, David J.; Solomon, Susan

1989-01-01

The results of ozone observations at northern midlatitudes in late 1982 through 1983, following the eruption of El Chichon are discussed, together with the observations of other trace gases which may be linked to possible variations in ozone chemistry. These results are related to the in situ aerosol observations following the El Chicon eruption, with particular attention given to data relevant to heterogeneous reactions, such as the aerosol surface area and weight percent H2SO4. It is shown that, at midlatitudes, the observed volcanic-particle surface area reached a maximum of about 50 sq microns/cu m (above a typical background value of about 0.75) at an altitude of 18-20 km in early 1983; this enhancement of surface area is about the same as that encountered in stratospheric clouds in the Antarctic, suggesting a possible basis for ozone depletion through heterogeneous chemistry. The fraction of ozone reduction that may have occurred as a result of heterogeneous chemicl effects is estimated.

Modelling two-way interactions between atmospheric pollution and weather using high-resolution GEM-MACH

NASA Astrophysics Data System (ADS)

Makar, Paul; Gong, Wanmin; Pabla, Balbir; Cheung, Philip; Milbrandt, Jason; Gravel, Sylvie; Moran, Michael; Gilbert, Samuel; Zhang, Junhua; Zheng, Qiong

2013-04-01

The Global Environmental Multiscale (GEM) model is the source of the Canadian government's operational numerical weather forecast guidance, and GEM-MACH is the Canadian operational air-quality forecast model. GEM-MACH comprises GEM and the 'Modelling Air-quality and Chemistry' module, a gas-phase, aqueous-phase and aerosol chemistry and microphysics subroutine package called from within GEM's physics module. The present operational GEM-MACH model is "on-line" (both chemistry and meteorology are part of the same modelling structure) but is not fully coupled (weather variables are provided as inputs to the chemistry, but the chemical variables are not used to modify the weather). In this work, we describe modifications made to GEM-MACH as part of the 2nd phase of the Air Quality Model Evaluation International Initiative, in order to bring the model to a fully coupled status and present the results of initial tests comparing uncoupled and coupled versions of the model to observations for a high-resolution forecasting system. Changes to GEM's cloud microphysics and radiative transfer packages were carried out to allow two-way coupling. The cloud microphysics package used here is the Milbrandt-Yau 2-moment (MY2) bulk microphysics scheme, which solves prognostic equations for the total droplet number concentration and the mass mixing ratios of six hydrometeor categories. Here, we have replaced the original cloud condensation nucleation parameterization of MY2 (empirically relating supersaturation and CCN number) with the aerosol activation scheme of Abdul-Razzak and Ghan (2002). The latter scheme makes use of the particle size and speciation distribution of GEM-MACH's chemistry code as well as meteorological inputs to predict the number of aerosol particles activated to form cloud droplets, which is then used in the MY2 microphysics. The radiative transfer routines of GEM assume a default constant concentration aerosol profile between the surface and 1500m, and a single set of optical properties for extinction, single scattering albedo, and asymmetry factor. Ozone in GEM is taken from a default 2D (latitude-height) monthly climatology. We have replaced the ozone below the model top with the ozone calculated from GEM-MACH's chemistry, and the default optical parameters associated with particulate matter have been replaced by those calculated with a Mie scattering algorithm. These changes were found to have a significant local impact on both weather and air-quality predictions for short-term test runs of 24 hours duration. In that particular case, the maximum number concentration of cloud droplets decreased by an order of magnitude, while the number of raindrops increased by an order of magnitude and changed in spatial distribution, but surface rainfall was found to decrease. The differences in meteorology had a profound effect on local pollutant plume concentrations at specific locations and times. We compare results over a longer time period, using two parallel forecast systems, one with feedbacks between meteorology and chemistry, one without. Both nest GEM-MACH from a North American domain (10 km horizontal grid spacing) to a 1535 x 1360 km, 2.5 km domain. These systems will be evaluated against monitoring networks within the high resolution domain.

Coupling Spectral-bin Cloud Microphysics with the MOSAIC Aerosol Model in WRF-Chem: Methodology and Results for Marine Stratocumulus Clouds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Wenhua; Fan, Jiwen; Easter, Richard C.

Aerosol-cloud interaction processes can be represented more physically with bin cloud microphysics relative to bulk microphysical parameterizations. However, due to computational power limitations in the past, bin cloud microphysics was often run with very simple aerosol treatments. The purpose of this study is to represent better aerosol-cloud interaction processes in the Chemistry version of Weather Research and Forecast model (WRF-Chem) at convection-permitting scales by coupling spectral-bin cloud microphysics (SBM) with the MOSAIC sectional aerosol model. A flexible interface is built that exchanges cloud and aerosol information between them. The interface contains a new bin aerosol activation approach, which replaces themore » treatments in the original SBM. It also includes the modified aerosol resuspension and in-cloud wet removal processes with the droplet loss tendencies and precipitation fluxes from SBM. The newly coupled system is evaluated for two marine stratocumulus cases over the Southeast Pacific Ocean with either a simplified aerosol setup or full-chemistry. We compare the aerosol activation process in the newly-coupled SBM-MOSAIC against the SBM simulation without chemistry using a simplified aerosol setup, and the results show consistent activation rates. A longer time simulation reinforces that aerosol resuspension through cloud drop evaporation plays an important role in replenishing aerosols and impacts cloud and precipitation in marine stratocumulus clouds. Evaluation of the coupled SBM-MOSAIC with full-chemistry using aircraft measurements suggests that the new model works realistically for the marine stratocumulus clouds, and improves the simulation of cloud microphysical properties compared to a simulation using MOSAIC coupled with the Morrison two-moment microphysics.« less

Coupling spectral-bin cloud microphysics with the MOSAIC aerosol model in WRF-Chem: Methodology and results for marine stratocumulus clouds

NASA Astrophysics Data System (ADS)

Gao, Wenhua; Fan, Jiwen; Easter, R. C.; Yang, Qing; Zhao, Chun; Ghan, Steven J.

2016-09-01

Aerosol-cloud interaction processes can be represented more physically with bin cloud microphysics relative to bulk microphysical parameterizations. However, due to computational power limitations in the past, bin cloud microphysics was often run with very simple aerosol treatments. The purpose of this study is to represent better aerosol-cloud interaction processes in the Chemistry version of Weather Research and Forecast model (WRF-Chem) at convection-permitting scales by coupling spectral-bin cloud microphysics (SBM) with the MOSAIC sectional aerosol model. A flexible interface is built that exchanges cloud and aerosol information between them. The interface contains a new bin aerosol activation approach, which replaces the treatments in the original SBM. It also includes the modified aerosol resuspension and in-cloud wet removal processes with the droplet loss tendencies and precipitation fluxes from SBM. The newly coupled system is evaluated for two marine stratocumulus cases over the Southeast Pacific Ocean with either a simplified aerosol setup or full-chemistry. We compare the aerosol activation process in the newly coupled SBM-MOSAIC against the SBM simulation without chemistry using a simplified aerosol setup, and the results show consistent activation rates. A longer time simulation reinforces that aerosol resuspension through cloud drop evaporation plays an important role in replenishing aerosols and impacts cloud and precipitation in marine stratocumulus clouds. Evaluation of the coupled SBM-MOSAIC with full-chemistry using aircraft measurements suggests that the new model works realistically for the marine stratocumulus clouds, and improves the simulation of cloud microphysical properties compared to a simulation using MOSAIC coupled with the Morrison two-moment microphysics.

Using Satellite Observations of Cloud Vertical Distribution to Improve Global Model Estimates of Cloud Radiative Effect on Key Tropospheric Oxidants

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James; Ham, Seung-Hee; Zhang, Bo; Kato, Seiji; Voulgarakis, Apostolos; Chen, Gao; Fairlie, Duncan; Duncan, Bryan; Yantosca, Robert

2017-01-01

Clouds directly affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. This effect is an important component of global tropospheric chemistry-climate interaction, and its understanding is thus essential for predicting the feedback of climate change on tropospheric chemistry.

Why Interstellar Ices Can Be Considered As Precursors For Prebiotic Chemistry

NASA Astrophysics Data System (ADS)

Hendecourt, Louis Le Sergeant d.; de Marcellus, Pierre; Meinert, Cornelia; Myrgorodska, Iuliia; Nahon, Laurent; Modica, Paola; Buhse, Thomas; Meierhenrich, Uwe J.

2015-08-01

Interstellar ices made of simple molecules (H2O, CO, CO2, CH3OH, NH3, CH4…) are abundant species observed in molecular clouds where stars and planetary systems form. Since the constitutive elements (H, O, C, N, S, P) are the most cosmically abundant and condensible, they favor the making of ices on grains. In the mantles formed, a rich organic chemistry develops, thanks to the protective nature of the grains. This chemistry leads to a high complexity. Radical chemistry generated by photo/thermo-chemical processes on the surfaces, leaves to the formation of organic residues as those produced in our laboratory using ice templates, and further studied, using methods that pertain mostly to analytical chemistry. The organic material formed may resemble the Soluble Organic Matter observed in pristine meteorites. From numerous amino acids [1], aldehydes and sugars [2] detected in these residues to chiral molecules and enantiomeric excesses produced by Vacuum Ultra-Violet Circularly Polarized Light from synchrotron radiation [3], one might seriously ask whether the chemistry of molecular clouds out of which stars, planetary systems and debris form, may not be seriously considered as the precursor of prebiotic chemistry in a given environment such as the surface of a telluric planet. I will present the general frame of these experiments in relation to the possibillity of feeding of the necessary prebiotic chemistry for the origin of life. Certainly, prebiotic chemistry is very different in itself than astrochemistry but the starting bricks issued from astrochemistry may well be necessary for the possibility of the emergence of life on planets under certain assumptions I will briefly discuss.REFERENCES[1] Meinert, C., Filippi, J.-J., de Marcellus, P., Le Sergeant d’Hendecourt, L. and Meierhenrich, U.J., ChemPlusChem, 77, 186-191 (2012).[2] de Marcellus, P., Meinert, C., Myrgorodska, I., Nahon, L., Buhse, T., Le Sergeantd’Hendecourt, L., Meierhenrich, U.J., PNAS, January 12th, 2015[3] Modica, P., Meinert, C. de Marcellus, Nahon, L., Meierhenrich, U.J., Le Sergeant d’Hendecourt, L. Astrophys.J, 788, 79

A framework for expanding aqueous chemistry in the ...

EPA Pesticide Factsheets

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM − KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM − KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from bio

Atmosphere, ocean, and land: Critical gaps in Earth system models

NASA Technical Reports Server (NTRS)

Prinn, Ronald G.; Hartley, Dana

1992-01-01

We briefly review current knowledge and pinpoint some of the major areas of uncertainty for the following fundamental processes: (1) convection, condensation nuclei, and cloud formation; (2) oceanic circulation and its coupling to the atmosphere and cryosphere; (3) land surface hydrology and hydrology-vegetation coupling; (4) biogeochemistry of greenhouse gases; and (5) upper atmospheric chemistry and circulation.

Solid-State Photochemistry as a Formation Mechanism for Titan's Stratospheric C4N2 Ice Clouds

NASA Technical Reports Server (NTRS)

Anderson, C. M.; Samuelson, R. E.; Yung, Y. L.; McLain, J. L.

2016-01-01

We propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid-state photochemistry occurring within extant ice cloud particles of HCN-HC3N mixtures. This formation process resembles the halogen-induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 per centimeter ice emission feature demonstrates, this solid-state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

Satellite view of the extreme haze clouds over China

NASA Astrophysics Data System (ADS)

Minghui, T.; Chen, L.; Wang, Z.

2013-12-01

Minghui Tao*, Liangfu Chen, Zifeng Wang State Key Laboratory of Remote Sensing Science, Jointly Sponsored by Institute of Remote Sensing and Digital Earth of Chinese Academy of Sciences and Beijing Normal University, Beijing 100101, China *Email: tmh1985@163.com ABSTRACT: In the past decades, great increases in anthropogenic emissions have caused dramatic changes in air quality and regional climate in China, which are further complicated by the natural processes such as dust events and atmospheric dynamics such as variations in intensity of the Asian monsoon. The common urban photochemistry smog, haze, and fog-haze pollution lead to poor air quality in major cities in eastern and middle parts of China. On the other hand, the heavy aerosol loading exerts marked influences on radiation, clouds, and precipitation over China. Satellites usually observed widespread haze clouds over eastern China. In most of previous studies, the dense haze clouds were directly connected with accumulation of anthropogenic emissions. However, satellite observations show that formation processes of haze clouds and local pollution near surface were different. Understanding the connections and interactions between haze clouds and local anthropogenic emissions is essential in chemistry and climate modeling of the aerosols over China. In January 2013, durative haze clouds covered most parts of eastern China, leading to extreme pollution events in many cities. With integrated A-train satellite observations and ground measurements, we investigated variations, optical properties, vertical structures as well as formation process of the extreme haze clouds over eastern China. Satellite-surface results were compared to analyze relations between the haze clouds and surface pollution. Different from traditional views, our results reveal that variation and formation of the haze clouds were driven by large-scale natural processes rather than local anthropogenic emissions. Figure 1. Aqua MODIS true color images of the haze clouds over eastern China on Jan 10, 2013.

3CPO, Cloud Chemistry and Cloud Physics Organization: Data index, June 1988

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tichler, J.; Norden, K.; Sharp, D.

This document is an index of the data that was collected as part of the Cloud Chemistry and Cloud Physics Organization (3CPO) cooperative convective storms program which took place in June 1988 in east central Illinois. The objective of 3CPO was to ''assemble at a common time and location, the necessary measurement facilities to provide a previously unattained description of convective storm characteristics in polluted environments. 6 figs., 2 tabs.

Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

NASA Technical Reports Server (NTRS)

Bergin, E. A.; Langer, W. D.; Goldsmith, P. F.

1995-01-01

We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

The Deep South Clouds & Aerosols project: Improving the modelling of clouds in the Southern Ocean region

NASA Astrophysics Data System (ADS)

Morgenstern, Olaf; McDonald, Adrian; Harvey, Mike; Davies, Roger; Katurji, Marwan; Varma, Vidya; Williams, Jonny

2016-04-01

Southern-Hemisphere climate projections are subject to persistent climate model biases affecting the large majority of contemporary climate models, which degrade the reliability of these projections, particularly at the regional scale. Southern-Hemisphere specific problems include the fact that satellite-based observations comparisons with model output indicate that cloud occurrence above the Southern Ocean is substantially underestimated, with consequences for the radiation balance, sea surface temperatures, sea ice, and the position of storm tracks. The Southern-Ocean and Antarctic region is generally characterized by an acute paucity of surface-based and airborne observations, further complicating the situation. In recognition of this and other Southern-Hemisphere specific problems with climate modelling, the New Zealand Government has launched the Deep South National Science Challenge, whose purpose is to develop a new Earth System Model which reduces these very large radiative forcing problems associated with erroneous clouds. The plan is to conduct a campaign of targeted observations in the Southern Ocean region, leveraging off international measurement campaigns in this area, and using these and existing measurements of cloud and aerosol properties to improve the representation of clouds in the nascent New Zealand Earth System Model. Observations and model development will target aerosol physics and chemistry, particularly sulphate, sea salt, and non-sulphate organic aerosol, its interactions with clouds, and cloud microphysics. The hypothesis is that the cloud schemes in most GCMs are trained on Northern-Hemisphere data characterized by substantial anthropogenic or terrestrial aerosol-related influences which are almost completely absent in the Deep South.

Time-dependent interstellar chemistry

NASA Technical Reports Server (NTRS)

Glassgold, A. E.

1985-01-01

Some current problems in interstellar chemistry are considered in the context of time-dependent calculations. The limitations of steady-state models of interstellar gas-phase chemistry are discussed, and attempts to chemically date interstellar clouds are reviewed. The importance of studying the physical and chemical properties of interstellar dust is emphasized. Finally, the results of a series of studies of collapsing clouds are described.

Gas-grain chemical models of star-forming molecular clouds as constrained by ISO and SWAS observations

NASA Astrophysics Data System (ADS)

Charnley, S. B.; Rodgers, S. D.; Ehrenfreund, P.

2001-11-01

We have investigated the gaseous and solid state molecular composition of dense interstellar material that periodically experiences processing in the shock waves associated with ongoing star formation. Our motivation is to confront these models with the stringent abundance constraints on CO2, H2O and O2, in both gas and solid phases, that have been set by ISO and SWAS. We also compare our results with the chemical composition of dark molecular clouds as determined by ground-based telescopes. Beginning with the simplest possible model needed to study molecular cloud gas-grain chemistry, we only include additional processes where they are clearly required to satisfy one or more of the ISO-SWAS constraints. When CO, N2 and atoms of N, C and S are efficiently desorbed from grains, a chemical quasi-steady-state develops after about one million years. We find that accretion of CO2 and H2O cannot explain the [CO2/H2O]ice ISO observations; as with previous models, accretion and reaction of oxygen atoms are necessary although a high O atom abundance can still be derived from the CO that remains in the gas. The observational constraints on solid and gaseous molecular oxygen are both met in this model. However, we find that we cannot explain the lowest H2O abundances seen by SWAS or the highest atomic carbon abundances found in molecular clouds; additional chemical processes are required and possible candidates are given. One prediction of models of this type is that there should be some regions of molecular clouds which contain high gas phase abundances of H2O, O2 and NO. A further consequence, we find, is that interstellar grain mantles could be rich in NH2OH and NO2. The search for these regions, as well as NH2OH and NO2 in ices and in hot cores, is an important further test of this scenario. The model can give good agreement with observations of simple molecules in dark molecular clouds such as TMC-1 and L134N. Despite the fact that S atoms are assumed to be continously desorbed from grain surfaces, we find that the sulphur chemistry independently experiences an ``accretion catastrophe''. The S-bearing molecular abundances cease to lie within the observed range after about 3 x 106 years and this indicates that there may be at least two efficient surface desorption mechanisms operating in dark clouds - one quasi-continous and the other operating more sporadically on this time-scale. We suggest that mantle removal on short time-scales is mediated by clump dynamics, and by the effects of star formation on longer time-scales. The applicability of this type of dynamical-chemical model for molecular cloud evolution is discussed and comparison is made with other models of dark cloud chemistry.

The Physics and Chemistry of Small Translucent Molecular Clouds. VII. SO + and H 2S

NASA Astrophysics Data System (ADS)

Turner, B. E.

1996-09-01

In this third paper on sulfur species, we have conducted a survey of SO+ (two transitions) and H2S (one transition) in our standard samples of 11 cirrus cores and 27 Clemens-Barvainis translucent objects whose structures and chemistry have been studied earlier in this series. SO+(2II½, J = 3/2-1/2) is seen weakly in 12 objects, while H2S (110 -101) is detected quite strongly in 31 objects. These results are modeled in terms of our previous hydrostatic equilibrium and n ˜r-α structures together with other chemical and physical properties derived earlier. The typical H2S fractional abundance is large, ˜1 × 10-8, and increases monotonically with increasing extinction in the 1.2-2.7 mag range (edge-to-center). Thus H2S displays the same characteristic transition between diffuse and dense cloud chemistry as do SO, SO2, CS, HCS +, HCO +, and other species studied in this series. By contrast, the SO + abundances are small, 1 × 10-9, and exhibit a marginal decrease with increasing extinction. The simple ion-molecule network as used by Turner for sulfur chemistry includes the sulfur hydride species and predicts the observed parameters of SO+ but predicts an H2S abundance 2 orders of magnitude less than observed. Of the 10 species presently analyzed in detail in the translucent cores, H2S is only the second (along with H2CO) that fails to be explained in detail by quiescent cloud ion-molecule chemistry. Various catalytic models of H2S on grains are discussed. Photocatalysis of H2S is found capable of producing the observed abundances but only for sizable accreted mantles. Other types of surface chemistry are also successful but are close to the limits of possible efficiencies. We have detected OCS and H2CS in one object, CB 17, with abundances of 1 × 10-9 and 7 × 10-9 respectively. Our ion-molecule model has been expanded to include OCS and H2CS chemistry. We find that the model fits observed abundances within a factor of 3 for both species.

Users' instructions for the NASA/MSFC cloud-rise preprocessor program, version 6, and the NASA/MSFC multilayer diffusion program, version 6: Research version for Univac 1108 system

NASA Technical Reports Server (NTRS)

Bjorklund, J. R.

1978-01-01

The cloud-rise preprocessor and multilayer diffusion computer programs were used by NASA in predicting concentrations and dosages downwind from normal and abnormal launches of rocket vehicles. These programs incorporated: (1) the latest data for the heat content and chemistry of rocket exhaust clouds; (2) provision for the automated calculation of surface water pH due to deposition of HCl from precipitation scavenging; (3) provision for automated calculation of concentration and dosage parameters at any level within the vertical grounds for which meteorological inputs have been specified; and (4) provision for execution of multiple cases of meteorological data. Procedures used to automatically calculate wind direction shear in a layer were updated.

Boundary Conditions for the Paleoenvironment: Chemical and Physical Processes in the Pre-Solar Nebula

NASA Technical Reports Server (NTRS)

Irvine, William M.; Schloerb, F. Peter

1997-01-01

The basic theme of this program is the study of molecular complexity and evolution in interstellar clouds and in primitive solar system objects. Research has included the detection and study of a number of new interstellar molecules and investigation of reaction pathways for astrochemistry from a comparison of theory and observed molecular abundances. The latter includes studies of cold, dark clouds in which ion-molecule chemistry should predominate, searches for the effects of interchange of material between the gas and solid phases in interstellar clouds, unbiased spectral surveys of particular sources, and systematic investigation of the interlinked chemistry and physics of dense interstellar clouds. In addition, the study of comets has allowed a comparison between the chemistry of such minimally thermally processed objects and that of interstellar clouds, shedding light on the evolution of the biogenic elements during the process of solar system formation.

Lower mass limit of an evolving interstellar cloud and chemistry in an evolving oscillatory cloud

NASA Technical Reports Server (NTRS)

Tarafdar, S. P.

1986-01-01

Simultaneous solution of the equation of motion, equation of state and energy equation including heating and cooling processes for interstellar medium gives for a collapsing cloud a lower mass limit which is significantly smaller than the Jeans mass for the same initial density. The clouds with higher mass than this limiting mass collapse whereas clouds with smaller than critical mass pass through a maximum central density giving apparently similar clouds (i.e., same Av, size and central density) at two different phases of its evolution (i.e., with different life time). Preliminary results of chemistry in such an evolving oscillatory cloud show significant difference in abundances of some of the molecules in two physically similar clouds with different life times. The problems of depletion and short life time of evolving clouds appear to be less severe in such an oscillatory cloud.

The relationships among cloud microphysics, chemistry, and precipitation rate in cold mountain clouds

NASA Astrophysics Data System (ADS)

Borys, Randolph D.; Lowenthal, Douglas H.; Mitchell, David L.

A study was conducted to examine the relationships among air pollutant loadings, cloud microphysics, and snowfall rates in cold mountain clouds. It was hypothesized that variations in pollutant loadings would be reflected in shifts in the cloud droplet size distribution. A field program was conducted at Storm Peak Laboratory (SPL) at an elevation of 3210 m MSL in northwestern Colorado. Cold precipitating clouds were sampled during January, 1995. Cloud water was collected and analyzed for major ion and trace element chemistry. Cloud droplet concentrations and size were measured continuously using a PMS FSSP-100. The results indicate a direct relationship between clear-air equivalent (CAE) sulfate concentrations in cloud water and cloud droplet concentrations, an indirect relationship between droplet number and droplet size, a direct relationship between droplet size and snowfall rate, and an indirect relationship between CAE sulfate concentration and snowfall rate.

A Model and Satellite-Based Analysis of the Tropospheric Ozone Distribution in Clear Versus Convectively Cloudy Conditions

NASA Technical Reports Server (NTRS)

Strode, Sarah A.; Douglass, Anne R.; Ziemke, Jerald R.; Manyin, Michael; Nielsen, J. Eric; Oman, Luke D.

2017-01-01

Satellite observations of in-cloud ozone concentrations from the Ozone Monitoring Instrument and Microwave Limb Sounder instruments show substantial differences from background ozone concentrations. We develop a method for comparing a free-running chemistry-climate model (CCM) to in-cloud and background ozone observations using a simple criterion based on cloud fraction to separate cloudy and clear-sky days. We demonstrate that the CCM simulates key features of the in-cloud versus background ozone differences and of the geographic distribution of in-cloud ozone. Since the agreement is not dependent on matching the meteorological conditions of a specific day, this is a promising method for diagnosing how accurately CCMs represent the relationships between ozone and clouds, including the lower ozone concentrations shown by in-cloud satellite observations. Since clouds are associated with convection as well as changes in chemistry, we diagnose the tendency of tropical ozone at 400 hPa due to chemistry, convection and turbulence, and large-scale dynamics. While convection acts to reduce ozone concentrations at 400 hPa throughout much of the tropics, it has the opposite effect over highly polluted regions of South and East Asia.

Prebiotic chemistry in clouds

NASA Technical Reports Server (NTRS)

Oberbeck, Verne R.; Marshall, John; Shen, Thomas

1991-01-01

The chemical evolution hypothesis of Woese (1979), according to which prebiotic reactions occurred rapidly in droplets in giant atmospheric reflux columns was criticized by Scherer (1985). This paper proposes a mechanism for prebiotic chemistry in clouds that answers Scherer's concerns and supports Woese's hypothesis. According to this mechanism, rapid prebiotic chemical evolution was facilitated on the primordial earth by cycles of condensation and evaporation of cloud drops containing clay condensation nuclei and nonvolatile monomers. For example, amino acids supplied by, or synthesized during entry of meteorites, comets, and interplanetary dust, would have been scavenged by cloud drops containing clay condensation nuclei and would be polymerized within cloud systems during cycles of condensation, freezing, melting, and evaporation of cloud drops.

New Frontiers Science at Venus from Orbit plus Atmospheric Gas Sampling

NASA Astrophysics Data System (ADS)

Smrekar, Suzanne; Dyar, Melinda; Hensley, Scott; Helbert, Joern; VOX Science and Engineering Teams

2017-10-01

Venus remains the most Earth-like body in terms of size, composition, surface age, and insulation. Venus Origins Explorer (VOX) determines how Earth’s twin diverged, and enables breakthroughs in our understanding of rocky planet evolution and habitability. At the time of the Decadal Survey the ability to map mineralogy from orbit (Helbert et al.) and present-day radar techniques to detect active deformation were not fully appreciated. VOX leverages these methods and in-situ noble gases to answer New Frontiers science objectives:1. Atmospheric physics/chemistry: noble gases and isotopes to constrain atmospheric sources, escape processes, and integrated volcanic outgassing; global search for current volcanically outgassed water.2. Past hydrological cycles: global tessera composition to determine the role of volatiles in crustal formation.3. Crustal physics/chemistry: global crustal mineralogy/chemistry, tectonic processes, heat flow, resolve the catastrophic vs. equilibrium resurfacing debate, active geologic processes and possible crustal recycling.4. Crustal weathering: surface-atmosphere weathering reactions from redox state and the chemical equilibrium of the near-surface atmosphere.5. Atmospheric properties/winds: map cloud particle modes and their temporal variations, and track cloud-level winds in the polar vortices.6. Surface-atmosphere interactions: chemical reactions from mineralogy; weathering state between new, recent and older flows; possible volcanically outgassed water.VOX’s Atmosphere Sampling Vehicle (ASV) dips into and samples the well-mixed atmosphere, using Venus Original Constituents Experiment (VOCE) to measure noble gases. VOX’s orbiter carries the Venus Emissivity Mapper (VEM) and the Venus Interferometric Synthetic Aperture Radar (VISAR), and maps the gravity field using Ka-band tracking.VOX is the logical next mission to Venus because it delivers: 1) top priority atmosphere, surface, and interior science; 2) key global data for comparative planetology; 3) high-resolution topography, composition, and imaging to optimize future landers; 4) opportunities for revolutionary discoveries with a 3-year long mission, proven implementation and 44 Tb of data.

Mesoscale modeling of smoke radiative feedback over the Sahel region

NASA Astrophysics Data System (ADS)

Yang, Z.; Wang, J.; Ichoku, C. M.; Ellison, L.; Zhang, F.; Yue, Y.

2013-12-01

This study employs satellite observations and a fully-coupled meteorology-chemistry-aerosol model, Weather Research and Forecasting model with Chemistry (WRF-Chem) to study the smoke radative feedback on surface energy budget, boundary layer processes, and atmospheric lapse rate in February 2008 over the Sahel region. The smoke emission inventories we use come from various sources, including but not limited to the Fire Locating and Modeling of Burning Emissions (FLAMBE) developed by NRL and the Fire Energetic and Emissions Research (FEER) developed by NASA GSFC. Model performance is evaluated using numerous satellite and ground-based datasets: MODIS true color images, ground-based Aerosol Optical Depth (AOD) measurements from AERONET, MODIS AOD retrievals, and Cloud-Aerosol Lidar data with Orthogonal Polarization (CALIOP) atmospheric backscattering and extinction products. Specification of smoke injection height of 650 m in WRF-Chem yields aerosol vertical profiles that are most consistent with CALIOP observations of aerosol layer height. Statistically, 5% of the CALIPSO valid measurements of aerosols in February 2008 show aerosol layers either above the clouds or between the clouds, reinforcing the importance of the aerosol vertical distribution for quantifying aerosol impact on climate in the Sahel region. The results further show that the smoke radiative feedbacks are sensitive to assumptions of black carbon and organic carbon ratio in the particle emission inventory. Also investigated is the smoke semi-direct effect as a function of cloud fraction.

Hydroxymethane sulfonate as a possible explanation for observed high levels of particulate sulfur during severe winter haze episodes in Beijing, China.

NASA Astrophysics Data System (ADS)

Moch, J.; Jacob, D.; Mickley, L. J.; Cheng, Y.; Li, M.; Munger, J. W.; Wang, Y.

2017-12-01

Observed PM2.5 during severe winter haze in Beijing, China, may reach levels as high as 880 μg m-3, with sulfur compounds contributing significantly to PM2.5 composition. Such sulfur has been traditionally assumed to be sulfate, even though models fail to generate such large sulfate enhancements under cold and hazy conditions. We show that particulate sulfur in wintertime Beijing possibly occurs as an S(IV)-HCHO adduct, hydroxymethane sulfonate (HMS), formed by reaction of aqueous-phase HCHO and S(IV) in cloud droplets. We use a 1-D chemistry model extending from the surface through the boundary layer to examine the potential role of HMS during the Beijing haze events of December 2011 and January 2013. Observed and assimilated meteorological fields including cloud liquid water were applied to the model, and we test the sensitivity of HMS formation to cloud pH and ambient SO2 and HCHO. Surface observations from the two haze events show excess ammonium in the aerosol, indicating cloud pH may be relatively high. Model results show that once cloud pH exceeds 4.5, HMS can accumulate rapidly, reaching a few hundred μg m-3 in a few hours. The timing of HMS formation is controlled by the presence of cloud liquid water, with eddy driven diffusion bringing HMS to the surface. The magnitude of HMS peaks is limited by the supply of HCHO. HMS episodes in the model end gradually over 1-3 days as fresh air is entrained into the boundary layer; in observations these episodes typically end when increasing wind speeds destabilize the boundary layer and disperses pollution. We find that consideration of HMS as a source of particulate sulfur significantly improves model match with observations. For example, assuming cloud pH of 5 and average surface SO2 and HCHO levels of 50 ppb and 5.5 ppb, we calculate mean HMS as 43.8 μg m-3 in January 2013, within 7 μg m-3 of observed particulate sulfur. Our 1-D model also captures the timing and magnitude of peak particulate sulfur in January 2013, with HMS approaching 100 μg m-3 during episodes. In contrast, a GEOS-Chem 3-D simulation without HMS chemistry yields peak particulate sulfur of 20 μg m-3. Our findings suggest that SO2 is not the limiting factor in winter haze events in Beijing and that, in order to reduce severe winter haze in this region, policymakers may need to address HCHO sources such as transportation.

Turbulent transport and chemistry of isoprene and monoterpenes within and above tropical forest canopies

NASA Astrophysics Data System (ADS)

Gerken, T.; Chamecki, M.; Fuentes, J. D.; Stoy, P. C.; Trowbridge, A.; Wei, D.

2016-12-01

The Amazon rainforest and other rainforests emit large quantities of biogenic volatile organic compounds (BVOCs), including isoprene and monoterpenes, which react with and produce atmospheric oxidants such as ozone and the hydroxyl radical. Some of the resulting reaction products condense to form secondary organic aerosols, which due to the typically clean tropical air can make up a large portion of the total atmospheric aerosols and may thus impact cloud development and regional climate. To better understand the role of tropical forests on cloud development and climate, it is necessary to quantify not only BVOC emissions, but also turbulent transport and the resulting atmospheric chemistry within both the forest canopy and atmospheric boundary-layer. To date, most research has ignored within-canopy chemical processes that are typically not resolved in regional models that treat the forest as a lower boundary condition. We use canopy-resolving Large Eddy Simulation (LES) to study the role of turbulence and chemistry in the isoprene lifetime under conditions observed during a 2014 field campaign in central Amazonia. The LES includes a simple chemical mechanism for the oxidation of isoprene and aggregated monoterpenes (34 reactions), which we use to quantify the impact of within-canopy and boundary-layer processes on the transport and air chemistry of isoprene, monoterpenes, and primary reaction products on their export at the top of the boundary layer. LES results show air parcel residence times in the dense Amazon rainforest, which govern the time available for in-canopy reactions, to range from a few seconds near the canopy top to 30 minutes near the ground. Such residence times are comparable to chemical lifetimes of many reactive species and the convective eddy turnover timescale. Additionally, monoterpene oxidation with ambient ozone levels can increase within-canopy hydroxyl radical concentrations from 5 x 104 to 3 x 105 radicals cm-3, thus greatly increasing the oxidative capacity of the near surface air; within-canopy oxidation is significant for isoprene (5%) and monoterpene chemistry (25%). Results demonstrate that monoterpene chemistry - in addition to isoprene chemistry - needs to be considered when investigating the role of BVOCs to surface-atmosphere interactions in tropical rainforests.

The Postshock Chemical Lifetimes of Outflow Tracers and a Possible New Mechanism to Produce Water Ice Mantles

NASA Technical Reports Server (NTRS)

Bergin, Edwin A.; Melnick, Gary J.; Neufeld, David A.

1998-01-01

We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of the chemical legacy in the wake of C-type shocks. We concentrate this study on the chemistry of H2O and O2, two molecules which are predicted to have abundances that are significantly affected in shock-heated gas. Two models are presented: (1) a three-stage model of preshock, shocked, and postshock gas; and (2) a Monte Carlo cloud simulation where we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. For both models we separately examine the pure gas-phase chemistry as well as the chemistry including the interactions of molecules with grain surfaces. In agreement with previous studies, we find that shock velocities in excess of 10 km/s are required to convert all of the oxygen not locked in CO into H2O before the gas has an opportunity to cool. For pure gas phase models the lifetime of the high water abundances, or "H2O legacy," in the postshock gas is approximately (4-7) x 10(exp 5) yr, independent of the gas density. A density dependence for the lifetime of H2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. Through the Monte Carlo cloud simulation we demonstrate that the time-average abundance of H2O, the weighted average of the amount of time gas spends in preshock, shock, and postshock stages, is a sensitive function of the frequency of shocks. Thus we predict that the abundance of H2O, and to a lesser extent O2, can be used to trace the history of shock activity in molecular gas. We use previous large-scale surveys of molecular outflows to constrain the frequency of 10 km/s shocks in regions with varying star formation properties and discuss the observations required to test these results. We discuss the postshock lifetimes for other possible outflow tracers (e.g., SiO and CH3OH) and show that the differences between the lifetimes for various tracers can produce potentially observable chemical variations between younger and older outflows. For gas-grain models we find that the abundance of water-ice on grain surfaces can be quite large and is comparable to that observed in molecular clouds. This offers a possible alternative method to create water mantles without resorting to grain surface chemistry: gas heating and chemical modification due to a C-type shock and subsequent depletion of the gas-phase species onto grain mantles.

Carbon Chemistry in Transitional Clouds from the GOT C+ Survey of CII 158 micron Emission in the Galactic Plane

NASA Astrophysics Data System (ADS)

Langer, W. D.; Velusamy, T.; Pineda, J.; Willacy, K.; Goldsmith, P. F.

2011-05-01

In understanding the lifecycle and chemistry of the interstellar gas, the transition from diffuse atomic to molecular gas clouds is a very important stage. The evolution of carbon from C+ to C0 and CO is a fundamental part of this transition, and C+ along with its carbon chemistry is a key diagnostic. Until now our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the dense molecular H2 phase traced by CO. However, we have generally been missing an important layer in diffuse and transition clouds, which is denoted by the warm "dark gas'', that is mostly H2 and little HI and CO, and is best traced with C+. Here, we discuss the chemistry in the transition from C+ to C0 and CO in these clouds as understood by a survey of the CII 1.9 THz (158 micron) line from a sparse survey of the inner galaxy over about 40 degrees in longitude as part of the Galactic Observations of Terahertz C+ (GOT C+) program, a Herschel Space Observatory Open Time Key Program to study interstellar clouds by sampling ionized carbon. Using the first results from GOT C+ along 11 LOSs, in a sample of 53 transition clouds, Velusamy, Langer et al. (A&A 521, L18, 2010) detected an excess of CII intensities indicative of a thick H2 layer (a significant warm H2, "dark gas'' component) around the 12CO core. Here we present a much larger, statistically significant sample of a few hundred diffuse and transition clouds traced by CII, along with auxiliary HI and CO data in the inner Galaxy between l=-30° and +30°. Our new and more extensive sample of transition clouds is used to elucidate the time dependent physical and carbon chemical evolution of diffuse to transition clouds, and transition layers. We consider the C+ to CO conversion pathways such as H++ O and C+ + H2 chemistry for CO production to constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse transition clouds.

Incorporation of new particle formation and early growth treatments into WRF/Chem: Model improvement, evaluation, and impacts of anthropogenic aerosols over East Asia

NASA Astrophysics Data System (ADS)

Cai, Changjie; Zhang, Xin; Wang, Kai; Zhang, Yang; Wang, Litao; Zhang, Qiang; Duan, Fengkui; He, Kebin; Yu, Shao-Cai

2016-01-01

New particle formation (NPF) provides an important source of aerosol particles and cloud condensation nuclei, which may result in enhanced cloud droplet number concentration (CDNC) and cloud shortwave albedo. In this work, several nucleation parameterizations and one particle early growth parameterization are implemented into the online-coupled Weather Research and Forecasting model coupled with chemistry (WRF/Chem) to improve the model's capability in simulating NPF and early growth of ultrafine particles over East Asia. The default 8-bin over the size range of 39 nm-10 μm used in the Model for Simulating Aerosol Interactions and Chemistry aerosol module is expanded to the 12-bin over 1 nm-10 μm to explicitly track the formation and evolution of new particles. Although model biases remain in simulating H2SO4, condensation sink, growth rate, and formation rate, the evaluation of July 2008 simulation identifies a combination of three nucleation parameterizations (i.e., COMB) that can best represent the atmospheric nucleation processes in terms of both surface nucleation events and the resulting vertical distribution of ultrafine particle concentrations. COMB consists of a power law of Wang et al. (2011) based on activation theory for urban areas in planetary boundary layer (PBL), a power law of Boy et al. (2008) based on activation theory for non-urban areas in PBL, and the ion-mediated nucleation parameterization of YU10 for above PBL. The application and evaluation of the improved model with 12-bin and the COMB nucleation parameterization in East Asia during January, April, July, and October in 2001 show that the model has an overall reasonably good skill in reproducing most observed meteorological variables and surface and column chemical concentrations. Relatively large biases in simulated precipitation and wind speeds are due to inaccurate surface roughness and limitations in model treatments of cloud formation and aerosol-cloud-precipitation interactions. Large biases in the simulated surface concentrations of PM10, NOx, CO, SO2, and VOCs at some sites are due in part to possible underestimations of emissions and in part to inaccurate meteorological predictions. The simulations of 2001 show that anthropogenic aerosols can increase aerosol optical depth by 64.0-228.3%, CDNC by 40.2-76.4%, and cloud optical thickness by 14.3-25.3%; they can reduce surface net shortwave radiation by up to 42.5-52.8 W m-2, 2-m temperature by up to 0.34-0.83 °C, and PBL height by up to 76.8-125.9 m. Such effects are more significant than those previously reported for the U.S. and Europe.

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Yokelson, R. J.; Singh, H. B.; Hobbs, P. V.; Crawford, J. H.; Iraci, L. T.

2004-01-01

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

The influence of an extensive dust event on snow chemistry in the southern Rocky Mountains

Treesearch

Charles Rhoades; Kelly Elder; E. Greene

2010-01-01

In mid-February 2006, windstorms in Arizona, Utah, and western Colorado generated a dust cloud that distributed a layer of dust across the surface of the snowpack throughout much of the Colorado Rockies; it remained visible throughout the winter. We compared the chemical composition of snowfall and snowpack collected during and after the dust deposition event with pre-...

The chemistry of dense interstellar clouds

NASA Technical Reports Server (NTRS)

Irvine, W. M.

1991-01-01

The basic theme of this program is the study of molecular complexity and evolution in interstellar and circumstellar clouds incorporating the biogenic elements. Recent results include the identification of a new astronomical carbon-chain molecule, C4Si. This species was detected in the envelope expelled from the evolved star IRC+10216 in observations at the Nobeyama Radio Observatory in Japan. C4Si is the carrier of six unidentified lines which had previously been observed. This detection reveals the existence of a new series of carbon-chain molecules, C sub n Si (n equals 1, 2, 4). Such molecules may well be formed from the reaction of Si(+) with acetylene and acetylene derivatives. Other recent research has concentrated on the chemical composition of the cold, dark interstellar clouds, the nearest dense molecular clouds to the solar system. Such regions have very low kinetic temperatures, on the order of 10 K, and are known to be formation sites for solar-type stars. We have recently identified for the first time in such regions the species of H2S, NO, HCOOH (formic acid). The H2S abundance appears to exceed that predicted by gas-phase models of ion-molecule chemistry, perhaps suggesting the importance of synthesis on grain surfaces. Additional observations in dark clouds have studied the ratio of ortho- to para-thioformaldehyde. Since this ratio is expected to be unaffected by both radiative and ordinary collisional processes in the cloud, it may well reflect the formation conditions for this molecule. The ratio is observed to depart from that expected under conditions of chemical equilibrium at formation, perhaps reflecting efficient interchange between cold dust grains in the gas phase.

A new chemistry option in WRF/Chem v. 3.4 for the simulation of direct and indirect aerosol effects using VBS: evaluation against IMPACT-EUCAARI data

NASA Astrophysics Data System (ADS)

Tuccella, P.; Curci, G.; Grell, G. A.; Visconti, G.; Crumeroylle, S.; Schwarzenboeck, A.; Mensah, A. A.

2015-02-01

A parameterization for secondary organic aerosol (SOA) production based on the volatility basis set (VBS) approach has been coupled with microphysics and radiative scheme in WRF/Chem model. The new chemistry option called "RACM/MADE/VBS" was evaluated on a cloud resolving scale against ground-based and aircraft measurements collected during the IMPACT-EUCAARI campaign, and complemented with satellite data from MODIS. The day-to-day variability and the diurnal cycle of ozone (O3) and nitrogen oxides (NOx) at the surface is captured by the model. Surface aerosol mass of sulphate (SO4), nitrate (NO3), ammonium (NH4), and organic matter (OM) is simulated with a correlation larger than 0.55. WRF/Chem captures the vertical profile of the aerosol mass in both the planetary boundary layer (PBL) and free troposphere (FT) as a function of the synoptic condition, but the model does not capture the full range of the measured concentrations. Predicted OM concentration is at the lower end of the observed mass. The bias may be attributable to the missing aqueous chemistry processes of organic compounds, the uncertainties in meteorological fields, the assumption on the deposition velocity of condensable organic vapours, and the uncertainties in the anthropogenic emissions of primary organic carbon. Aerosol particle number concentration (condensation nuclei, CN) is overestimated by a factor 1.4 and 1.7 within PBL and FT, respectively. Model bias is most likely attributable to the uncertainties of primary particle emissions (mostly in the PBL) and to the nucleation rate. The overestimation of simulated cloud condensation nuclei (CCN) is more contained with respect to that of CN. The CCN efficiency, which is a measure of the ability of aerosol particles to nucleate cloud droplets, is underestimated by a factor of 1.5 and 3.8 in the PBL and FT, respectively. The comparison with MODIS data shows that the model overestimates the aerosol optical thickness (AOT). The domain averages (for one day) are 0.38 ± 0.12 and 0.42 ± 0.10 for MODIS and WRF/Chem data, respectively. Cloud water path (CWP) is overestimated on average by a factor of 1.7, whereas modelled cloud optical thickness (COT) agrees with observations within 10%. In a sensitivity test where the SOA was not included, simulated CWP is reduced by 40%, and its distribution function shifts toward lower values with respect to the reference run with SOA. The sensitivity test exhibits also 10% more optically thin clouds (COT < 40) and an average COT roughly halved. Moreover, the run with SOA shows convective clouds with an enhanced content of liquid and frozen hydrometers, and stronger updrafts and downdrafts. Considering that the previous version of WRF/Chem coupled with a modal aerosol module predicted very low SOA content (SORGAM mechanism) the new proposed option may lead to a better characterization of aerosol-cloud feedbacks.

Do airborne microbes matter for atmospheric chemistry and cloud formation?

PubMed

Konstantinidis, Konstantinos T

2014-06-01

The role of airborne microbial cells in the chemistry of the atmosphere and cloud formation remains essentially speculative. Recent studies have indicated that microbes might be more important than previously anticipated for atmospheric processes. However, more work and direct communication between microbiologists and atmospheric scientists and modellers are necessary to better understand and model bioaerosol-cloud-precipitation-climate interactions. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Molecular complexes in close and far away

PubMed Central

Klemperer, William; Vaida, Veronica

2006-01-01

In this review, gas-phase chemistry of interstellar media and some planetary atmospheres is extended to include molecular complexes. Although the composition, density, and temperature of the environments discussed are very different, molecular complexes have recently been considered as potential contributors to chemistry. The complexes reviewed include strongly bound aggregates of molecules with ions, intermediate-strength hydrogen bonded complexes (primarily hydrates), and weakly bonded van der Waals molecules. In low-density, low-temperature environments characteristic of giant molecular clouds, molecular synthesis, known to involve gas-phase ion-molecule reactions and chemistry at the surface of dust and ice grains is extended here to involve molecular ionic clusters. At the high density and high temperatures found on planetary atmospheres, molecular complexes contribute to both atmospheric chemistry and climate. Using the observational, laboratory, and theoretical database, the role of molecular complexes in close and far away is discussed. PMID:16740667

Sources and Variability of Aerosols and Aerosol-Cloud Interactions in the Arctic

NASA Astrophysics Data System (ADS)

Liu, H.; Zhang, B.; Taylor, P. C.; Moore, R.; Barahona, D.; Fairlie, T. D.; Chen, G.; Ham, S. H.; Kato, S.

2017-12-01

Arctic sea ice in recent decades has significantly declined. This requires understanding of the Arctic surface energy balance, of which clouds are a major driver. However, the mechanisms for the formation and evolution of clouds in the Arctic and the roles of aerosols therein are highly uncertain. Here we conduct data analysis and global model simulations to examine the sources and variability of aerosols and aerosol-cloud interactions in the Arctic. We use the MERRA-2 reanalysis data (2006-present) from the NASA Global Modeling and Assimilation Office (GMAO) to (1) quantify contributions of different aerosol types to the aerosol budget and aerosol optical depths in the Arctic, (2) ­examine aerosol distributions and variability and diagnose the major pathways for mid-latitude pollution transport to the Arctic, including their seasonal and interannual variability, and (3) characterize the distribution and variability of clouds (cloud optical depth, cloud fraction, cloud liquid and ice water path, cloud top height) in the Arctic. We compare MERRA-2 aerosol and cloud properties with those from C3M, a 3-D aerosol and cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We also conduct perturbation experiments using the NASA GEOS-5 chemistry-climate model (with GOCART aerosol module coupled with two-moment cloud microphysics), and discuss the roles of various types of aerosols in the formation and evolution of clouds in the Arctic.

Is ozone model bias driven by errors in cloud predictions? A quantitative assessment using satellite cloud retrievals in WRF-Chem

NASA Astrophysics Data System (ADS)

Ryu, Y. H.; Hodzic, A.; Barré, J.; Descombes, G.; Minnis, P.

2017-12-01

Clouds play a key role in radiation and hence O3 photochemistry by modulating photolysis rates and light-dependent emissions of biogenic volatile organic compounds (BVOCs). It is not well known, however, how much of the bias in O3 predictions is caused by inaccurate cloud predictions. This study quantifies the errors in surface O3 predictions associated with clouds in summertime over CONUS using the Weather Research and Forecasting with Chemistry (WRF-Chem) model. Cloud fields used for photochemistry are corrected based on satellite cloud retrievals in sensitivity simulations. It is found that the WRF-Chem model is able to detect about 60% of clouds in the right locations and generally underpredicts cloud optical depths. The errors in hourly O3 due to the errors in cloud predictions can be up to 60 ppb. On average in summertime over CONUS, the errors in 8-h average O3 of 1-6 ppb are found to be attributable to those in cloud predictions under cloudy sky conditions. The contribution of changes in photolysis rates due to clouds is found to be larger ( 80 % on average) than that of light-dependent BVOC emissions. The effects of cloud corrections on O­3 are about 2 times larger in VOC-limited than NOx-limited regimes, suggesting that the benefits of accurate cloud predictions would be greater in VOC-limited than NOx-limited regimes.

Experimental interstellar organic chemistry: Preliminary findings

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.

1971-01-01

In a simulation of interstellar organic chemistry in dense interstellar clouds or on grain surfaces, formaldehyde, water vapor, ammonia and ethane are deposited on a quartz cold finger and ultraviolet-irradiated in high vacuum at 77K. The HCHO photolytic pathway which produces an aldehyde radical and a superthermal hydrogen atom initiates solid phase chain reactions leading to a range of new compounds, including methanol, ethanol, acetaldehyde, acetonitrile, acetone, methyl formate, and possibly formic acid. Higher nitriles are anticipated. Genetic relations among these interstellar organic molecules (e.g., the Cannizzaro and Tischenko reactions) must exist. Some of them, rather than being synthesized from smaller molecules, may be degradation products of larger organic molecules, such as hexamethylene tetramine, which are candidate consitituents of the interstellar grains. The experiments reported here may also be relevant to cometary chemistry.

Chemistry in interstellar space. [environment characteristics influencing reaction dynamics

NASA Technical Reports Server (NTRS)

Donn, B.

1973-01-01

The particular characteristics of chemistry in interstellar space are determined by the unique environmental conditions involved. Interstellar matter is present at extremely low densities. Large deviations from thermodynamic equilibrium are, therefore, to be expected. A relatively intense ultraviolet radiation is present in many regions. The temperatures are in the range from 5 to 200 K. Data concerning the inhibiting effect of small activation energies in interstellar clouds are presented in a table. A summary of measured activation energies or barrier heights for exothermic exchange reactions is also provided. Problems of molecule formation are discussed, taking into account gas phase reactions and surface catalyzed processes.

On the Surface Formation of NH3 and HNCO in Dark Molecular Clouds - Searching for Wöhler Synthesis in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Fedoseev, Gleb; Lamberts, Thanja; Linnartz, Harold; Ioppolo, Sergio; Zhao, Dongfeng

Despite its potential to reveal the link between the formation of simple species and more complex molecules (e.g., amino acids), the nitrogen chemistry of the interstellar medium (ISM) is still poorly understood. Ammonia (NH _{3}) is one of the few nitrogen-bearing species that have been observed in interstellar ices toward young stellar objects (YSOs) and quiescent molecular clouds. The aim of the present work is to experimentally investigate surface formation routes of NH _{3} and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant cryogenic temperatures. This study focuses on the formation of NH _{3} and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing start to become predominant. Our work confirms the surface formation of ammonia through the sequential addition of three hydrogen/deuterium atoms to a single nitrogen atom at low temperature. The H/D fractionation of the formed ammonia is also shown. Furthermore, we show the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH _{3}. Finally, we discuss the implications of HNCO in astrobiology, as a possible starting point for the formation of more complex prebiotic species.

Regional Impacts of extending inorganic and organic cloud chemistry with AQCHEM-KMT

EPA Science Inventory

Starting with CMAQ version 5.1, AQCHEM-KMT has been offered as a readily expandable option for cloud chemistry via application of the Kinetic PreProcessor (KPP). AQCHEM-KMT treats kinetic mass transfer between the gas and aqueous phases, ionization, chemical kinetics, droplet sc...

Interstellar clouds - From a dynamical perspective on their chemistry

NASA Technical Reports Server (NTRS)

Prasad, S. S.

1985-01-01

The possibility is examined that in the course of its dynamical evolution, a single mass of interstellar gas would exhibit properties of diffuse clouds, dense clouds and finally also of clouds perturbed by shocks or intense UV or X-ray radiation generated by a star of its own creation. This concept provides a common thread through the bewildering diversity of physical and chemical compositional properties shown by interstellar clouds. From this perspective, instead of being static objects, interstellar clouds are possibly incessantly evolving from initially diffuse to later dense state and then to star formation which ultimately restructures or disperses the remaining cloud material to begin the whole evolutionary process once again. Based on a simplified study of interstellar chemistry from a dynamical perspective, the ideas are presented as an heuristic: to encourage thought on the future direction of molecular astrophysics and the need to consider the chemical behavior of interstellar clouds in conjunction with, rather than in isolation from, their dynamical behavior. A physical basis must be sought for the semiempirical temperature formula which has been given a critical role in the collapse of diffuse clouds. Self-shielding effects in the chemistry of CO were neglected and this drawback should be removed; the ability of the model to explain the fractional abundances of more complex molecules, such as cyanopolyynes, should be examined.

Carbon chemistry in dense molecular clouds: Theory and observational constraints

NASA Technical Reports Server (NTRS)

Blake, Geoffrey A.

1990-01-01

For the most part, gas phase models of the chemistry of dense molecular clouds predict the abundances of simple species rather well. However, for larger molecules and even for small systems rich in carbon these models often fail spectacularly. Researchers present a brief review of the basic assumptions and results of large scale modeling of the carbon chemistry in dense molecular clouds. Particular attention is to the influence of the gas phase C/O ratio in molecular clouds, and the likely role grains play in maintaining this ratio as clouds evolve from initially diffuse objects to denser cores with associated stellar and planetary formation. Recent spectral line surveys at centimeter and millimeter wavelengths along with selected observations in the submillimeter have now produced an accurate inventory of the gas phase carbon budget in several different types of molecular clouds, though gaps in our knowledge clearly remain. The constraints these observations place on theoretical models of interstellar chemistry can be used to gain insights into why the models fail, and show also which neglected processes must be included in more complete analyses. Looking toward the future, larger molecules are especially difficult to study both experimentally and theoretically in such dense, cold regions, and some new methods are therefore outlined which may ultimately push the detectability of small carbon chains and rings to much heavier species.

Aqueous Chemistry in the Clouds of Venus: A Possible Source for the UV Absorber

NASA Astrophysics Data System (ADS)

Baines, Kevin H.; Delitsky, M. L.

2013-10-01

The identity and cause of the UV absorber near the Venusian cloudtops 62-70 km altitude) has been an enduring mystery. Given the role of sulfur in Venus’s atmosphere, where, somewhat analogous to water on Earth, it cycles through gas, liquid, and (possibly) solid phases in the atmosphere, it has been a prime suspect as at least a key component, perhaps as long-lived solid poly-sulfur aerosols, Sn, where n > 4. However, the narrow range of altitudes inhabited by the UV absorber (thought to form and reside primarily above 62 km altitude) seems incompatible with Sn, which should vertically disperse after formation. Here, we point to another process that could lead to somewhat more exotic chemistries that favor formation and sequestration at high altitudes: Aqueous chemistry within H2SO4-nH2O cloud particles. Due to (1) the decrease of temperature and (2) the increase in the fraction of water (“n” in the previous formula) of each cloud droplet with altitude, high-altitude particles near the cloudtops are - via the “heterogeneous uptake” process - significantly more capable of capturing and concentrating trace gases, in particular HCl. For example, the heterogeneous uptake of HCl in H2SO4 droplets near the 65-km cloudtops is at least three times greater than that found in the middle of the clouds near 55 km altitude. Other factors such as local mixing ratios and the concentration of other solvents in the droplet also modify the uptake. Within the cloud droplets, solution chemistry between HCl and H2SO4 may lead to the formation of chlorosulfonic acid, ClSO3H, which is a weak acid that readily breaks down into other species, such as SO2Cl2 (sulfuryl chloride) and SOCl2 (thionyl chloride). Together, these three materials have UV-blue absorptions at 0.21, 0.29, 0.39 and 0.47 micron. Thus, H2SO4 aerosols at high altitudes may take on lasting UV absorption characteristics, dependent on temperature (altitude) and other conditions, Balloons floating at benign Earth-surface-like temperature/pressure conditions near 56-km altitude may be able to sample such aerosols and their complex contents as measured in periodic downdrafts of materials from higher altitudes.

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3

DOE PAGES

Prather, M. J.

2015-05-27

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observed statistics for the vertical correlation of cloud layers, Cloud-J 7.3 provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations represented by four quadrature atmospheres produces mean J values in an atmospheric column with root-mean-square errors of 4% or less compared with 10–20% errors using simpler approximations.more » Cloud-J is practical for chemistry-climate models, requiring only an average of 2.8 Fast-J calls per atmosphere, vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections is also incorporated into Cloud-J.« less

An improved ice cloud formation parameterization in the EMAC model

NASA Astrophysics Data System (ADS)

Bacer, Sara; Pozzer, Andrea; Karydis, Vlassis; Tsimpidi, Alexandra; Tost, Holger; Sullivan, Sylvia; Nenes, Athanasios; Barahona, Donifan; Lelieveld, Jos

2017-04-01

Cirrus clouds cover about 30% of the Earth's surface and are an important modulator of the radiative energy budget of the atmosphere. Despite their importance in the global climate system, there are still large uncertainties in understanding the microphysical properties and interactions with aerosols. Ice crystal formation is quite complex and a variety of mechanisms exists for ice nucleation, depending on aerosol characteristics and environmental conditions. Ice crystals can be formed via homogeneous nucleation or heterogeneous nucleation of ice-nucleating particles in different ways (contact, immersion, condensation, deposition). We have implemented the computationally efficient cirrus cloud formation parameterization by Barahona and Nenes (2009) into the EMAC (ECHAM5/MESSy Atmospheric Chemistry) model in order to improve the representation of ice clouds and aerosol-cloud interactions. The parameterization computes the ice crystal number concentration from precursor aerosols and ice-nucleating particles accounting for the competition between homogeneous and heterogeneous nucleation and among different freezing modes. Our work shows the differences and the improvements obtained after the implementation with respect to the previous version of EMAC.

Mesoscale modeling of smoke transport over Central Africa: influences of trade winds, subtropical high, ITCZ and vertical statistics

NASA Astrophysics Data System (ADS)

Yang, Z.; Wang, J.; Hyer, E. J.; Ichoku, C. M.

2012-12-01

A fully-coupled meteorology-chemistry-aerosol model, Weather Research and Forecasting model with Chemistry (WRF-Chem), is used to simulate the transport of smoke aerosol over the Central Africa during February 2008. Smoke emission used in this study is specified from the Fire Locating and Modeling of Burning Emissions (FLAMBE) database derived from Moderate Resolution Imaging Spectroradiometer (MODIS) fire products. Model performance is evaluated using MODIS true color images, measured Aerosol Optical Depth (AOD) from space-borne MODIS (550 nm) and ground-based AERONET (500 nm), and Cloud-Aerosol Lidar data with Orthogonal Polarization (CALIOP) level 1 and 2 products. The simulated smoke transport is in good agreement with the validation data. Analyzing from three smoke events, smoke is constrained in a narrow belt between the Equator and 10°N near the surface, with the interplay of trade winds, subtropical high, and ITCZ. At the 700 hpa level, smoke expands farther meridionally. Topography blocks the smoke transport to the southeast of study area, because of high mountains located near the Great Rift Valley region. The simulation with injection height of 650 m is consistent with CALIOP measurements. The particular phenomenon, aerosol above cloud, is studied statistically from CALIOP observations. The total percentage of aerosol above cloud is about 5%.

H2O2 modulates the energetic metabolism of the cloud microbiome

NASA Astrophysics Data System (ADS)

Wirgot, Nolwenn; Vinatier, Virginie; Deguillaume, Laurent; Sancelme, Martine; Delort, Anne-Marie

2017-12-01

Chemical reactions in clouds lead to oxidation processes driven by radicals (mainly HO⚫, NO3⚫, or HO2⚫) or strong oxidants such as H2O2, O3, nitrate, and nitrite. Among those species, hydrogen peroxide plays a central role in the cloud chemistry by driving its oxidant capacity. In cloud droplets, H2O2 is transformed by microorganisms which are metabolically active. Biological activity can therefore impact the cloud oxidant capacity. The present article aims at highlighting the interactions between H2O2 and microorganisms within the cloud system. First, experiments were performed with selected strains studied as a reference isolated from clouds in microcosms designed to mimic the cloud chemical composition, including the presence of light and iron. Biotic and abiotic degradation rates of H2O2 were measured and results showed that biodegradation was the most efficient process together with the photo-Fenton process. H2O2 strongly impacted the microbial energetic state as shown by adenosine triphosphate (ATP) measurements in the presence and absence of H2O2. This ATP depletion was not due to the loss of cell viability. Secondly, correlation studies were performed based on real cloud measurements from 37 cloud samples collected at the PUY station (1465 m a.s.l., France). The results support a strong correlation between ATP and H2O2 concentrations and confirm that H2O2 modulates the energetic metabolism of the cloud microbiome. The modulation of microbial metabolism by H2O2 concentration could thus impact cloud chemistry, in particular the biotransformation rates of carbon compounds, and consequently can perturb the way the cloud system is modifying the global atmospheric chemistry.

The Atmosphere and Climate of Venus

NASA Astrophysics Data System (ADS)

Bullock, M. A.; Grinspoon, D. H.

Venus lies just sunward of the inner edge of the Sun's habitable zone. Liquid water is not stable. Like Earth and Mars, Venus probably accreted at least an ocean's worth of water, although there are alternative scenarios. The loss of this water led to the massive, dry CO2 atmosphere, extensive H2SO4 clouds (at least some of the time), and an intense CO2 greenhouse effect. This chapter describes the current understanding of Venus' atmosphere, established from the data of dozens of spacecraft and atmospheric probe missions since 1962, and by telescopic observations since the nineteenth century. Theoretical work to model the temperature, chemistry, and circulation of Venus' atmosphere is largely based on analogous models developed in the Earth sciences. We discuss the data and modeling used to understand the temperature structure of the atmosphere, as well as its composition, cloud structure, and general circulation. We address what is known and theorized about the origin and early evolution of Venus' atmosphere. It is widely understood that Venus' dense CO2 atmosphere is the ultimate result of the loss of an ocean to space, but the timing of major transitions in Venus' climate is very poorly constrained by the available data. At present, the bright clouds allow only 20% of the sunlight to drive the energy balance and therefore determine conditions at Venus' surface. Like Earth and Mars, differential heating between the equator and poles drives the atmospheric circulation. Condensable species in the atmosphere create clouds and hazes that drive feedbacks that alter radiative forcing. Also in common with Earth and Mars, the loss of light, volatile elements to space produces long-term changes in composition and chemistry. As on Earth, geologic processes are most likely modifying the atmosphere and clouds by injecting gases from volcanos as well as directly through chemical reactions with the surface. The sensitivity of Venus' atmospheric energy balance is quantified in this chapter in terms of the initial forcing due to a perturbation, radiative response, and indirect responses, which are feedbacks — either positive or negative. When applied to one Venus climate model, we found that the albedo-radiative feedback is more important than greenhouse forcing for small changes in atmospheric H2O and SO2. An increase in these gases cools the planet by making the clouds brighter. On geologic timescales the reaction of some atmospheric species (SO2, CO, OCS, S, H2O, H2S, HCl, HF) with surface minerals could cause significant changes in atmospheric composition. Laboratory data and thermochemical modeling have been important for showing that atmospheric SO2 would be depleted in ~10 m.y. if carbonates are available at the surface. Without replenishment, the clouds would disappear. Alternatively, the oxidation of pyrite could add SO2 to the atmosphere while producing stable Fe oxides at the surface. The correlation of near-infrared high emissivity (dark) surface features with three young, large volcanos on Venus is strong evidence for recent volcanic activity at these sites, certainly over the timescale necessary to support the clouds. We address the nature of heterogeneous reactions with the surface and the implications for climate change on Venus. Chemical and mineralogical signatures of past climates must exist at the surface and below, so in situ experiments on the composition of surface layers are vital for reconstructing Venus' past climate. Many of the most Earth-like planets found around other stars will probably resemble Venus or a younger version of Venus. We finish the chapter with discussing what Venus can tell us about life in the universe, since it is an example of a planetary climate rendered uninhabitable. It also resembles our world's likely future. As with the climate history of Venus, however, the timing of predictable climate transitions on the Earth is poorly constrained by the data.

Astrochemistry

NASA Astrophysics Data System (ADS)

Millar, T. J.

2015-08-01

In the last 40 years a wide range of molecules, including neutrals, cations and anions, containing up to 13 atoms—in addition to detections of {{\\text{C}}60} and {{\\text{C}}70} —have been found in the harsh environment of the interstellar medium. The exquisite sensitivity and very high spectral and, more recently, spatial resolution, of modern telescopes has enabled the physics of star formation to be probed through rotational line emission. In this article, I review the basic properties of interstellar clouds and the processes that initiate the chemistry and generate chemical complexity, particularly in regions of star and planet formation. Our understanding of astrochemistry has evolved over the years. Before 1990, the general consensus was that molecules were formed in binary, gas-phase, or volume, reactions, most importantly ion-neutral reactions despite the very low ionization in clouds. Since then, observations have indicated unambiguously that there is also a contribution from surface processes, particularly on the icy mantles that form around refractory grain cores in cold, dense gas. The balance between these two processes depends on particular physical conditions and can vary during the life cycle of a particular volume of interstellar cloud. The complex chemistry that occurs in space is driven mostly through interaction of the gas with cosmic ray protons, a source of ionization that enables a rich ion-neutral chemistry. In addition, I show that the interaction between the gas and the dust in cold, dense regions also leads to additional chemical complexity through reactions that take place in ices at only a few tens of degrees above absolute zero. Although densities are low compared to those in terrestrial environments, the extremely long life times of interstellar clouds and their enormous sizes, enable complex molecules to be synthesised and detected. I show that in some instances, particularly in reactions involving deuterium, the rotational populations of reactants, together with spin-selection rules, can determine the detailed abundances. Although the review is mainly focused on regions associated with star formation, I also consider chemistry in other interesting astronomical regions—in the early Universe and in the envelopes formed by mass loss during the final stages of stellar evolution.

Carbon Isotope Chemistry in Molecular Clouds

NASA Technical Reports Server (NTRS)

Robertson, Amy N.; Willacy, Karen

2012-01-01

Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

Evaluation of WRF Performance Driven by GISS-E2-R Global Model for the 2014 Rainy Season in Mexico

NASA Astrophysics Data System (ADS)

Almanza, V.; Zavala, M. A.; Lei, W.; Shindell, D. T.; Molina, L. T.

2017-12-01

Precipitation and cloud fields as well as the spatial distribution of emissions are important during the estimation of the radiative effects of atmospheric pollutants in future climate applications. In particular, landfalling hurricanes and tropical storms greatly affect the amount and distribution of annual precipitation, and thus have a direct impact on the wet deposition of pollutants and aerosol-cloud interactions. Therefore, long-term simulations in chemistry mode driven by the outputs of a global model need to consider the influence of these phenomena on the radiative effects, particularly for countries such as Mexico that have high number of landfalling hurricanes and tropical storms. In this work the NASA earth system GISS-E2-R global model is downscaled with the WRF model over a domain encompassing Mexico. We use the North American Regional Reanalysis (NARR) and Era-Interim reanalysis, along with available surface observations and data from the Tropical Rainfall Measuring Mission (TRMM) products to evaluate the contribution of spectral nudging, domain size and resolution in resolving the precipitation and cloud fraction fields for the rainy season in 2014. We focus on this year since 10 tropical cyclones made landfall in central Mexico. The results of the evaluation are useful to assess the performance of the model in representing the present conditions of precipitation and cloud fraction in Mexico. In addition, it provides guidelines for conducting the operational runs in chemistry mode for the future years.

Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

1991-01-01

Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

Shocking Changes to Molecular Clouds

NASA Astrophysics Data System (ADS)

Melnick, Gary J.

1998-05-01

Supersonic motions are commonly observed in molecular clouds as evidenced by larger-than-thermal line widths measured in most species. The shocks that ensue can profoundly effect these clouds, not only dynamically, but chemically. Because shocks compress and heat the gas, chemical reactions that are extremely slow at typical molecular cloud temperatures (T ~ 10-30 K) can proceed rapidly in the wake of a shock. In many cases, compositional changes brought on by a passing shock can endure long after the gas has cooled and returned to its pre-shock state. We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of such chemical relics in the wake of non-dissociative shocks. Using a Monte Carlo cloud simulation, we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. Particular attention is paid to the chemistry of H_2O and O_2, two molecules which are predicted to have abundances that are significantly affected by shock-heated gas. Both pure gas-phase and gas-grain chemistry are considered. In agreement with previous studies, we find that shocks with velocities in excess of 10 km s(-1) can chemically process all oxygen not locked in CO into H_2O on timescales of a shock passage time ( ~ \\:few hundred years). For pure gas-phase models, the high water abundance lingers for ~ (4-7) x 10(5) yr, independent of the gas density. A density dependence for the lifetime of H_2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. We demonstrate that the time-averaged abundance of H_2O and O_2 (as well as other tracers, such as SiO and CH_3OH) is a sensitive function of the frequency of shocks. As such, the abundance of H_2O, and to a lesser extent O_2, can be used to trace the shock history in molecular clouds. Equally important, we find that depletion of shock-produced water onto grains can be quite large and is comparable to that observed in molecular clouds. This offers an alternative method to create water-ice mantles without resorting to grain surface chemistry. Observationally, a combination of space-based (for H_2O and O_2) and ground-based (for SiO, CH_3OH, and others) telescopes will be needed to investigate these predictions.

Dust, Pollution, and Biomass Burning Aerosols in Asian Pacific: A Column Satellite-Surface Perspective

NASA Technical Reports Server (NTRS)

Tsay, Si-Chee

2004-01-01

Airborne dusts from northern China contribute a significant part of the air quality problem and, to some extent, regional climatic impact in Asia during spring-time. However, with the economical growth in China, increases in the emission of air pollutants generated from industrial and vehicular sources will not only impact the radiation balance, but adverse health effects to humans all year round. In addition, both of these dust and air pollution clouds can transport swiftly across the Pacific reaching North America within a few days, possessing an even larger scale effect. The Asian dust and air pollution aerosols can be detected by its colored appearance on current Earth observing satellites (e.g., MODIS, SeaWiFS, TOMS, etc.) and its evolution monitored by satellites and surface network. Biomass burning has been a regular practice for land clearing and land conversion in many countries, especially those in Africa, South America, and Southeast Asia. However, the unique climatology of Southeast Asia is very different than that of Africa and South America, such that large-scale biomass burning causes smoke to interact extensively with clouds during the peak-burning season of March to April. Significant global sources of greenhouse gases (e.g., CO2, CH4), chemically active gases (e.g., NO, CO, HC, CH3Br), and atmospheric aerosols are produced by biomass burning processes. These gases influence the Earth-atmosphere system, impacting both global climate and tropospheric chemistry. Some aerosols can serve as cloud condensation nuclei, which play an important role in determining cloud lifetime and precipitation, hence, altering the earth's radiation and water budget. Biomass burning also affects the biogeochemical cycling of nitrogen and carbon compounds from the soil to the atmosphere; the hydrological cycle (i.e., run off and evaporation); land surface reflectivity and emissivity; as well as ecosystem biodiversity and stability. Two new initiatives, EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) and BASE-ASIA (Biomass-burning Aerosols in South East-Asia: Smoke Impact Assessment) will be presented and discussed their contribution to better understand the impacts of aerosols on regional-to-global climate, hydrological and carbon cycles, and tropospheric chemistry.

A short overview of the microbial population in clouds: Potential roles in atmospheric chemistry and nucleation processes

NASA Astrophysics Data System (ADS)

Delort, Anne-Marie; Vaïtilingom, Mickael; Amato, Pierre; Sancelme, Martine; Parazols, Marius; Mailhot, Gilles; Laj, Paolo; Deguillaume, Laurent

2010-11-01

Recent studies showed that living microorganisms, including bacteria, fungi and yeasts, are present in the atmospheric water phase (fog and clouds) and their role in chemical processes may have been underestimated. At the interface between atmospheric science and microbiology, information about this field of science suffers from the fact that not all recent findings are efficiently conveyed to both scientific communities. The purpose of this paper is therefore to provide a short overview of recent work linked to living organisms in the atmospheric water phase, from their activation to cloud droplets and ice crystal, to their potential impact on atmospheric chemical processes. This paper is focused on the microorganisms present in clouds and on the role they could play in atmospheric chemistry and nucleation processes. First, the life cycle of microorganisms via the atmosphere is examined, including their aerosolization from sources, their integration into clouds and their wet deposition on the ground. Second, special attention is paid to the possible impacts of microorganisms on liquid and ice nucleation processes. Third, a short description of the microorganisms that have been found in clouds and their variability in numbers and diversity is presented, emphasizing some specific characteristics that could favour their occurrence in cloud droplets. In the last section, the potential role of microbial activity as an alternative route to photochemical reaction pathways in cloud chemistry is discussed.

How Is the Oxidative Capacity of the Cloud Aqueous Phase Modified By Bacteria?

NASA Astrophysics Data System (ADS)

Deguillaume, L.; Mouchel-Vallon, C.; Passananti, M.; Wirgot, N.; Joly, M.; Sancelme, M.; Bianco, A.; Cartier, N.; Brigante, M.; Mailhot, G.; Delort, A. M.; Chaumerliac, N. M.

2014-12-01

The aqueous phase photochemical reactions of constituents present in atmospheric water like H2O2, NO3-, NO2- and Fe(III) aqua-complexes or organic complexes can form radicals such as the hydroxyl radical HO within the water drop. However, the literature lacks of data precising the rate of HO formation and the relative contribution of the photochemical sources of HO. The production of radicals in cloud aqueous phase drives the oxidative capacity of the cloud medium and the efficiency of organic matter oxidation. The oxidation of organic compounds is suspected to lead to oxygenated species that could contribute to secondary organic aerosol (SOA) mass (Ervens et al., 2011). In current cloud chemistry models, HO concentrations strongly depend on the organic and iron amount. For high concentrations of organic compounds, this radical is efficiently consumed during the day due to the oxidation process. When iron concentrations are typical from continental cloud, the photolysis of Fe(III) complexes and the Fenton reaction drive the HO concentrations in the cloud models. The concept of biocatalysed reactions contributing to atmospheric chemistry as an alternative route to photochemistry is quite new (Vaïtilingom et al., 2013); it emerged from the recent discovery of metabolically active microorganisms in clouds. Microorganisms are well-known to degrade organic matter but they could also interact with oxidant species such as H2O2 (or their precursors) thanks to their oxidative and nitrosative stress metabolism that will act directly on these species and on their interactions with iron (metalloproteins and siderophores). For the moment, biological impact on radical chemistry within cloud has not been yet considered in cloud chemistry models. Bacterial activity will be introduced as catalysts in a multiphase cloud chemistry model using degradation rates measured in the laboratory. For example, biodegradation rates of the oxidants H2O2 by model bacteria will be tested in the model. Interactions of bacteria with iron through siderophore production will be also parameterized in the model. For this, we will perform idealistic scenarii to quantify the effect of bacteria on the aqueous budget of oxidants. Ervens et al., ACP, 11, 11069-11102, 2011. Vaïtilingom et al., PNAS, 110-2, 559-564, 2013.

Theoretical Modeling of Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Charnley, Steven

2009-01-01

The chemistry of complex interstellar organic molecules will be described. Gas phase processes that may build large carbon-chain species in cold molecular clouds will be summarized. Catalytic reactions on grain surfaces can lead to a large variety of organic species, and models of molecule formation by atom additions to multiply-bonded molecules will be presented. The subsequent desorption of these mixed molecular ices can initiate a distinctive organic chemistry in hot molecular cores. The general ion-molecule pathways leading to even larger organics will be outlined. The predictions of this theory will be compared with observations to show how possible organic formation pathways in the interstellar medium may be constrained. In particular, the success of the theory in explaining trends in the known interstellar organics, in predicting recently-detected interstellar molecules, and, just as importantly, non-detections, will be discussed.

Evolutionary models of interstellar chemistry

NASA Technical Reports Server (NTRS)

Prasad, Sheo S.

1987-01-01

The goal of evolutionary models of interstellar chemistry is to understand how interstellar clouds came to be the way they are, how they will change with time, and to place them in an evolutionary sequence with other celestial objects such as stars. An improved Mark II version of an earlier model of chemistry in dynamically evolving clouds is presented. The Mark II model suggests that the conventional elemental C/O ratio less than one can explain the observed abundances of CI and the nondetection of O2 in dense clouds. Coupled chemical-dynamical models seem to have the potential to generate many observable discriminators of the evolutionary tracks. This is exciting, because, in general, purely dynamical models do not yield enough verifiable discriminators of the predicted tracks.

Complex Protostellar Chemistry

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Johnson, Natasha M.

2012-01-01

Two decades ago, our understanding chemistry in protostars was simple -- matter either fell into the central star or was trapped in planetary-scale objects. Some minor chemical changes might occur as the dust and gas fell inward, but such effects were overwhelmed by the much larger-scale processes that occurred even in bodies as small as asteroids. The chemistry that did occur in the nebula was relatively easy to model because the fall from the cold molecular cloud into the growing star was a one-way trip down a well-known temperature pressure gradient; the only free variable was time. However, just over 10 years ago it was suggested that some material could be processed in the inner nebula, flow outward, and become incorporated into comets. This outward flow was confirmed when the Stardust mission returned crystalline mineral fragments from Comet Wild 2 that must have been processed close to the Sun before they were incorporated into the comet. In this week's Science Express, Ciesla and Sandford demonstrate that even the outermost regions of the solar nebula can be a chemically active environment. Their finding could have consequences for the rest of the nebula. Our understanding of the chemistry in protostellar systems has made enormous progress over the last few decades, fueled by an increased awareness of the complex dynamics of these evolving energetic nebulae. We can no longer consider just the simple local environment to explain the composition of a planet, asteroid, or comet as was done in the past, but must now consider chemical processes that might take place within the nebula as a whole as well as the probability of transport and mixing the products of such reactions throughout the system. just as we now find it impossible to explain the complex chemistry of the terrestrial atmosphere without reference to detailed transport models that interconnect highly dissimilar chemical environments, so chemical models of protostars and of the solar nebula must eventually treat these environments as tightly coupled, interactive systems. The demonstration that the chemistry on the surfaces of outward-flowing, dynamically mixing icy grain surfaces both mimics the chemistry in cold cloud cores and strikes at the central assumption of the photochemical self-shielding model for oxygen isotopes in solar system solids only adds emphasis to this conclusion.

Is the gas-phase OH+H2CO reaction a source of HCO in interstellar cold dark clouds? A kinetic, dynamic and modelling study

PubMed Central

Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.

2018-01-01

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients (k) of the gas-phase OH+H2CO reaction between 22 and 107 K. k values greatly increase from 2.1×10-11 cm3 s-1 at 107 K to 1.2×10-10 cm3 s-1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H2CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10K (2.6×10-10 cm3 s-1). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 105-106 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented. PMID:29880977

Is the Gas-phase OH+H2CO Reaction a Source of HCO in Interstellar Cold Dark Clouds? A Kinetic, Dynamic, and Modeling Study

NASA Astrophysics Data System (ADS)

Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.

2017-11-01

The chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T ˜ 10-100 K). Scarce kinetic information is currently available for these kinds of reactions at T < 200 K. In this work, we use the Cinétique de Réaction en Ecoulement Supersonique Uniforme (CRESU; Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients (k) of the gas-phase OH+H2CO reaction between 22 and 107 K. The k values greatly increase from 2.1 × 10-11 cm3 s-1 at 107 K to 1.2 × 10-10 cm3 s-1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface that generates highly accurate potential and includes long-range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H2CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10 K (2.6 × 10-10 cm3 s-1). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 105-106 yr. The different sources of production of HCO are presented and the uncertainties in the chemical networks are discussed. The present reaction is shown to account for a few percent of the total HCO production rate. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. Extensions to photodissociation regions and diffuse cloud environments are also addressed.

Is the gas-phase OH+H2CO reaction a source of HCO in interstellar cold dark clouds? A kinetic, dynamic and modelling study.

PubMed

Ocaña, A J; Jiménez, E; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Agúndez, M; Cernicharo, J; Zanchet, A; Del Mazo, P; Roncero, O; Aguado, A

2017-11-20

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU ( Cinétique de Réaction en Ecoulement Supersonique Uniforme , which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients ( k ) of the gas-phase OH+H 2 CO reaction between 22 and 107 K. k values greatly increase from 2.1×10 -11 cm 3 s -1 at 107 K to 1.2×10 -10 cm 3 s -1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H 2 CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10K (2.6×10 -10 cm 3 s -1 ). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 10 5 -10 6 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented.

Climate change on Venus and future spacecraft mission priorities

NASA Astrophysics Data System (ADS)

Bullock, M.; Grinspoon, D.

Weathering of surface minerals in the sulfur-rich lower atmosphere of Venus may well have played a significant role in the recent evolution of the planet's climate. SO 2 in the atmosphere is interesting because it is the primary precursor of Venus' bright H 2SO 4 /H 2O clouds, it is a greenhouse gas, it is most likely outgassed by volcanoes [Prinn, 1985], it probably reacts with the surface, and it is apparently much higher in abundance that would be expected from thermochemical equilibrium with the surface [Fegley and Treiman, 1992] (although interpretations of Vega 1 and 2 UV spectrometer data challenge the latter, see Bertaux et al., [1996]). Changes in the atmospheric abundance of SO 2 would be accompanied by alterations in the optical properties of the clouds and in the greenhouse effect, thereby affecting surface temperatures [Bullock and Grinspoon, 2001]. Fegley and Prinn , [1989] demonstrated e perimentally that the reaction CaCO3 +x SO 2 ==> CaSO 4 + CO proceeds rapidly under Venus-like conditions, and concluded that SO 2 and hence the H 2 SO 4 /H 2O clouds would disappear in 1.9 My unless SO 2 in the atmosphere were continually replenished by volcanic outgassing. Using a coupled chemical kinetic reaction-diffusion and climate model, [ Bullock and Grinspoon, 2001] calculated that volcanism must supply SO 2 to the atmosphere on approximately 30 My timescales in order to maintain clouds with their current optical properties. Clues to the nature of the recent Venus climate may be obtained by elucidating the sensitivity of cloud properties to changes in a mospheric SO 2 andt H 2O and by investigations into the styles and depths of chemical weathering at the surface. Future robotic spacecraft missions have the pot ential to provide significant insights into recent climate change on Venus and on the role that sulfur may have played. Among the most important and scientifically valuable investigations are: 1. High spectral, spatial, and temporal resolution near-IR i aging spectrometrym from Venus orbit in order to retrieve accurate SO 2, H 2O and CO abundances and variability beneath the clouds. Coupling gas abundance and variability to cloud morphology , cloud optical properties, and to atmospheric dynamics would enable a far better understanding of how clouds and climate respond to changing atmospheric chemistry. 2. Visible to near-IR high resolution images of the surface from 15-20 km in order to complement the global synthetic aperture radar imagery of the Magellan mission (e.g. [M o r o z, 2002]). Remaining scientific issues about Venus' geologic history, which is vigorously debated, may well be resolved by obtaining near-visual wavelength datasets of selected areas on Venus. These can be used to calibrate the global radar dataset in terms of surface properties and geomorphology. 3. Elemental and mineralogical analyses of the surface and subsurface, in order to establish both fundamental mineralogy and weathering products as a function of depth. Visual images of the surface by the Venera landers clearly show broken slabs a few cm in thickness [S u r k o v et al., 1984]. This provides hints as to the nature and extent of weathering of the surface. A detailed mineralogy of the top 10 cm of the surface would provide highly valuable information on the nature and rates of surface-atmosphere interactions and their possible role in alterations of atmospheric chemistry and climate. Although Venus is a difficult planet to study because of its shroud of sulfuric acid clouds and its otherwise harsh environment, it is the only planet that shares the similarity with Earth of having a climate that is actively modified by its geology . As the study of Earth's climate becomes of greater and greater significance to society, so too does the necessity of thinking of planetary climate 'outside the box'. The continued exploration of Venus is one of the most promising avenues to accomplish this. Bertaux, J.L., et al., J. Geophys. Res. , 101 , 12,709-12,745, 1996. Bullock, M.A., and D.H. Grinspoon, Icarus, 150 , 19-37, 2001. Fegley, B., and R.G. Prinn, Nature, 337 , 55-58, 1989. Fegley, B., and A.H. Treiman, in Venus and Mars, pp. 7-71, AGU, Washington, DC,1992. Moroz, V.I., Planet. Space Sci., 50 , 287-297, 2002. Prinn, R.G., in Recent Advances in Planetary Meteorology, Cambridge UniversityPress, Cambridge, 1985. Surkov, Y.A., et al., in Proc. 14th Lunar Planet. Sci. Conf., pp. B393-B402, J.Geophys. Res., 1984.

Impact of natural and anthropogenic aerosols on stratocumulus and precipitation in the Southeast Pacific: a regional modelling study using WRF-Chem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Q.; Gustafson, W. I.; Fast, J. D.

2012-09-28

Cloud-system resolving simulations with the chemistry version of the Weather Research and Forecasting (WRF-Chem) model are used to quantify the relative impacts of regional anthropogenic and oceanic emissions on changes in aerosol properties, cloud macro- and microphysics, and cloud radiative forcing over the Southeast Pacific (SEP) during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) (15 October–16 November 2008). Two distinct regions are identified. The near-coast polluted region is characterized by low surface precipitation rates, the strong suppression of non-sea-salt particle activation due to sea-salt particles, a predominant albedo effect in aerosol indirect effects, and limited impact of aerosols associated withmore » anthropogenic emissions on clouds. Opposite sensitivities to natural marine and anthropogenic aerosol perturbations are seen in cloud properties (e.g., cloud optical depth and cloud-top and cloud-base heights), precipitation, and the top-of-atmosphere and surface shortwave fluxes over this region. The relatively clean remote region is characterized by large contributions of aerosols from non-regional sources (lateral boundaries) and much stronger drizzle at the surface. Under a scenario of five-fold increase in regional anthropogenic emissions, this relatively clean region shows large cloud responses, for example, a 13% increase in cloud-top height and a 9% increase in albedo in response to a moderate increase (25% of the reference case) in cloud condensation nuclei (CCN) concentration. The reduction of precipitation due to this increase in anthropogenic aerosols more than doubles the aerosol lifetime in the clean marine boundary layer. Therefore, the aerosol impacts on precipitation are amplified by the positive feedback of precipitation on aerosol, which ultimately alters the cloud micro- and macro-physical properties, leading to strong aerosol-cloud-precipitation interactions. The high sensitivity is also related to an increase in cloud-top entrainment rate (by 16% at night) due to the increased anthropogenic aerosols. The simulated aerosol-cloud-precipitation interactions due to the increased anthropogenic aerosols have a stronger diurnal cycle over the clean region compared to the near-coast region with stronger interactions at night. During the day, solar heating results in more frequent decoupling of the cloud and sub-cloud layers, thinner clouds, reduced precipitation, and reduced sensitivity to the increase in anthropogenic emissions. This study shows the importance of natural aerosols in accurately quantifying anthropogenic forcing within a regional modeling framework. Finally, the results of this study also imply that the energy balance perturbations from increased anthropogenic emissions are larger in the more susceptible clean environment than in already polluted environment and are larger than possible from the first indirect effect alone.« less

Cyanide and isocyanide abundances in the cold, dark cloud TMC-1

NASA Technical Reports Server (NTRS)

Irvine, W. M.; Schloerb, F. P.

1984-01-01

Cold, dark molecular clouds are particularly useful for the study of interstellar chemistry because their physical parameters are better understood than those of heterogeneous, complex giant molecular clouds. Another advantage is their relatively small distance from the solar system. The present investigaation has the objective to provide accurate abundance ratios for several cyanides and isocyanides in order to constrain models of dark cloud chemistry. The relative abundances of such related species can be particularly useful for the study of chemical processes. The cloud TMC-1 considered in the current study has a remarkably high abundance of acetylene and polyacetylene derivatives. Data at 3 mm, corresponding to the J = 1 to 0 transitions of HCN, H(C-13)N, HN(C-13), HC(N-15), and H(N-15)C were obtained.

Global impact of mineral dust on cloud droplet number concentration

NASA Astrophysics Data System (ADS)

Karydis, Vlassis A.; Tsimpidi, Alexandra P.; Bacer, Sara; Pozzer, Andrea; Nenes, Athanasios; Lelieveld, Jos

2017-05-01

The importance of wind-blown mineral dust for cloud droplet formation is studied by considering (i) the adsorption of water on the surface of insoluble particles, (ii) particle coating by soluble material (atmospheric aging) which augments cloud condensation nuclei (CCN) activity, and (iii) the effect of dust on inorganic aerosol concentrations through thermodynamic interactions with mineral cations. The ECHAM5/MESSy Atmospheric Chemistry (EMAC) model is used to simulate the composition of global atmospheric aerosol, while the ISORROPIA-II thermodynamic equilibrium model treats the interactions of K+-Ca2+-Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O aerosol with gas-phase inorganic constituents. Dust is considered a mixture of inert material with reactive minerals and its emissions are calculated online by taking into account the soil particle size distribution and chemical composition of different deserts worldwide. The impact of dust on droplet formation is treated through the unified dust activation parameterization that considers the inherent hydrophilicity from adsorption and acquired hygroscopicity from soluble salts during aging. Our simulations suggest that the presence of dust increases cloud droplet number concentration (CDNC) over major deserts (e.g., up to 20 % over the Sahara and the Taklimakan desert) and decreases CDNC over polluted areas (e.g., up to 10 % over southern Europe and 20 % over northeastern Asia). This leads to a global net decrease in CDNC by 11 %. The adsorption activation of insoluble aerosols and the mineral dust chemistry are shown to be equally important for the cloud droplet formation over the main deserts; for example, these effects increase CDNC by 20 % over the Sahara. Remote from deserts the application of adsorption theory is critically important since the increased water uptake by the large aged dust particles (i.e., due to the added hydrophilicity by the soluble coating) reduce the maximum supersaturation and thus cloud droplet formation from the relatively smaller anthropogenic particles (e.g., CDNC decreases by 10 % over southern Europe and 20 % over northeastern Asia by applying adsorption theory). The global average CDNC decreases by 10 % by considering adsorption activation, while changes are negligible when accounting for the mineral dust chemistry. Sensitivity simulations indicate that CDNC is also sensitive to the mineral dust mass and inherent hydrophilicity, and not to the chemical composition of the emitted dust.

Application of an online-coupled regional climate model, WRF-CAM5, over East Asia for examination of ice nucleation schemes: Part I. Comprehensive model evaluation and trend analysis for 2006 and 2011

DOE PAGES

Chen, Ying; Zhang, Yang; Fan, Jiwen; ...

2015-08-18

Online-coupled climate and chemistry models are necessary to realistically represent the interactions between climate variables and chemical species and accurately simulate aerosol direct and indirect effects on cloud, precipitation, and radiation. In this Part I of a two-part paper, simulations from the Weather Research and Forecasting model coupled with the physics package of Community Atmosphere Model (WRF-CAM5) are conducted with the default heterogeneous ice nucleation parameterization over East Asia for two full years: 2006 and 2011. A comprehensive model evaluation is performed using satellite and surface observations. The model shows an overall acceptable performance for major meteorological variables at themore » surface and in the boundary layer, as well as column variables (e.g., precipitation, cloud fraction, precipitating water vapor, downward longwave and shortwave radiation). Moderate to large biases exist for cloud condensation nuclei over oceanic areas, cloud variables (e.g., cloud droplet number concentration, cloud liquid and ice water paths, cloud optical depth, longwave and shortwave cloud forcing). These biases indicate a need to improve the model treatments for cloud processes, especially cloud droplets and ice nucleation, as well as to reduce uncertainty in the satellite retrievals. The model simulates well the column abundances of chemical species except for column SO 2 but relatively poor for surface concentrations of several species such as CO, NO 2, SO 2, PM 2.5, and PM 10. Several reasons could contribute to the underestimation of major chemical species in East Asia including underestimations of anthropogenic emissions and natural dust emissions, uncertainties in the spatial and vertical distributions of the anthropogenic emissions, as well as biases in meteorological, radiative, and cloud predictions. Despite moderate to large biases in the chemical predictions, the model performance is generally consistent with or even better than that reported for East Asia with only a few exceptions. The model generally reproduces the observed seasonal variations and the difference between 2006 and 2011 for most variables or chemical species. Overall, these results demonstrate promising skills of WRF-CAM5 for long-term simulations at a regional scale and suggest several areas of potential improvements.« less

Application of an Online-Coupled Regional Climate Model, WRF-CAM5, over East Asia for Examination of Ice Nucleation Schemes: Part I. Comprehensive Model Evaluation and Trend Analysis for 2006 and 2011

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ying; Zhang, Yang; Fan, Jiwen

Online-coupled climate and chemistry models are necessary to realistically represent the interactions between climate variables and chemical species and accurately simulate aerosol direct and indirect effects on cloud, precipitation, and radiation. In this Part I of a two-part paper, simulations from the Weather Research and Forecasting model coupled with the physics package of Community Atmosphere Model (WRF-CAM5) are conducted with the default heterogeneous ice nucleation parameterization over East Asia for two full years: 2006 and 2011. A comprehensive model evaluation is performed using satellite and surface observations. The model shows an overall acceptable performance for major meteorological variables at themore » surface and in the boundary layer, as well as column variables (e.g., precipitation, cloud fraction, precipitating water vapor, downward longwave and shortwave radiation). Moderate to large biases exist for cloud condensation nuclei over oceanic areas, cloud variables (e.g., cloud droplet number concentration, cloud liquid and ice water paths, cloud optical depth, longwave and shortwave cloud forcing). These biases indicate a need to improve the model treatments for cloud processes, especially cloud droplets and ice nucleation, as well as to reduce uncertainty in the satellite retrievals. The model simulates well the column abundances of chemical species except for column SO 2 but relatively poor for surface concentrations of several species such as CO, NO 2, SO 2, PM2.5, and PM10. Several reasons could contribute to the underestimation of major chemical species in East Asia including underestimations of anthropogenic emissions and natural dust emissions, uncertainties in the spatial and vertical distributions of the anthropogenic emissions, as well as biases in meteorological, radiative, and cloud predictions. Despite moderate to large biases in the chemical predictions, the model performance is generally consistent with or even better than that reported for East Asia with only a few exceptions. The model generally reproduces the observed seasonal variations and the difference between 2006 and 2011 for most variables or chemical species. Overall, these results demonstrate promising skills of WRF-CAM5 for long-term simulations at a regional scale and suggest several areas of potential improvements.« less

Application of an online-coupled regional climate model, WRF-CAM5, over East Asia for examination of ice nucleation schemes: Part I. Comprehensive model evaluation and trend analysis for 2006 and 2011

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ying; Zhang, Yang; Fan, Jiwen

Online-coupled climate and chemistry models are necessary to realistically represent the interactions between climate variables and chemical species and accurately simulate aerosol direct and indirect effects on cloud, precipitation, and radiation. In this Part I of a two-part paper, simulations from the Weather Research and Forecasting model coupled with the physics package of Community Atmosphere Model (WRF-CAM5) are conducted with the default heterogeneous ice nucleation parameterization over East Asia for two full years: 2006 and 2011. A comprehensive model evaluation is performed using satellite and surface observations. The model shows an overall acceptable performance for major meteorological variables at themore » surface and in the boundary layer, as well as column variables (e.g., precipitation, cloud fraction, precipitating water vapor, downward longwave and shortwave radiation). Moderate to large biases exist for cloud condensation nuclei over oceanic areas, cloud variables (e.g., cloud droplet number concentration, cloud liquid and ice water paths, cloud optical depth, longwave and shortwave cloud forcing). These biases indicate a need to improve the model treatments for cloud processes, especially cloud droplets and ice nucleation, as well as to reduce uncertainty in the satellite retrievals. The model simulates well the column abundances of chemical species except for column SO 2 but relatively poor for surface concentrations of several species such as CO, NO 2, SO 2, PM 2.5, and PM 10. Several reasons could contribute to the underestimation of major chemical species in East Asia including underestimations of anthropogenic emissions and natural dust emissions, uncertainties in the spatial and vertical distributions of the anthropogenic emissions, as well as biases in meteorological, radiative, and cloud predictions. Despite moderate to large biases in the chemical predictions, the model performance is generally consistent with or even better than that reported for East Asia with only a few exceptions. The model generally reproduces the observed seasonal variations and the difference between 2006 and 2011 for most variables or chemical species. Overall, these results demonstrate promising skills of WRF-CAM5 for long-term simulations at a regional scale and suggest several areas of potential improvements.« less

Ab initio study of C + H3+ reactions

NASA Technical Reports Server (NTRS)

Talbi, D.; DeFrees, D. J.

1991-01-01

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

NASA Technical Reports Server (NTRS)

Jacob, D. J.

1986-01-01

The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

Diffuse interstellar clouds as a chemical laboratory - The chemistry of diatomic carbon species

NASA Technical Reports Server (NTRS)

Federman, S. R.; Huntress, W. T., Jr.

1989-01-01

The chemistry of C2, CH, and CO in diffuse interstellar clouds is analyzed and compared to absorption line measurements toward background stars. Analytical expressions in terms of column densities are derived for the rate equations. The results indicate that in clouds with 4 mag of visual extinction, the abundance of C+ has to decrease by a factor of about 15 from the value traditionally used for clouds with 1 mag of extinction. The rate coefficients for the reactions C+ + CH - C2+ + H and C+ + H2 - CH2+ + h-nu need to be reduced from previous estimates. Chemical arguments are presented for the revised rate coefficients.

The Chemistry of Extragalactic Carbon Stars

NASA Technical Reports Server (NTRS)

Woods, Paul; Walsh, C.; Cordiner, M. A.; Kemper, F.

2013-01-01

Prompted by the ongoing interest in Spitzer Infrared Spectrometer spectra of carbon stars in the Large Magellanic Cloud, we have investigated the circumstellar chemistry of carbon stars in low-metallicity environments. Consistent with observations, our models show that acetylene is particularly abundant in the inner regions of low metallicity carbon-rich asymptotic giant branch stars - more abundant than carbon monoxide. As a consequence, larger hydrocarbons have higher abundances at the metallicities of the Magellanic Clouds than in stars with solar metallicity. We also find that the oxygen and nitrogen chemistry is suppressed at lower metallicity, as expected. Finally, we calculate molecular line emission from carbon stars in the Large and Small Magellanic Cloud and find that several molecules should be readily detectable with the Atacama Large Millimeter Array at Full Science operations.

A New Technique for the Retrieval of Near Surface Water Vapor Using DIAL Measurements

NASA Technical Reports Server (NTRS)

Ismail, Syed; Kooi, Susan; Ferrare, Richard; Winker, David; Hair, Johnathan; Nehrir, Amin; Notari, Anthony; Hostetler, Chris

2015-01-01

Water vapor is one of the most important atmospheric trace gas species and influences radiation, climate, cloud formation, surface evaporation, precipitation, storm development, transport, dynamics, and chemistry. For improvements in NWP (numerical weather prediction) and climate studies, global water vapor measurements with higher accuracy and vertical resolution are needed than are currently available. Current satellite sensors are challenged to characterize the content and distribution of water vapor in the Boundary Layer (BL) and particularly near the first few hundred meters above the surface within the BL. These measurements are critically needed to infer surface evaporation rates in cloud formation and climate studies. The NASA Langley Research Center Lidar Atmospheric Sensing Experiment (LASE) system, which uses the Differential Absorption Lidar (DIAL) technique, has demonstrated the capability to provide high quality water vapor measurements in the BL and across the troposphere. A new retrieval technique is investigated to extend these DIAL water vapor measurements to the surface. This method uses signals from both atmospheric backscattering and the strong surface returns (even over low reflectivity oceanic surfaces) using multiple gain channels to cover the large signal dynamic range. Measurements can be made between broken clouds and in presence of optically thin cirrus. Examples of LASE measurements from a variety of conditions encountered during NASA hurricane field experiments over the Atlantic Ocean are presented. Comparisons of retrieved water vapor profiles from LASE near the surface with dropsonde measurements show very good agreement. This presentation also includes a discussion of the feasibility of developing space-based DIAL capability for high resolution water vapor measurements in the BL and above and an assessment of the technology needed for developing this capability.

NASA's Earth Observing System (EOS): Observing the Atmosphere, Land, Oceans, and Ice from Space

NASA Technical Reports Server (NTRS)

King, Michael D.

2004-01-01

The Earth Observing System (EOS) is a space-based observing system comprised of a series of satellite sensors by which scientists can monitor the Earth, a Data and Information System (EOSDIS) enabling researchers worldwide to access the satellite data, and an interdisciplinary science research program to interpret the satellite data. During this year, the last of the first series of EOS missions, Aura, was launched. Aura is designed exclusively to conduct research on the composition, chemistry, and dynamics of the Earth's upper and lower atmosphere, employing multiple instruments on a single spacecraft. Aura is the third in a series of major Earth observing satellites to study the environment and climate change and is part of NASA's Earth Science Enterprise. The first and second missions, Terra and Aqua, are designed to study the land, oceans, atmospheric constituents (aerosols, clouds, temperature, and water vapor), and the Earth's radiation budget. The other seven EOS spacecraft include satellites to study (i) land cover & land use change, (ii) solar irradiance and solar spectral variation, (iii) ice volume, (iv) ocean processes (vector wind and sea surface topography), and (v) vertical variations of clouds, water vapor, and aerosols up to and including the stratosphere. Aura's chemistry measurements will also follow up on measurements that began with NASA's Upper Atmosphere Research Satellite and continue the record of satellite ozone data collected from the TOMS missions. In this presentation I will describe how scientists are using EOS data to examine the health of the earth's atmosphere, including atmospheric chemistry, aerosol properties, and cloud properties, with a special but not exclusive look at the latest earth observing mission, Aura.

NASA's Earth Observing System (EOS): Observing the Atmosphere, Land, Oceans, and Ice from Space

NASA Technical Reports Server (NTRS)

King, Michael D.

2005-01-01

The Earth Observing System (EOS) is a space-based observing system comprised of a series of satellite sensors by whch scientists can monitor the Earth, a Data and Information System (EOSDIS) enabling researchers worldwide to access the satellite data, and an interdisciplinary science research program to interpret the satellite data. During this year, the last of the first series of EOS missions, Aura, was launched. Aura is designed exclusively to conduct research on the composition, chemistry, and dynamics of the Earth's upper and lower atmosphere, employing multiple instruments on a single spacecraft. Aura is the third in a series of major Earth observing satellites to study the environment and climate change and is part of NASA's Earth Science Enterprise. The first and second missions, Terra and Aqua, are designed to study the land, oceans, atmospheric constituents (aerosols, clouds, temperature, and water vapor), and the Earth's radiation budget. The other seven EOS spacecraft include satellites to study (i) land cover & land use change, (ii) solar irradiance and solar spectral variation, (iii) ice volume, (iv) ocean processes (vector wind and sea surface topography), and (v) vertical variations of clouds, water vapor, and aerosols up to and including the stratosphere. Aura's chemistry measurements will also follow up on measurements that began with NASA's Upper Atmosphere Research Satellite and continue the record of satellite ozone data collected from the TOMS missions. In this presentation I will describe how scientists are using EOS data to examine the health of the earth's atmosphere, including atmospheric chemistry, aerosol properties, and cloud properties, with a special look at the latest earth observing mission, Aura.

Effects of surface-active organic matter on carbon dioxide nucleation in atmospheric wet aerosols: a molecular dynamics study.

PubMed

Daskalakis, Vangelis; Charalambous, Fevronia; Panagiotou, Fostira; Nearchou, Irene

2014-11-21

Organic matter (OM) uptake in cloud droplets produces water-soluble secondary organic aerosols (SOA) via aqueous chemistry. These play a significant role in aerosol properties. We report the effects of OM uptake in wet aerosols, in terms of the dissolved-to-gas carbon dioxide nucleation using molecular dynamics (MD) simulations. Carbon dioxide has been implicated in the natural rainwater as well as seawater acidity. Variability of the cloud and raindrop pH is assumed in space and time, as regional emissions, local human activities and geophysical characteristics differ. Rain scavenging of inorganic SOx, NOx and NH3 plays a major role in rain acidity in terms of acid-base activity, however carbon dioxide solubility also remains a key parameter. Based on the MD simulations we propose that the presence of surface-active OM promotes the dissolved-to-gas carbon dioxide nucleation in wet aerosols, even at low temperatures, strongly decreasing carbon dioxide solubility. A discussion is made on the role of OM in controlling the pH of a cloud or raindrop, as a consequence, without involving OM ionization equilibrium. The results are compared with experimental and computational studies in the literature.

Sulfate aerosols and polar stratospheric cloud formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolbert, M.A.

Before the discovery of the Antarctic ozone hole, it was generally assumed that gas-phase chemical reactions controlled the abundance of stratospheric ozone. However, the massive springtime ozone losses over Antarctica first reported by Farman et al in 1985 could not be explained on the basis of gas-phase chemistry alone. In 1986, Solomon et al suggested that chemical reactions occurring on the surfaces of polar stratospheric clouds (PSCs) could be important for the observed ozone losses. Since that time, an explosion of laboratory, field, and theoretical research in heterogeneous atmospheric chemistry has occurred. Recent work has indicated that the most importantmore » heterogeneous reaction on PSCs is ClONO[sub 2] + HCl [yields] Cl[sub 2] + HNO[sub 3]. This reaction converts inert chlorine into photochemically active Cl[sub 2]. Photolysis of Cl[sub 2] then leads to chlorine radicals capable of destroying ozone through very efficient catalytic chain reactions. New observations during the second Airborne Arctic Stratospheric Expedition found stoichiometric loss of ClONO[sub 2] and HCl in air processed by PSCs in accordance with reaction 1. Attention is turning toward understanding what kinds of aerosols form in the stratospheric, their formation mechanism, surface area, and specific chemical reactivity. Some of the latest findings, which underline the importance of aerosols, were presented at a recent National Aeronautics and Space Administration workshop in Boulder, Colorado.« less

Sulfur chemistry in dense interstellar clouds

NASA Technical Reports Server (NTRS)

Prasad, S. S.; Huntress, W. T., Jr.

1982-01-01

A model is presented for the gas phase chemistry of molecules containing sulfur in dense interstellar clouds. The sulfur chemistry is different from that used in previous models as a result of an extensive search of the recent literature and the availability of new laboratory data. The changes have a significant effect on the calculated abundance of sulfur compounds. The linked chemistry of sulfur and oxygen in the present model requires a severe depletion of sulfur and low fractional abundances of both O and O2 in the dense clouds. In contrast, the high abundance of SO and the low abundance of CS relative to SO in the HVS in the KL may indicate an oxygen-rich, high temperature environment compared to OMC-1. The formation of S-H bonds is slow because of the absence of radiative association between S(+) and H2. The present model underestimates the abundance of H2S unless a radiative association reaction between HS(+) and H2 is postulated.

An Intercomparison of Research Scanning Polarimeter Cloud Droplet Number Concentrations with Aerosol Properties over the Atlantic Ocean

NASA Astrophysics Data System (ADS)

Sinclair, K.; van Diedenhoven, B.; Cairns, B.; Alexandrov, M. D.; Ziemba, L. D.; Moore, R.; Crosbie, E.; Hostetler, C. A.

2016-12-01

Cloud droplet number concentration (CDNC) is a key parameter of of liquid clouds and is essential for the understanding of aerosol-cloud interaction. It couples surface aerosol composition and chemistry on the one hand and cloud reflectivity on the other. It impacts radiative forcing, cloud evolution, precipitation, global climate and, through observation, can be used to monitor the cloud albedo effect, or the first indirect effect. The North Atlantic and Marine Ecosystems Study (NAAMES), which is a NASA-led ship and air campaign that takes place off the east coast of Newfoundland, observed many low cloud decks and aerosols over a marine environment. This campaign has completed two of four deployments and provides an excellent opportunity for the Research Scanning Polarimeter (RSP) to cross-validate its approach of sensing CDNC with the Langley Aerosol Research Group Experiment's (LARGE's) Cloud Droplet Probe (CDP). The RSP is an airborne scanning sensor that provides high-precision measurements of polarized and full-intensity radiances at multiple angles over a wide spectral range. Each of the four NAAMES deployments are aligned to a specific annual event in the plankton cycle, along with other variations in environmental conditions. The Fall 2015 and spring 2016 deployments allow us to demonstrate and characterize the RSP's performance over a range of CDNCs and cloud types. We also assess correlations between the RSP CDNC measurements and atmospheric aerosol load. Using the LARGE Cloud Particle Counter (CPC) and Aerosol Mass Spectrometer (AMS), links between the size and type of aerosols and the RSP CDNC retrievals are explored.

Aggregation Kinetics of Diesel Soot Nanoparticles in Wet Environments.

PubMed

Chen, Chengyu; Huang, Weilin

2017-02-21

Soot produced during incomplete combustion consists mainly of carbonaceous nanoparticles (NPs) with severe adverse environmental and health effects, and its environmental fate and transport are largely controlled by aggregation. In this study, we examined the aggregation behavior for diesel soot NPs under aqueous condition in an effort to elucidate the fundamental processes that govern soot particle-particle interactions in wet environments such as rain droplets or surface aquatic systems. The influence of electrolytes and aqueous pH on colloidal stability of these NPs was investigated by measuring their aggregation kinetics in different aqueous solution chemistries. The results showed that the NPs had negatively charged surfaces and exhibited both reaction- and diffusion-limited aggregation regimes with rates depended upon solution chemistry. The aggregation kinetics data were in good agreement with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical coagulation concentrations (CCC) were quantified and the Hamaker constant was derived for the soot (1.4 × 10 -20 J) using the colloidal chemistry approach. The study indicated that, depending upon local aqueous chemistry, single soot NPs could remain stable against self-aggregation in typical freshwater environments and in neutral cloud droplets but are likely to aggregate under salty (e.g., estuaries) or acidic (e.g., acid rain droplets) aquatic conditions or both.

Chemistry in dynamically evolving clouds

NASA Technical Reports Server (NTRS)

Tarafdar, S. P.; Prasad, S. S.; Huntress, W. T., Jr.; Villere, K. R.; Black, D. C.

1985-01-01

A unified model of chemical and dynamical evolution of isolated, initially diffuse and quiescent interstellar clouds is presented. The model uses a semiempirically derived dependence of the observed cloud temperatures on the visual extinction and density. Even low-mass, low-density, diffuse clouds can collapse in this model, because the inward pressure gradient force assists gravitational contraction. In contrast, previous isothermal collapse models required the low-mass diffuse clouds to be unrealistically cold before gravitational contraction could start. Theoretically predicted dependences of the column densities of various atoms and molecules, such as C and CO, on visual extinction in diffuse clouds are in accord with observations. Similarly, the predicted dependences of the fractional abundances of various chemical species (e.g., CO, H2CO, HCN, HCO(+)) on the total hydrogen density in the core of the dense clouds also agree with observations reported to date in the literature. Compared with previous models of interstellar chemistry, the present model has the potential to explain the wide spectrum of chemical and physical properties of both diffuse and dense clouds with a common formalism employing only a few simple initial conditions.

Photolysis frequency and cloud dynamics during DC3 and SEAC4RS

NASA Astrophysics Data System (ADS)

Hall, S. R.; Ullmann, K.; Madronich, S.; Hair, J. W.; Butler, C. F.; Fenn, M. A.

2013-12-01

Cloud shading plays a critical role in extending the lifetime of short-lived chemical species. During convection, photochemistry is reduced such that short-lived species may be transported from the boundary layer to the upper troposphere/ lower stratosphere. In the anvil outflow, shading continues within and below the cloud. However, near the highly scattering cloud top, the chemistry is greatly accelerated. In this rapidly evolving environment, accurate photolysis frequencies are required to study photochemical evolution of the complex composition. During the Deep Convective Clouds and Chemistry (DC3, 2012) and the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, 2013) campaigns, photolysis frequencies were determined by measurement of spectrally resolved actinic flux by the Charge-coupled device Actinic Flux Spectroradiometer (CAFS) on the NASA DC-8 and the HIAPER Airborne Radiation Package (HARP) on the NCAR G-V aircraft. Vertical flight profiles allowed in situ characterization of the radiation environment. Input of geometrical cloud characteristics into the Tropospheric Ultraviolet and Visible (TUV) Radiation was used to constrain cloud optical depths for more spatially and temporally stable conditions.

Vertical Distribution of Water at Phoenix

NASA Technical Reports Server (NTRS)

Tamppari, L. K.; Lemmon, M. T.

2011-01-01

Phoenix results, combined with coordinated observations from the Mars Reconnaissance Orbiter of the Phoenix lander site, indicate that the water vapor is nonuniform (i.e., not well mixed) up to a calculated cloud condensation level. It is important to understand the mixing profile of water vapor because (a) the assumption of a well-mixed atmosphere up to a cloud condensation level is common in retrievals of column water abundances which are in turn used to understand the seasonal and interannual behavior of water, (b) there is a long history of observations and modeling that conclude both that water vapor is and is not well-mixed, and some studies indicate that the water vapor vertical mixing profile may, in fact, change with season and location, (c) the water vapor in the lowest part of the atmosphere is the reservoir that can exchange with the regolith and higher amounts may have an impact on the surface chemistry, and (d) greater water vapor abundances close to the surface may enhance surface exchange thereby reducing regional transport, which in turn has implications to the net transport of water vapor over seasonal and annual timescales.

Implementation of aerosol-cloud interactions in the regional atmosphere-aerosol model COSMO-MUSCAT(5.0) and evaluation using satellite data

NASA Astrophysics Data System (ADS)

Dipu, Sudhakar; Quaas, Johannes; Wolke, Ralf; Stoll, Jens; Mühlbauer, Andreas; Sourdeval, Odran; Salzmann, Marc; Heinold, Bernd; Tegen, Ina

2017-06-01

The regional atmospheric model Consortium for Small-scale Modeling (COSMO) coupled to the Multi-Scale Chemistry Aerosol Transport model (MUSCAT) is extended in this work to represent aerosol-cloud interactions. Previously, only one-way interactions (scavenging of aerosol and in-cloud chemistry) and aerosol-radiation interactions were included in this model. The new version allows for a microphysical aerosol effect on clouds. For this, we use the optional two-moment cloud microphysical scheme in COSMO and the online-computed aerosol information for cloud condensation nuclei concentrations (Cccn), replacing the constant Cccn profile. In the radiation scheme, we have implemented a droplet-size-dependent cloud optical depth, allowing now for aerosol-cloud-radiation interactions. To evaluate the models with satellite data, the Cloud Feedback Model Intercomparison Project Observation Simulator Package (COSP) has been implemented. A case study has been carried out to understand the effects of the modifications, where the modified modeling system is applied over the European domain with a horizontal resolution of 0.25° × 0.25°. To reduce the complexity in aerosol-cloud interactions, only warm-phase clouds are considered. We found that the online-coupled aerosol introduces significant changes for some cloud microphysical properties. The cloud effective radius shows an increase of 9.5 %, and the cloud droplet number concentration is reduced by 21.5 %.

Coupled Sulfur and Chlorine Chemistry in Venus' Upper Cloud Layer

NASA Astrophysics Data System (ADS)

Mills, Franklin P.

2006-09-01

Venus' atmosphere likely contains a rich variety of sulfur and chlorine compounds because HCl, SO2, and OCS have all been observed. Photodissociation of CO2 and SO2 in the upper cloud layer produces oxygen which can react directly or indirectly with SO2 to form SO3 and eventually H2SO4. Photodissociation of HCl within and above the upper cloud layer produces chlorine which can react with CO and O2 to form ClCO and ClC(O)OO. These two species have been identified as potentially critical intermediaries in the production of CO2. Much less work has been done on the potential coupling between sulfur and chlorine chemistry that may occur within the upper cloud layer. Several aspects have been examined in recent modeling: (1) linkage of the CO2 and sulfur oxidation cycles (based on ideas from Yung and DeMore, 1982), (2) reaction of Cl with SO2 to form ClSO2 (based on ideas from DeMore et al., 1985), and (3) the chemistry of SmCln for m,n = 1,2 (based on preliminary work in Mills, 1998). Initial results suggest the chemistry of SmCln may provide a pathway for accelerated production of polysulfur, Sx, if the oxygen abundance in the upper cloud layer is as small as is implied by the observational limit on O2 (Trauger and Lunine, 1983). Initial results also suggest that ClSO2 can act as a buffer which helps increase the scale height of SO2 and decrease the rate of production of H2SO4. This presentation will describe the results from this modeling; discuss their potential implications for the CO2, sulfur oxidation, and polysulfur cycles; and outline key observations from Venus Express that can help resolve existing questions concerning the chemistry of Venus' upper cloud. Partial funding for this research was provided by the Australian Research Council.

Optical observations related to the molecular chemistry in diffuse interstellar clouds

NASA Technical Reports Server (NTRS)

Federman, S. R.

1987-01-01

Observations, which have been published since 1979, of molecular species in diffuse clouds are discussed. Particular attention is given to the ultraviolet measurements of CO with the Copernicus and IUE satellites and to ground-based optical measurements of CH, CH(+), CN, and 02. These data encompass large enough samples to test the chemical schemes expected to occur in diffuse clouds. Upper limits for other species (e.g., H2O, H2O(+), and C3) place restrictions on the pathways for molecular production. Moreover, analysis of the rotational distribution of the C2 molecule results in the determination of the physical conditions of the cloud. These parameters, including density, temperature, and the intensity of the radiation field, are necessary for modeling the chemistry.

The chemistry of planet-forming regions is not interstellar.

PubMed

Pontoppidan, Klaus M; Blevins, Sandra M

2014-01-01

Advances in infrared and submillimeter technology have allowed for detailed observations of the molecular content of the planet-forming regions of protoplanetary disks. In particular, disks around solar-type stars now have growing molecular inventories that can be directly compared with both prestellar chemistry and that inferred for the early solar nebula. The data directly address the old question of whether the chemistry of planet-forming matter is similar or different and unique relative to the chemistry of dense clouds and protostellar envelopes. The answer to this question may have profound consequences for the structure and composition of planetary systems. The practical challenge is that observations of emission lines from disks do not easily translate into chemical concentrations. Here, we present a two-dimensional radiative transfer model of RNO 90, a classical protoplanetary disk around a solar-mass star, and retrieve the concentrations of dominant molecular carriers of carbon, oxygen and nitrogen in the terrestrial region around 1 AU. We compare our results to the chemical inventory of dense clouds and protostellar envelopes, and argue that inner disk chemistry is, as expected, fundamentally different from prestellar chemistry. We find that the clearest discriminant may be the concentration of CO2, which is extremely low in disks, but one of the most abundant constituents of dense clouds and protostellar envelopes.

Ionisation in ultra-cool, cloud forming extrasolar planetary atmospheres

NASA Astrophysics Data System (ADS)

Helling, Christiane; the LEAP Team

2015-04-01

Transit spectroscopy provides evidence that extrasolare planets are covered in clouds, a finding that has been forecast by cloud model simulations 15 years ago. Atmospheres are strongly affected by clouds through their large opacity and their chemical activity. Cloud formation models allow to predict cloud particle sizes, their chemical composition and the composition of the remaining atmospheric gas (Woitke & Helling 2004, A&A 414; Helling & Woitke 2006, A&A 455), for example, as input for radiative transfer codes like Drift-Phoenix (Witte et al. 2009; A&A 506). These cloud particles are charged and can discharge, for example in form of lighting (Helling et al. 2013, ApJ 767; Bailey et al. 2014, ApJ 784). Earth observations demonstrate that lighting effects not only the local chemistry but also the electron budget of the atmosphere. This talk will present our work on cloud formation modelling and ionisation processes in cloud forming atmospheres. An hierarchy of ionisation processes leads to a vertically inhomogenously ionised atmosphere which has implications for planetary mass loss and global circulation pattern of planetary atmospheres. Processes involved, like Cosmic Ray ionisation, do also activate the local chemistry such that large hydrocarbon molecules form (Rimmer et al. 2014, IJAsB 13).

Quantifying spatial variability of AgI cloud seeding benefits and Ag enrichments in snow

NASA Astrophysics Data System (ADS)

Fisher, J.; Benner, S. G.; Lytle, M. L.; Kunkel, M. L.; Blestrud, D.; Holbrook, V. P.; Parkinson, S.; Edwards, R.

2016-12-01

Glaciogenic cloud seeding is an important scientific technology for enhancing water resources across in the Western United States. Cloud seeding enriches super cooled liquid water layers with plumes of silver iodide (AgI), an artificial ice nuclei. Recent studies using target-control regression analysis and modeling estimate glaciogenic cloud seeding increases snow precipitation between 3-15% annually. However, the efficacy of cloud seeding programs is difficult to assess using weather models and statistics alone. This study will supplement precipitation enhancement statistics and Weather Research and Forecasting (WRF) model outputs with ultra-trace chemistry. Combining precipitation enhancement estimates with trace chemistry data (to estimate AgI plume targeting accuracy) may provide a more robust analysis. Precipitation enhancement from the 2016 water year will be modeled two ways. First, by using double-mass curve. Annual SNOTEL data of the cumulative SWE in unseeded areas and cumulative SWE in seeded areas will be compared before, and after, the cloud seeding program's initiation in 2003. Any change in the double-mass curve's slope after 2003 may be attributed to cloud seeding. Second, WRF model estimates of precipitation will be compared to the observed precipitation at SNOTEL sites. The difference between observed and modeled precipitation in AgI seeded regions may also be attributed to cloud seeding (assuming modeled and observed data are comparable at unseeded SNOTEL stations). Ultra-trace snow chemistry data from the 2016 winter season will be used to validate whether estimated precipitation increases are positively correlated with the mass of silver in the snowpack.

Synthesis and Surface-Specific Analysis of Molecular Constituents Relevant to Biogenic Secondary Organic Aerosol Material

NASA Astrophysics Data System (ADS)

Be, A. G.; Upshur, M. A.; Chase, H. M.; Geiger, F.; Thomson, R. J.

2017-12-01

Secondary organic aerosol (SOA) particles formed from the oxidation of biogenic volatile organic compounds (BVOCs) remain a principal, yet elusive, class of airborne particulate matter that impacts the Earth's radiation budget. Given the characteristic molecular complexity comprising biogenic SOA particles, chemical information selective to the gas-aerosol interface may be valuable in the investigation of such systems, as surface considerations likely dictate the phenomena driving particle evolution mechanisms and climate effects. In particular, cloud activation processes may be parameterized using the surface tension depression that coincides with partitioning of surface-active organic species to the gas-droplet interface. However, the extent to which surface chemical processes, such as cloud droplet condensation, are influenced by the chemical structure and reactivity of individual surface-active molecules in SOA particles is largely unknown. We seek to study terpene-derived organic species relevant to the surfaces of biogenic SOA particles via synthesis of putative oxidation products followed by analysis using surface-selective physicochemical measurements. Using dynamic surface tension measurements, considerable differences are observed in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from abundant terpene precursors. Furthermore, sum frequency generation spectroscopy is utilized for comparison of the surface vibrational spectral responses of synthesized reference compounds with those observed for laboratory aerosol toward probing the surface composition of SOA material. Such ongoing findings highlight the underlying importance of molecular structure and reactivity when considering the surface chemistry of biogenic terpene-derived atmospheric aerosols.

Vapor-deposited water and nitric acid ices

NASA Astrophysics Data System (ADS)

Leu, Ming-Taun; Keyser, Leon F.

Ices formed by vapor deposition have been the subject of numerous laboratory investigations in connection with snow and glaciers on the ground, ice clouds in the terrestrial atmosphere, surfaces of other planets and their satellites, and the interstellar medium. In this review we will focus on these specific subjects: (1) heterogeneous chemistry on the surfaces of polar stratospheric clouds (PSCs) and (2) surfaces of satellites of the outer planets in our solar system. Stratospheric ozone provides a protective shield for mankind and the global biosphere from harmful ultraviolet solar radiation. In past decades, theoretical atmospheric models for the calculation of ozone balance frequently used only homogeneous gas-phase reactions in their studies. Since the discovery of the Antarctic ozone hole in 1985, however, it has been demonstrated that knowledge of heterogeneous reactions on the surface of PSCs is definitely needed to understand this significant natural event due to the anthropogenic emission of chlorofluorocarbons (CFCs). We will briefly discuss the experimental techniques for the investigation of heterogeneous chemistry on ice surfaces carried out in our laboratories. The experimental apparatus used include: several flow-tube reactors, an electron-impact ionization mass spectrometer, a Fourier transform infrared spectrometer, a BET adsorption apparatus, and a scanning environmental electron microscope. The adsorption experiments and electron microscopic work have demonstrated that the vapor-deposited ices are highly porous. Therefore, it is necessary to develop theoretical models for the elucidation of the uptake and reactivity of trace gases in porous ice substrates. Several measurements of uptake and reaction probabilities of these trace gases on water ices and nitric acid ices have been performed under ambient conditions in the upper troposphere and lower stratosphere, mainly in the temperature range 180-220 K. The trace gases of atmospheric importance in heterogeneous chemistry include: ClONO2, HCl, HOCl, and HNO3. In addition, recent interest in the possible landing of a robotic spacecraft on the surface of Europa, one of the Galilean satellites of Jupiter, and ground based telescopic observations demand detailed knowledge of the physical properties of the icy surfaces of the outer planets and their satellites. Lower temperature studies in the range 77-150 K using both electron microscopy and adsorption isotherms (BET surface area measurements) have revealed some intriguing observations that may provide some insights for remote sensing of these satellite surfaces. Finally, we will attempt to summarize our recent results and suggest future research directions in both theoretical and laboratory investigations.

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

PubMed

Křepelová, Adéla; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

2010-12-17

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

Insights on How NASA's Earth Observing System (EOS) Monitors Our World Environment

NASA Technical Reports Server (NTRS)

King, Michael D.

2000-01-01

The Earth Observing System (EOS) is a space-based observing system comprised of a series of satellite sensors by which scientists can monitor the Earth, a Data and Information System (EOSDIS) enabling researchers worldwide to access the satellite data, and an interdisciplinary science research program to interpret the satellite data. During this year, four EOS science missions were launched, representing observations of (1) total solar irradiance, (2) Earth radiation budget, (3) land cover and land use change, (4) ocean processes (vector wind, sea surface temperature, and ocean color), (5) atmospheric processes (aerosol and cloud properties, water vapor, and temperature and moisture profiles), and (6) tropospheric chemistry. In succeeding years many more satellites will be launched that will contribute immeasurably to our understanding of the Earth's environment. In this presentation I will describe how scientists are using EOS data to examine land use and natural hazards, environmental air quality, including dust storms over the world's deserts, cloud and radiation properties, sea surface temperature, and winds over the ocean.

Assessing regional scale predictions of aerosols, marine stratocumulus, and their interactions during VOCALS-REx using WRF-Chem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Qing; Gustafson, William I.; Fast, Jerome D.

2011-12-02

In the recent chemistry version (v3.3) of the Weather Research and Forecasting (WRF-Chem) model, we have coupled the Morrison double-moment microphysics scheme with interactive aerosols so that full two-way aerosol-cloud interactions are included in simulations. We have used this new WRF-Chem functionality in a study focused on assessing predictions of aerosols, marine stratocumulus clouds, and their interactions over the Southeast Pacific using measurements from the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) and satellite retrievals. This study also serves as a detailed analysis of our WRF-Chem simulations contributed to the VOCALS model Assessment (VOCA) project. The WRF-Chem 31-day (October 15-November 16,more » 2008) simulation with aerosol-cloud interactions (AERO hereafter) is also compared to a simulation (MET hereafter) with fixed cloud droplet number concentrations assumed by the default in Morrison microphysics scheme with no interactive aerosols. The well-predicted aerosol properties such as number, mass composition, and optical depth lead to significant improvements in many features of the predicted stratocumulus clouds: cloud optical properties and microphysical properties such as cloud top effective radius, cloud water path, and cloud optical thickness, and cloud macrostructure such as cloud depth and cloud base height. These improvements in addition to the aerosol direct and semi-direct effects, in turn, feed back to the prediction of boundary-layer characteristics and energy budgets. Particularly, inclusion of interactive aerosols in AERO strengths temperature and humidity gradients within capping inversion layer and lowers the MBL depth by 150 m from that of the MET simulation. Mean top-of-the-atmosphere outgoing shortwave fluxes, surface latent heat, and surface downwelling longwave fluxes are in better agreement with observations in AERO, compared to the MET simulation. Nevertheless, biases in some of the simulated meteorological quantities (e.g., MBL temperature and humidity over the remote ocean) and aerosol quantities (e.g., overestimations of supermicron sea salt mass) might affect simulated stratocumulus and energy fluxes over the SEP, and require further investigations. Although not perfect, the overall performance of the regional model in simulating mesoscale aerosol-cloud interactions is encouraging and suggests that the inclusion of spatially varying aerosol characteristics is important when simulating marine stratocumulus over the southeastern Pacific.« less

Evaluating Lightning-generated NOx (LNOx) Parameterization based on Cloud Top Height at Resolutions with Partially-resolved Convection for Upper Tropospheric Chemistry Studies

NASA Astrophysics Data System (ADS)

Wong, J.; Barth, M. C.; Noone, D. C.

2012-12-01

Lightning-generated nitrogen oxides (LNOx) is an important precursor to tropospheric ozone production. With a meteorological time-scale variability similar to that of the ozone chemical lifetime, it can nonlinearly perturb tropospheric ozone concentration. Coupled with upper-air circulation patterns, LNOx can accumulate in significant amount in the upper troposphere with other precursors, thus enhancing ozone production (see attached figure). While LNOx emission has been included and tuned extensively in global climate models, its inclusions in regional chemistry models are seldom tested. Here we present a study that evaluates the frequently used Price and Rind parameterization based on cloud-top height at resolutions that partially resolve deep convection using the Weather Research and Forecasting model with Chemistry (WRF-Chem) over the contiguous United States. With minor modifications, the parameterization is shown to generate integrated flash counts close to those observed. However, the modeled frequency distribution of cloud-to-ground flashes do not represent well for storms with high flash rates, bringing into question the applicability of the intra-cloud/ground partitioning (IC:CG) formulation of Price and Rind in some studies. Resolution dependency also requires attention when sub-grid cloud-tops are used instead of the originally intended grid-averaged cloud-top. LNOx passive tracers being gathered by monsoonal upper tropospheric anticyclone.

Boundary Conditions for the Paleoenvironment: Chemical and Physical Processes in Dense Interstellar Clouds: Summary of Research

NASA Technical Reports Server (NTRS)

Irvine, William M.

1999-01-01

The basic theme of this program was the study of molecular complexity and evolution for the biogenic elements and compounds in interstellar clouds and in primitive solar system objects. Research included the detection and study of new interstellar and cometary molecules and investigation of reaction pathways for astrochemistry from a comparison of theory and observed molecular abundances. The latter includes studies of cold, dark clouds in which ion-molecule chemistry should predominate, searches for the effects of interchange of material between the gas and solid phases in interstellar clouds, unbiased spectral surveys of particular sources, and systematic investigation of the interlinked chemistry and physics of dense interstellar clouds. In addition, the study of comets has allowed a comparison between the chemistry of such minimally thermally processed objects and that of interstellar clouds, shedding light on the evolution of the biogenic elements during the process of solar system formation. One PhD dissertation on this research was completed by a graduate student at the University of Massachusetts. An additional 4 graduate students at the University of Massachusetts and 5 graduate students from other institutions participated in research supported by this grant, with 6 of these thus far receiving PhD degrees from the University of Massachusetts or their home institutions. Four postdoctoral research associates at the University of Massachusetts also participated in research supported by this grant, receiving valuable training.

The Physics and Chemistry of Small Translucent Molecular Clouds. VIII. HCN and HNC

NASA Astrophysics Data System (ADS)

Turner, B. E.; Pirogov, L.; Minh, Y. C.

1997-07-01

We have conducted a survey of HCN and HNC (two rotational transitions each) in our standard sample of 11 cirrus cores and 27 Clemens-Barvainis translucent cores whose structures and chemistry have been studied earlier in this series. Both species are seen in all 38 objects. HCNH+ has been searched in three objects. These results are modeled in terms of our previous hydrostatic equilibrium and n ~ r-α structures together with other chemical and physical properties derived earlier. A detailed program has been written to handle the complex radiative transfer of the hyperfine splitting (hfs) of HCN. It is shown that serious errors are made in deriving HCN abundances by methods that ignore the hfs. Both HCN and HNC abundances are high, typically 1(-8) in most sources. The chemically important ratio HCN/HNC is found to be ~2.5 if these species are spatially centrally peaked and ~6 if not. Both species abundances increase monotonically with increasing extinction in the 1.2-2.7 mag range (edge to center), thus displaying the same characteristic transition between diffuse and dense cloud chemistry as do most other species we have studied. HCN/HNC decreases with increasing extinction to a value of 1.3 at Av0 ~ 10, approaching the expected value of 1.0 for dense clouds. Two types of ion-molecule chemistry models have been carried out: a full model using the Standard Model rate file and comprising 409 species (by Lee and Herbst), and a simplified model comprising 21 nitrogen-bearing species for conditions relevant to translucent clouds. Good agreement between observations and chemistry models is achieved throughout the translucent extinction range. Important conclusions are that (1) neutral-neutral reactions such as N + CH2 dominate the chemistry of HCN; (2) low ion-polar reaction rates are strongly favored over high ones; (3) the reaction C+ + NH3 --> H2NC+ --> HNC is unimportant, thus largely uncoupling the CN and NH chemistries; (4) the ratio HCN/HNC is not a particularly important diagnostic of the CN chemistry; (5) model NH3 abundances are at least a factor 100 lower than observed in translucent clouds, even if the reaction N+H+3-->NH+2 is permitted at Langevin rate.

Aqueous-phase source of formic acid in clouds

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1983-01-01

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

The role of aqueous chemistry in determining the composition and cloud structure of the upper troposphere on Uranus

NASA Technical Reports Server (NTRS)

Carlson, Barbara E.; Prather, Michael J.; Rossow, William B.

1987-01-01

Aqueous chemistry on Uranus affects the atmospheric abundances of NH3 and H2S below the methane cloud base. Here a complete thermochemical equilibrium model for the H2O-NH3-H2S system is presented. Inclusion of H2S increases the aqueous removal of NH3 to 20-30 percent, but aqueous chemistry alone cannot account for the depletion of NH3 in the 150-200-K region of the atmosphere required to fit microwave observations. Formation of NH4SH clouds can account for the observed depletion provided the H2S/NH3 ratio is enhanced by a factor of 4 relative to solar. Perturbations to the chemical balance between N and S, for example by the general circulation on Uranus, would then produce regions with either NH3 or H2S aloft.

The Relationships Between Insoluble Precipitation Residues, Clouds, and Precipitation Over California's Southern Sierra Nevada During Winter Storms

NASA Technical Reports Server (NTRS)

Creamean, Jessie M.; White, Allen B.; Minnis, Patrick; Palikonda, Rabindra; Spangenberg, Douglas A.; Prather, Kimberly A.

2016-01-01

Ice formation in orographic mixed-phase clouds can enhance precipitation and depends on the type of aerosols that serve as ice nucleating particles (INP). The resulting precipitation from these clouds is a viable source of water, especially for regions such as the California Sierra Nevada. Thus, a better understanding of the sources of INP that impact orographic clouds is important for assessing water availability in California. This study presents a multi-site, multi-year analysis of single particle insoluble residues in precipitation samples that likely influenced cloud ice and precipitation formation above Yosemite National Park. Dust and biological particles represented the dominant fraction of the residues (64% on average). Cloud glaciation, determined using GOES satellite observations, not only depended on high cloud tops (greater than 6.2 km) and low temperatures (less than -26 C), but also on the composition of the dust and biological residues. The greatest prevalence of ice-phase clouds occurred in conjunction with biologically-rich residues and mineral dust rich in calcium, followed by iron and aluminosilicates. Dust and biological particles are known to be efficient INP, thus these residues are what likely influenced ice formation in clouds above the sites and subsequent precipitation quantities reaching the surface during events with similar meteorology. The goal of this study is to use precipitation chemistry information to gain a better understanding of the potential sources of INP in the south-central Sierra Nevada, where cloud-aerosol-precipitation interactions are under-studied and where mixed-phase orographic clouds represent a key element in the generation of precipitation and thus the water supply in California.

The chemistry-climate model ECHAM6.3-HAM2.3-MOZ1.0

NASA Astrophysics Data System (ADS)

Schultz, Martin G.; Stadtler, Scarlet; Schröder, Sabine; Taraborrelli, Domenico; Franco, Bruno; Krefting, Jonathan; Henrot, Alexandra; Ferrachat, Sylvaine; Lohmann, Ulrike; Neubauer, David; Siegenthaler-Le Drian, Colombe; Wahl, Sebastian; Kokkola, Harri; Kühn, Thomas; Rast, Sebastian; Schmidt, Hauke; Stier, Philip; Kinnison, Doug; Tyndall, Geoffrey S.; Orlando, John J.; Wespes, Catherine

2018-05-01

The chemistry-climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

SEM Imaging and Chemical Analysis of Aerosol Particles from Surface and Hi-altitudes in New Jersey.

NASA Astrophysics Data System (ADS)

Bandamede, M.; Boaggio, K.; Bancroft, L.; Hurler, K.; Magee, N. B.

2016-12-01

We report on Scanning Electron Microscopy analysis of aerosol particle morphology and chemistry. The work includes the first comparative SEM analysis of aerosol particles captured by balloon at high altitude. The particles were acquired in an urban/suburban environment in central New-Jersey. Particles were sampled from near the surface using ambient air filtration and at high-altitudes using a novel balloon-borne instrument (ICE-Ball, see abstract by K. Boaggio). Particle images and 3D geometry are acquired by a Hitachi SU-5000 SEM, with resolution to approximately 3 nm. Elemental analysis on particles is provided by Energy Dispersive X-Ray Spectroscopy (EDS, EDAX, Inc.). Uncoated imaging is conducted in low vacuum within the variable-pressure SEM, which provides improved detection and analysis of light-element compositions including Carbon. Preliminary results suggest that some similar particle types and chemical species are sampled at both surface and high-altitude. However, as expected, particle morphologies, concentrations, chemistry, and apparent origin vary significantly at different altitudes and under different atmospheric flow regimes. Improved characterization of high-altitude aerosol particles, and differences from surface particulate composition, may advance inputs for atmospheric cloud and radiation models.

Effects of Precursor Concentration and Acidic Sulfate in Aqueous Glyoxal−OH Radical Oxidation and Implications for Secondary Organic Aerosol

PubMed Central

2009-01-01

Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30−3000 μM) and the presence of acidic sulfate (0−840 μM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 μM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA. PMID:19924930

Detection of interstellar HCS and its metastable isomer HSC: new pieces in the puzzle of sulfur chemistry

NASA Astrophysics Data System (ADS)

Agúndez, M.; Marcelino, N.; Cernicharo, J.; Tafalla, M.

2018-03-01

We present the first identification in interstellar space of the thioformyl radical (HCS) and its metastable isomer HSC. These species were detected toward the molecular cloud L483 through observations carried out with the IRAM 30 m telescope in the λ3 mm band. We derive beam-averaged column densities of 7 × 1012 cm-2 for HCS and 1.8 × 1011 cm-2 for HSC, which translate into fractional abundances relative to H2 of 2 × 10-10 and 6 × 10-12, respectively. Although the amount of sulfur locked by these radicals is low, their detection allows placing interesting constraints on the chemistry of sulfur in dark clouds. Interestingly, the H2CS/HCS abundance ratio is found to be quite low, 1, in contrast with the oxygen analog case, in which the H2CO/HCO abundance ratio is around 10 in dark clouds. Moreover, the radical HCS is found to be more abundant than its oxygen analog, HCO. The metastable species HOC, the oxygen analog of HSC, has not yet been observed in space. These observational constraints are compared with the outcome of a recent model of the chemistry of sulfur in dark clouds. The model underestimates the fractional abundance of HCS by at least one order of magnitude, overestimates the H2CS/HCS abundance ratio, and does not provide an abundance prediction for the metastable isomer HSC. These observations should prompt a revision of the chemistry of sulfur in interstellar clouds.

Investigation of diverse bacteria in cloud water at Mt. Tai, China.

PubMed

Xu, Caihong; Wei, Min; Chen, Jianmin; Sui, Xiao; Zhu, Chao; Li, Jiarong; Zheng, Lulu; Sui, Guodong; Li, Weijun; Wang, Wenxing; Zhang, Qingzhu; Mellouki, Abdelwahid

2017-02-15

Bacteria are abundant in atmospheric water phase with the potential to influence atmospheric processes and human health, yet relatively little information is known about the bacterial characteristics at high altitudes. Here we investigated the bacterial community by high throughput sequencing in 24 cloud water samples collected from September 26 to October 31, at the summit of Mt. Tai (36°15' N, 117°06' E, 1534m a.s.l) in China. Diverse bacterial population were identified and the gram-negative bacteria contributed the majority of total bacteria including Proteobacteria (81.6%) and Bacteroidetes (3.9%), followed by gram-positive bacteria Firmicutes (7.1%) and Actinobacteria (2.3%). These gram-negative taxa mainly inhabited in leaf-surface and cold environments. Meanwhile bacteria involved in the cloud condensation nuclei and ice nuclei formation were observed such as Sphingomonas (6.7%), Pseudomonas (4.1%), and Bacillus (1.1%). In addition, Sphingmonas was more active than that in daytime and participated in the cloud chemistry process. Meanwhile O 3 and SO 2 critically contributed to the variation of bacterial community. It is the first report on the bacterial community structure of cloud water over Asian area. Our results can serve as an important reference for environmental scientists, and biologists. Copyright © 2016. Published by Elsevier B.V.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust.

PubMed

Gaston, Cassandra J; Pratt, Kerri A; Suski, Kaitlyn J; May, Nathaniel W; Gill, Thomas E; Prather, Kimberly A

2017-02-07

Playas emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dusts for cloud formation, most climate models assume that all dust is nonhygroscopic; however, measurements are needed to clarify the role of dusts in aerosol-cloud interactions. Here, we report measurements of CCN activation from playa dusts and parameterize these results in terms of both κ-Köhler theory and adsorption activation theory for inclusion in atmospheric models. κ ranged from 0.002 ± 0.001 to 0.818 ± 0.094, whereas Frankel-Halsey-Hill (FHH) adsorption parameters of A FHH = 2.20 ± 0.60 and B FHH = 1.24 ± 0.14 described the water uptake properties of the dusts. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that mineralogy, including salts, plays in water uptake by dust. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values. However, several samples were poorly predicted suggesting that chemical heterogeneities as a function of size or chemically distinct particle surfaces can determine the hygroscopicity of playa dusts. Our results further demonstrate the importance of dust in aerosol-cloud interactions.

The East and Southeast Asia Initiatives: Aerosol Column Measurements

NASA Technical Reports Server (NTRS)

Tsay, Si-Chee; Hsu, Christina N.; Li, Zhanqing

2003-01-01

Airborne dusts from northern China contribute a significant part of the air quality problem and, to some extent, regional climatic impact in Asia during spring- time. However, with the economical growth in China, increases in the emission of air pollutants generated from industrial and vehicular sources will not only impact the radiation balance, but adverse health effects to humans all year round. In addition, both of these dust and air pollution clouds can transport swiftly across the Pacific reaching North America within a few days, possessing an even larger scale effect. The Asian dust and air pollution aerosols can be detected by its colored appearance on current Earth observing satellites (e.g., MODIS, SeaWiFS, TOMS, etc.) and its evolution monitored by satellites and surface network. Biomass burning has been a regular practice for land clearing and land conversion in many countries, especially those in Africa, South America, and Southeast Asia. However, the unique climatology of Southeast Asia is very different than that of Africa and South America, such that large-scale biomass burning causes smoke to interact extensively with clouds during the peak-burning season of March to April. Significant global sources of greenhouse gases (e.g., CO2, CH4), chemically active gases (e.g., NO, CO, HC, CH3,Br), and atmospheric aerosols are produced by biomass burning processes. These gases influence the Earth- atmosphere system, impacting both global climate and tropospheric chemistry. Some aerosols can serve as cloud condensation nuclei, which play an important role in determining cloud lifetime and precipitation, hence, altering the earth's radiation and water budget. Biomass burning also affects the biogeochemical cycling of nitrogen and carbon compounds from the soil to the atmosphere; the hydrological cycle (i.e., run off and evaporation); land surface reflectivity and emissivity; as well as ecosystem biodiversity and stability. Two new initiatives, EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) and BASE-ASIA (Biomass-burning Aerosols in South East-Asia: Smoke Impact Assessment) will be presented and discussed their contribution to better understand the impacts of aerosols on regional-to- global climate, hydrological and carbon cycles, and tropospheric chemistry.

Multi-year application of WRF-CAM5 over East Asia-Part II: Interannual variability, trend analysis, and aerosol indirect effects

NASA Astrophysics Data System (ADS)

Zhang, Yang; Wang, Kai; He, Jian

2017-09-01

Following a comprehensive evaluation of WRF-CAM5 in Part I, Part II describes analyses of interannual variability, multi-year variation trends, and the direct, indirect, and total effects of anthropogenic aerosols. The interannual variations of chemical column and surface concentrations, and ozone (O3)/particulate matter (PM) indicators are strongly correlated to anthropogenic emission changes. Despite model biases, the model captures well the observed interannual variations of temperature at 2-m, cloud fraction, shortwave cloud forcing, downwelling shortwave radiation, cloud droplet number concentration, column O3, and column formaldehyde (HCHO) for the whole domain. While the model reproduces the volatile organic compound (VOC)-limited regimes of O3 chemistry at sites in Hong Kong, Taiwan, Japan, South Korea, and from the Acid Deposition Monitoring Network in East Asia (EANET) and the degree of sulfate neutralization at the EANET sites, it has limited capability in capturing the interannual variations of the ratio of O3 and nitrogen dioxide (O3/NO2) and PM chemical regime indicators, due to uncertainties in the emissions of precursors for O3 and secondary PM, the model assumption for ammonium bisulfate (NH4HSO4) as well as lack of gas/particle partitioning of total ammonia and total nitrate. While the variation trends in multi-year periods in aerosol optical depth and column concentrations of carbon monoxide, sulfur dioxide, and NO2 are mainly caused by anthropogenic emissions, those of major meteorological and cloud variables partly reflect feedbacks of chemistry to meteorological variables. The impacts of anthropogenic aerosol indirect effects either dominate or play an important role in the aerosol total effects for most cloud and chemical predictions, whereas anthropogenic aerosol direct effects influence most meteorological and radiation variables. The direct, indirect, and total effects of anthropogenic aerosols exhibit a strong interannual variability in 2001, 2006, and 2011.

D/H Measurements in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Keane, Jacqueline

2007-05-01

It is generally accepted that a considerable fraction of early Earths water was delivered by asteroids, comets, and planetesimals. The local planets and comets were assembled from the material in circumstellar disks, which in turn evolved from the envelopes and clouds surrounding protostars. Here at the University of Hawaii-NASA Astrobiology Institute the key research goal is to connect the major aspects of starformation and planetary water, in effect aiming to understand the terms of a "watery Drake Equation". To achieve this goal, we use the infrared and submillimeter telescopes on Mauna Kea to survey several molecules in a variety of starforming clouds. Observations show that water is the most common interstellar ice component. Moreover, there is evidence for enhanced water ice formation in the inner parts of protostellar envelopes. Simple molecules form on the icy grain mantles from surface reactions or thermal annealing of the ice, in turn these molecules drive a rich gas phase chemistry that produces more complex prebiotic molecules. Ice bands, therefore, serve as unique tracers of the chemical and thermal history of circumstellar environments. Here we will discuss constraints on the reservoirs of water and organic molecules in starforming regions, taking in to account the latest observational and theoretical measurements. Recent observations of a number of deuterated molecules, including water, will be discussed in terms of grain surface chemistry and its role in driving the enhanced fractionation of methanol like species, while at the same time inhibiting the deuteration of water.

21st Century Trends in Antarctic Temperature and Polar Stratospheric Cloud (PSC) Area in the GEOS Chemistry-Climate Model

NASA Technical Reports Server (NTRS)

Hurwitz, M. M.; Newman, P. A.

2010-01-01

This study examines trends in Antarctic temperature and APSC, a temperature proxy for the area of polar stratospheric clouds, in an ensemble of Goddard Earth Observing System (GEOS) chemistry-climate model (CCM) simulations of the 21st century. A selection of greenhouse gas, ozone-depleting substance, and sea surface temperature scenarios is used to test the trend sensitivity to these parameters. One scenario is used to compare temperature trends in two versions of the GEOS CCM. An extended austral winter season is examined in detail. In May, June, and July, the expected future increase in CO2-related radiative cooling drives temperature trends in the Antarctic lower stratosphere. At 50 hPa, a 1.3 K cooling is expected between 2000 and 2100. Ozone levels increase, despite this robust cooling signal and the consequent increase in APSC, suggesting the enhancement of stratospheric transport in future. In the lower stratosphere, the choice of climate change scenarios does not affect the magnitude of the early winter cooling. Midwinter temperature trends are generally small. In October, APSC trends have the same sign as the prescribed halogen trends. That is, there are negative APSC trends in "grealistic future" simulations, where halogen loading decreases in accordance with the Montreal Protocol and CO2 continues to increase. In these simulations, the speed of ozone recovery is not influenced by either the choice of sea surface temperature and greenhouse gas scenarios or by the model version.

Chemistry on the mesoscale: Modeling and measurement issues

NASA Technical Reports Server (NTRS)

Thompson, Anne; Pleim, John; Walcek, Christopher; Ching, Jason; Binkowski, Frank; Tao, Wei-Kuo; Dickerson, Russell; Pickering, Kenneth

1993-01-01

The topics covered include the following: Regional Acid Deposition Model (RADM) -- a coupled chemistry/mesoscale model; convection in RADM; unresolved issues for mesoscale modeling with chemistry -- nonprecipitating clouds; unresolved issues for mesoscale modeling with chemistry -- aerosols; tracer studies with Goddard Cumulus Ensemble Model (GCEM); field observations of trace gas transport in convection; and photochemical consequences of convection.

A new WRF-Chem treatment for studying regional-scale impacts of cloud processes on aerosol and trace gases in parameterized cumuli

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L. K.; Shrivastava, M.; Easter, R. C.

A new treatment of cloud effects on aerosol and trace gases within parameterized shallow and deep convection, and aerosol effects on cloud droplet number, has been implemented in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) version 3.2.1 that can be used to better understand the aerosol life cycle over regional to synoptic scales. The modifications to the model include treatment of the cloud droplet number mixing ratio; key cloud microphysical and macrophysical parameters (including the updraft fractional area, updraft and downdraft mass fluxes, and entrainment) averaged over the population of shallow clouds, or a single deep convectivemore » cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. These changes have been implemented in both the WRF-Chem chemistry packages as well as the Kain–Fritsch (KF) cumulus parameterization that has been modified to better represent shallow convective clouds. Testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS). The simulation results are used to investigate the impact of cloud–aerosol interactions on regional-scale transport of black carbon (BC), organic aerosol (OA), and sulfate aerosol. Based on the simulations presented here, changes in the column-integrated BC can be as large as –50% when cloud–aerosol interactions are considered (due largely to wet removal), or as large as +40% for sulfate under non-precipitating conditions due to sulfate production in the parameterized clouds. The modifications to WRF-Chem are found to account for changes in the cloud droplet number concentration (CDNC) and changes in the chemical composition of cloud droplet residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to the latest version of WRF-Chem, and it is anticipated that they will be included in a future public release of WRF-Chem.« less

A new WRF-Chem treatment for studying regional-scale impacts of cloud processes on aerosol and trace gases in parameterized cumuli

DOE PAGES

Berg, L. K.; Shrivastava, M.; Easter, R. C.; ...

2015-02-24

A new treatment of cloud effects on aerosol and trace gases within parameterized shallow and deep convection, and aerosol effects on cloud droplet number, has been implemented in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) version 3.2.1 that can be used to better understand the aerosol life cycle over regional to synoptic scales. The modifications to the model include treatment of the cloud droplet number mixing ratio; key cloud microphysical and macrophysical parameters (including the updraft fractional area, updraft and downdraft mass fluxes, and entrainment) averaged over the population of shallow clouds, or a single deep convectivemore » cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. These changes have been implemented in both the WRF-Chem chemistry packages as well as the Kain–Fritsch (KF) cumulus parameterization that has been modified to better represent shallow convective clouds. Testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS). The simulation results are used to investigate the impact of cloud–aerosol interactions on regional-scale transport of black carbon (BC), organic aerosol (OA), and sulfate aerosol. Based on the simulations presented here, changes in the column-integrated BC can be as large as –50% when cloud–aerosol interactions are considered (due largely to wet removal), or as large as +40% for sulfate under non-precipitating conditions due to sulfate production in the parameterized clouds. The modifications to WRF-Chem are found to account for changes in the cloud droplet number concentration (CDNC) and changes in the chemical composition of cloud droplet residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to the latest version of WRF-Chem, and it is anticipated that they will be included in a future public release of WRF-Chem.« less

Processing of ammonia-containing ices by heavy ions and its relevance to outer Solar System surfaces

NASA Astrophysics Data System (ADS)

Pilling, Sergio; Seperuelo Duarte, Eduardo; da Silveira, Enio F.; Domaracka, Alicja; Balanzat, Emmanuel; Rothard, Hermann; Boduch, Philippe

Ammonia-containing ices have been detected or postulated as important components of the icy surfaces of planetary satellites (e.g. Enceladus, Miranda), in the outer Solar System objects (e.g. Charon, Quaoar) and in Oort cloud comets. We present experimental studies of the interaction of heavy, highly-charged, and energetic ions with ammonia-containing ices (pure NH3 ; NH3 :CO; NH3 :H2 O and NH3 :H2 O:CO) in an attempt to simulate the physical chemistry induced by heavy-ion cosmic rays and heavy-ion solar wind particles at outer Solar System surfaces. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared spectrometer (FTIR) at different ion fluences. The dissociation cross-section and sputtering yield of ammonia and other ice compounds have been determined. Half-life of frozen ammonia due to heavy ion bombardment at different Solar System surfaces has been estimated. Radiolysis products have been identified and their implications for the chemistry on outer Solar System surfaces are discussed.

Hubble's Role in Studies of Venus' Clouds, Climate and Habitability

NASA Astrophysics Data System (ADS)

Jessup, Kandis-Lea; Marcq, Emmanuel; Mills, Franklin; Bertaux, Jean-Loup; Lee, Yeon Joo; Limaye, Sanjay; Roman, Anthony; Yung, Yuk

2018-06-01

Venus’ slow rotation fosters thick cloud formation, via long solar days, low Coriolis forces and strong subsolar convection. Thus, Venus and other slow rotators may maintain an Earth-like climate at ~ 2x the stellar flux as rapid rotators – if the cloud albedo is high, buffering climate change (Yang et al. 2014). However, Venus’ dense H2SO4 clouds host an absorbing source that drives solar heating, fostering rather than buffering climate change. As such, the response of an atmosphere to the available stellar flux and its impact on habitability will be quite different for a slow rotator planet with Venus-like vs. Earth-like buffering clouds.2010/2011 HST/STIS observations of Venus have provided data relevant for studying several of the mechanisms that determine Venus’ climate. These observations showed unambiguously that SO2 photolysis is not the sole process balancing the growth and loss of the cloud top SO (and SO2). As the parent species of Venus’ H2SO4 clouds, these results indicated that additional sulfur chemistry must be considered when defining the mechanisms controlling Venus’ H2SO4 formation process (Jessup et al. 2015). The STIS observations also showed decisively that vertical transport of Venus’ key UV absorbers: SO2, SO and the unnamed absorber are sensitive to the underlying surface elevation (Jessup et al. 2018). This implies that observations made over varying terrain types can be used to parameterize a) the energy and momentum released during surface-atmosphere interactions, which is essential for understanding Venus’ slow body and fast cloud rotation; and b) the sensitivity of the vertical profiles of the species having the greatest impact on Venus’ energy balance and climate to the underlying terrain. Cross-calibration of STIS and Venus Express data also enabled definitive identification of a 6 year decline in the cloud albedo resulting in a nearly 40% increase in the solar heating rate, suggesting dramatic climate change unparalleled in the solar system (Lee et al. 2018). Studies of the links between these phenomena, the super-rotation speed and the solar cycle will be revelatory for inter-stellar habitability studies.

A new laboratory facility to study the interactions of aerosols, cloud droplets/ice crystals, and trace gases in a turbulent environment: The Π Chamber

NASA Astrophysics Data System (ADS)

Cantrell, W. H., II; Chang, K.; Ciochetto, D.; Niedermeier, D.; Bench, J.; Shaw, R. A.

2014-12-01

A detailed understanding of gas-aerosol-cloud interaction within the turbulent atmosphere is of prime importance for an accurate understanding of Earth's climate system. As one example: While every cloud droplet began as an aerosol particle, not every aerosol particle becomes a cloud droplet. The particle to droplet transformation requires that the particle be exposed to some critical concentration of water vapor, which differs for different combinations of particle size and chemical composition. Similarly, the formation of ice particles in mixed phase clouds is also catalyzed by aerosol particles. Even in the simplest scenarios it is challenging to gain a full understanding of the aerosol activation and ice nucleation processes. At least two other factors contribute significantly to the complexity observed in the atmosphere. First, aerosols and cloud particles are not static entities, but are continuously interacting with their chemical environment, and therefore changing in their properties. Second, clouds are ubiquitously turbulent, so thermodynamic and compositional variables, such as water vapor or other trace gas concentrations, fluctuate in space and time. Indeed, the coupling between turbulence and microphysical processes is one of the major research challenges in cloud physics. We have developed a multiphase, turbulent reaction chamber, (dubbed the Π Chamber, after the internal volume of 3.14 cubic meters) designed to address the problems outlined above. It is capable of pressures ranging from sea level to ~ 100 mbar, and can sustain temperatures of +40 to -55 ºC. We can independently control the temperatures on the surfaces of three heat transfer zones. This allows us to establish a temperature gradient between the floor and ceiling inducing Rayleigh-Benard convection and inducing a turbulent environment. Interior surfaces are electropolished stainless steel to facilitate cleaning before and after chemistry experiments. At present, supporting instrumentation includes a suite of aerosol generation and characterization techniques, a laser Doppler interferometer, and a holographic cloud particle imaging system.We will present detailed specifications, an overview of the supporting instrumentation, and initial characterization experiments from the Π chamber.

Evaluation of modeled cloud chemistry mechanism against laboratory irradiation experiments: The HxOy/iron/carboxylic acid chemical system

NASA Astrophysics Data System (ADS)

Long, Yoann; Charbouillot, Tiffany; Brigante, Marcello; Mailhot, Gilles; Delort, Anne-Marie; Chaumerliac, Nadine; Deguillaume, Laurent

2013-10-01

Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the HxOy/iron (HxOy = H2O2, HO2rad /O2rad - and HOrad ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to a stable complex whose photoreactivity has currently not been investigated. The updated aqueous chemical mechanism was compared with data from irradiation experiments using natural cloud water. The new reactions considered in the model (i.e., iron complex formation with oxalic and formic acids) correctly reproduced the experimental observations.

The excitation of OH by H2 revisited - I: fine-structure resolved rate coefficients

NASA Astrophysics Data System (ADS)

Kłos, J.; Ma, Q.; Dagdigian, P. J.; Alexander, M. H.; Faure, A.; Lique, F.

2017-11-01

Observations of OH in molecular clouds provide crucial constraints on both the physical conditions and the oxygen and water chemistry in these clouds. Accurate modelling of the OH emission spectra requires the calculation of rate coefficients for excitation of OH by collisions with the most abundant collisional partner in the molecular clouds, namely the H2 molecule. We report here theoretical calculations for the fine-structure excitation of OH by H2 (both para- and ortho-H2) using a recently developed highly accurate potential energy surface. Full quantum close coupling rate coefficients are provided for temperatures ranging from 10 to 150 K. Propensity rules are discussed and the new OH-H2 rate coefficients are compared to the earlier values that are currently used in astrophysical modelling. Significant differences were found: the new rate coefficients are significantly larger. As a first application, we simulate the excitation of OH in typical cold molecular clouds and star-forming regions. The new rate coefficients predict substantially larger line intensities. As a consequence, OH abundances derived from observations will be reduced from the values predicted by the earlier rate coefficients.

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

DOE PAGES

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; ...

2017-01-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

NASA Astrophysics Data System (ADS)

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; Berg, Larry K.; Fast, Jerome D.; Easter, Richard C.; Shrivastava, Manish; Thomas, Jennie L.

2017-10-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain-Fritsch + Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

Modeling the chemistry of the dense interstellar clouds. I - Observational constraints for the chemistry

NASA Technical Reports Server (NTRS)

Federman, S. R.; Huntress, W. T., Jr.; Prasad, S. S.

1990-01-01

A search for correlations arising from molecular line data is made in order to place constraints on the chemical models of interstellar clouds. At 10 to the 21st H2/sq cm, N(CO) for dark clouds is a factor of six greater than the value for diffuse clouds. This implies that the strength of the UV radiation field where CO shields itself from dissociation is about one-half the strength of the average Galactic field. The dark cloud data indicate that the abundance of CO continues to increase with A(V) for directions with A(V) of 4 mag or less, although less steeply with N(H2) than for diffuse clouds. For H2CO, a quadratic relationship is obtained in plots versus H2 column density. The data suggest a possible turnover at the highest values for A(V). NH3 shows no correlation with H2, C(O-18), HC3N, or HC5N; a strong correlation is found between HC5N and HC3N, indicating a chemical link between the cyanopolyynes.

Laboratory studies of stratospheric aerosol chemistry

NASA Technical Reports Server (NTRS)

Molina, Mario J.

1996-01-01

In this report we summarize the results of the two sets of projects funded by the NASA grant NAG2-632, namely investigations of various thermodynamic and nucleation properties of the aqueous acid system which makes up stratospheric aerosols, and measurements of reaction probabilities directly on ice aerosols with sizes corresponding to those of polar stratospheric cloud particles. The results of these investigations are of importance for the assessment of the potential stratospheric effects of future fleets of supersonic aircraft. In particular, the results permit to better estimate the effects of increased amounts of water vapor and nitric acid (which forms from nitrogen oxides) on polar stratospheric clouds and on the chemistry induced by these clouds.

The free radical chemistry of cloud droplets and its impact upon the composition of rain

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1982-01-01

Calculations are presented that simulate the free radical chemistries of the gas phase and aqueous phase within a warm cloud during midday. It is demonstrated that in the presence of midday solar fluxes, the heterogeneous scavenging of OH and HO2 from the gas phase by cloud droplets can represent a major source of free radicals to cloud water, provided the accommodation or sticking coefficient for these species impinging upon water droplets is not less than 0.0001. The aqueous-phase of HO2 radicals are found to be converted to H2O2 by aqueous-phase chemical reactions at a rate that suggests that this mechanism could produce a significant fraction of the H2O2 found in cloud droplets. The rapid oxidation of sulfur species dissolved in cloudwater by this free-radical-produced H2O2 as well as by aqueous-phase OH radicals could conceivably have a significant impact upon the chemical composition of rain.

Recent Discoveries and Future Challenges in Atmospheric Organic Chemistry.

PubMed

Glasius, Marianne; Goldstein, Allen H

2016-03-15

Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.

HD 209458b in new light: evidence of nitrogen chemistry, patchy clouds and sub-solar water

NASA Astrophysics Data System (ADS)

MacDonald, Ryan J.; Madhusudhan, Nikku

2017-08-01

Interpretations of exoplanetary transmission spectra have been undermined by apparent obscuration due to clouds/hazes. Debate rages on whether weak H2O features seen in exoplanet spectra are due to clouds or inherently depleted oxygen. Assertions of solar H2O abundances have relied on making a priori model assumptions, for example, chemical/radiative equilibrium. In this work, we attempt to address this problem with a new retrieval paradigm for transmission spectra. We introduce poseidon, a two-dimensional atmospheric retrieval algorithm including generalized inhomogeneous clouds. We demonstrate that this prescription allows one to break vital degeneracies between clouds and prominent molecular abundances. We apply poseidon to the best transmission spectrum presently available, for the hot Jupiter HD 209458b, uncovering new insights into its atmosphere at the day-night terminator. We extensively explore the parameter space with an unprecedented 108 models, spanning the continuum from fully cloudy to cloud-free atmospheres, in a fully Bayesian retrieval framework. We report the first detection of nitrogen chemistry (NH3 and/or HCN) in an exoplanet atmosphere at 3.7-7.7σ confidence, non-uniform cloud coverage at 4.5-5.4σ, high-altitude hazes at >3σ and sub-solar H2O at ≳3-5σ, depending on the assumed cloud distribution. We detect NH3 at 3.3σ, and 4.9σ for fully cloudy and cloud-free scenarios, respectively. For the model with the highest Bayesian evidence, we constrain H2O at 5-15 ppm (0.01-0.03) × solar and NH3 at 0.01-2.7 ppm, strongly suggesting disequilibrium chemistry and cautioning against equilibrium assumptions. Our results herald a new promise for retrieving cloudy atmospheres using high-precision Hubble Space Telescope and James Webb Space Telescope spectra.

Nonequilibrium chemistry in shocked molecular clouds. [interstellar gases

NASA Technical Reports Server (NTRS)

Iglesias, E. R.; Silk, J.

1978-01-01

The gas-phase chemistry is studied behind a 10-km/s shock propagating into a dense molecular cloud. The principal conclusions are that: the concentrations of certain molecules (CO, NH3, HCN, N2) are unperturbed by the shock; other molecules (H2CO, CN, HCO(+)) are greatly decreased in abundance; and substantial amounts of H2O, HCO, and CH4 are produced. Approximately 1 million yr (independent of the density) must elapse after shock passage before chemical equilibrium is attained.

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

Why do global climate models struggle to represent low-level clouds in the West African summer monsoon?

NASA Astrophysics Data System (ADS)

Knippertz, Peter; Hannak, Lisa; Fink, Andreas H.; Kniffka, Anke; Pante, Gregor

2017-04-01

Climate models struggle to realistically represent the West African monsoon (WAM), which hinders reliable future projections and the development of adequate adaption measures. Low-level clouds over southern West Africa (5-10°N, 8°W-8°E) during July-September are an integral part of the WAM through their effect on the surface energy balance and precipitation, but their representation in climate models has so far received little attention. These clouds usually form during the night near the level of the nocturnal low-level jet ( 950 hPa), thicken and spread until the mid-morning ( 09 UTC), and then break up and rise in the course of the day, typically to about 850 hPa. The low thermal contrast to the surface and the frequent presence of obscuring higher-level clouds make detection of the low-level clouds from space rather challenging. Here we use 30 years of output from 18 models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5) as well as 20 years of output from 8 models participating in the Year of Tropical Convection (YoTC) experiments to identify cloud biases and their causes. A great advantage of the YoTC dataset is the 6-hourly output frequency, which allows an analysis of the diurnal cycle, and the availability of temperature and moisture tendencies from parameterized processes such as convection, radiation and boundary-layer turbulence. A comparison to earlier analyses based on CMIP3 output reveals rather limited improvements with regard to the represenation of low-level cloud and winds. Compared to ERA-Interim re-analyses, which shows satisfactory agreement with surface observations, many of the CMIP5 and YoTC models still have large biases in low-level cloudiness of both signs and a tendency to too high elevation and too weak diurnal cycles. At the same time, these models tend to have too strong low-level jets, the impact of which is unclear due to concomitant effects on temperature and moisture advection as well as turbulent mixing. Part of the differences between the models and ERA-Interim appear to be related to the different subgrid cloud schemes used. While nighttime tendencies in temperature and humidity are broadly realistic in most models, daytime tendencies show large variation in the vertical transport of heat and moisture. Many models simulate too low near-surface relative humidities, leading to insufficient low cloud cover, abundant solar radiation, and thus a too large diurnal cycle in temperature and relative humidity. Currently, targeted model sensitivity experiments are conducted to test possible feedback mechanisms between low clouds, radiation, boundary-layer dynamics, precipitation and the WAM circulation in the framework of the EU-funded DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) project (http://www.dacciwa.eu).

Assessing the CAM5 Physics Suite in the WRF-Chem Model: Implementation, Resolution Sensitivity, and a First Evaluation for a Regional Case Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Po-Lun; Rasch, Philip J.; Fast, Jerome D.

A suite of physical parameterizations (deep and shallow convection, turbulent boundary layer, aerosols, cloud microphysics, and cloud fraction) from the global climate model Community Atmosphere Model version 5.1 (CAM5) has been implemented in the regional model Weather Research and Forecasting with chemistry (WRF-Chem). A downscaling modeling framework with consistent physics has also been established in which both global and regional simulations use the same emissions and surface fluxes. The WRF-Chem model with the CAM5 physics suite is run at multiple horizontal resolutions over a domain encompassing the northern Pacific Ocean, northeast Asia, and northwest North America for April 2008 whenmore » the ARCTAS, ARCPAC, and ISDAC field campaigns took place. These simulations are evaluated against field campaign measurements, satellite retrievals, and ground-based observations, and are compared with simulations that use a set of common WRF-Chem Parameterizations. This manuscript describes the implementation of the CAM5 physics suite in WRF-Chem provides an overview of the modeling framework and an initial evaluation of the simulated meteorology, clouds, and aerosols, and quantifies the resolution dependence of the cloud and aerosol parameterizations. We demonstrate that some of the CAM5 biases, such as high estimates of cloud susceptibility to aerosols and the underestimation of aerosol concentrations in the Arctic, can be reduced simply by increasing horizontal resolution. We also show that the CAM5 physics suite performs similarly to a set of parameterizations commonly used in WRF-Chem, but produces higher ice and liquid water condensate amounts and near-surface black carbon concentration. Further evaluations that use other mesoscale model parameterizations and perform other case studies are needed to infer whether one parameterization consistently produces results more consistent with observations.« less

Quantification of marine aerosol subgrid variability and its correlation with clouds based on high-resolution regional modeling: Quantifying Aerosol Subgrid Variability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Guangxing; Qian, Yun; Yan, Huiping

One limitation of most global climate models (GCMs) is that with the horizontal resolutions they typically employ, they cannot resolve the subgrid variability (SGV) of clouds and aerosols, adding extra uncertainties to the aerosol radiative forcing estimation. To inform the development of an aerosol subgrid variability parameterization, here we analyze the aerosol SGV over the southern Pacific Ocean simulated by the high-resolution Weather Research and Forecasting model coupled to Chemistry. We find that within a typical GCM grid, the aerosol mass subgrid standard deviation is 15% of the grid-box mean mass near the surface on a 1 month mean basis.more » The fraction can increase to 50% in the free troposphere. The relationships between the sea-salt mass concentration, meteorological variables, and sea-salt emission rate are investigated in both the clear and cloudy portion. Under clear-sky conditions, marine aerosol subgrid standard deviation is highly correlated with the standard deviations of vertical velocity, cloud water mixing ratio, and sea-salt emission rates near the surface. It is also strongly connected to the grid box mean aerosol in the free troposphere (between 2 km and 4 km). In the cloudy area, interstitial sea-salt aerosol mass concentrations are smaller, but higher correlation is found between the subgrid standard deviations of aerosol mass and vertical velocity. Additionally, we find that decreasing the model grid resolution can reduce the marine aerosol SGV but strengthen the correlations between the aerosol SGV and the total water mixing ratio (sum of water vapor, cloud liquid, and cloud ice mixing ratios).« less

NASA's East and Southeast Asia Initiatives: BASE-ASIA and EAST-AIRE

NASA Technical Reports Server (NTRS)

Tsay, S.; Maring, H.

2005-01-01

Airborne dust from northern China influences air quality and regional climate in Asia during springtime. However, with the economic growth in China, increased emission of particulate air pollutants from industrial and vehicular sources will not only impact the earth's radiation balance, but also adversely affect human health year round. In addition, both of dust and aerosol pollutants can be transported swiftly across the Pacific affecting North America within a few days. Asian dust and pollutant aerosols can be detected by their colored appearance using current Earth observing satellites (e.g., MODIS, SeaWiFS, TOMS, etc.) and by sunphotometers deployed on the surface of the earth. Biomass burning has been a regular practice for land clearing and conversion in many countries, especially those in Africa, South America, and Southeast Asia. However, the climatology of Southeast Asia is very different than that of Africa and South America, such that large-scale biomass burning causes smoke to interact extensively with clouds during the peak-burning season of March to April. Globally significant sources of greenhouse gases (eg., CO2, CH4), chemically active gases (e.g., NO, CO, HC, CH3Br), and atmospheric aerosols are produced by biomass burning. These gases influence the Earth-atmosphere system, impacting both global climate and tropospheric chemistry. Some aerosols can serve as cloud condensation nuclei, which play a role in determining cloud lifetime and precipitation, altering the earth's radiation and water budgets. Biomass burning also affects the biogeochemical cycling of nitrogen and carbon compounds; the hydrological cycle; land surface reflectivity and emissivity; and ecosystem biodiversity and stability. Two NASA initiatives, EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) and BASE-ASIA (Biomass-burning Aerosols in South East-Asia: Smoke Impact Assessment) will be presented. The objectives of these initiatives is to develop a better understanding of the impacts of aerosols on regional-to-global climate, hydrological and carbon cycles, and tropospheric chemistry.

Enhancement of PM2.5 Concentrations by Aerosol-Meteorology Interactions Over China

NASA Astrophysics Data System (ADS)

Zhang, Xin; Zhang, Qiang; Hong, Chaopeng; Zheng, Yixuan; Geng, Guannan; Tong, Dan; Zhang, Yuxuan; Zhang, Xiaoye

2018-01-01

Aerosol-meteorology interactions can change surface aerosol concentrations via different mechanisms such as altering radiation budget or cloud microphysics. However, few studies investigated the impacts of different mechanisms on temporal and spatial distribution of PM2.5 concentrations over China. Here we used the fully coupled Weather Research and Forecasting model with online chemistry (WRF-Chem) to quantify the enhancement of PM2.5 concentrations by aerosol-meteorology feedback in China in 2014 for different seasons and separate the relative impacts of aerosol radiation interactions (ARIs) and aerosol-cloud interactions (ACIs). We found that ARIs and ACIs could increase population-weighted annual mean PM2.5 concentration over China by 4.0 μg/m3 and 1.6 μg/m3, respectively. We found that ARIs play a dominant role in aerosol-meteorology interactions in winter, while the enhancement of PM2.5 concentration by ARIs and ACIs is comparable in other three seasons. ARIs reduced the wintertime monthly mean wind speed and planetary boundary layer (PBL) height by up to 0.1 m/s and 160 m, respectively, but increased the relative humidity by up to 4%, leading to accumulation of pollutants within PBL. Also, ARIs reduced dry deposition velocity of aerosols by up to 20%, resulting in an increase in PM2.5 lifetime and concentrations. ARIs can increase wintertime monthly mean surface PM2.5 concentration by a maximum of 30 μg/m3 in Sichuan Basin. ACIs can also increase PM2.5 concentration with more significant impacts in wet seasons via reduced wet scavenging and enhanced in-cloud chemistry. Dominant processes in PM2.5 enhancement are also clarified in different seasons. Results show that physical process is more important than chemical processes in winter in ARIs, while chemical process of secondary inorganic aerosols production may be crucial in wet seasons via ACIs.

Sea spray as a source of ice nucleating particles - results from the AIDA Ocean03 campaign

NASA Astrophysics Data System (ADS)

Salter, M. E.; Ickes, L.; Adams, M.; Bierbauer, S.; Bilde, M.; Christiansen, S.; Ekman, A.; Gorokhova, E.; Höhler, K.; Kiselev, A. A.; Leck, C.; Mohr, C.; Mohler, O.; Murray, B. J.; Porter, G.; Ullrich, R.; Wagner, R.

2017-12-01

Clouds and their radiative effects are one of the major influences on the radiative fluxes in the atmosphere, but at the same time they remain the largest uncertainty in climate models. This lack of understanding is especially pronounced in the high Arctic. Summertime clouds can persist over long periods in this region, which is difficult to replicate in models based on our current understanding. The clouds most often encountered in the summertime high Arctic consist of a mixture of ice crystals and super-cooled water droplets, so-called mixed-phase clouds. This cloud type is sensitive to the availability of aerosol particles, which can act as cloud condensation nuclei and ice nuclei. However, since the high Arctic is a pristine region, aerosol particles are not very abundant, and the hypothesis of open leads in the Arctic as a potentially important source of cloud and ice nucleating particles via bubble bursting has emerged. In this context, we have conducted a series of experiments at the AIDA chamber at KIT, designed to investigate the mechanisms linking marine biology, seawater chemistry and aerosol physics/potential cloud impacts. During this campaign, two marine diatom species (Melosira arctica and Skeletonema marinoi) as well as sea surface microlayer samples collected during several Arctic Ocean research cruises were investigated. To aerosolize the samples, a variety of methods were used including a sea spray simulation chamber to mimic the process of bubble-bursting. The ice nucleating efficiency (mixed-phase cloud regime) of the samples was determined either directly in the AIDA chamber during adiabatic expansions, or using the INKA continuous flow diffusion chamber, or a cold stage. Results from the campaign along with the potential implications are presented.

Fine-scale application of WRF-CAM5 during a dust storm episode over East Asia: Sensitivity to grid resolutions and aerosol activation parameterizations

NASA Astrophysics Data System (ADS)

Wang, Kai; Zhang, Yang; Zhang, Xin; Fan, Jiwen; Leung, L. Ruby; Zheng, Bo; Zhang, Qiang; He, Kebin

2018-03-01

An advanced online-coupled meteorology and chemistry model WRF-CAM5 has been applied to East Asia using triple-nested domains at different grid resolutions (i.e., 36-, 12-, and 4-km) to simulate a severe dust storm period in spring 2010. Analyses are performed to evaluate the model performance and investigate model sensitivity to different horizontal grid sizes and aerosol activation parameterizations and to examine aerosol-cloud interactions and their impacts on the air quality. A comprehensive model evaluation of the baseline simulations using the default Abdul-Razzak and Ghan (AG) aerosol activation scheme shows that the model can well predict major meteorological variables such as 2-m temperature (T2), water vapor mixing ratio (Q2), 10-m wind speed (WS10) and wind direction (WD10), and shortwave and longwave radiation across different resolutions with domain-average normalized mean biases typically within ±15%. The baseline simulations also show moderate biases for precipitation and moderate-to-large underpredictions for other major variables associated with aerosol-cloud interactions such as cloud droplet number concentration (CDNC), cloud optical thickness (COT), and cloud liquid water path (LWP) due to uncertainties or limitations in the aerosol-cloud treatments. The model performance is sensitive to grid resolutions, especially for surface meteorological variables such as T2, Q2, WS10, and WD10, with the performance generally improving at finer grid resolutions for those variables. Comparison of the sensitivity simulations with an alternative (i.e., the Fountoukis and Nenes (FN) series scheme) and the default (i.e., AG scheme) aerosol activation scheme shows that the former predicts larger values for cloud variables such as CDNC and COT across all grid resolutions and improves the overall domain-average model performance for many cloud/radiation variables and precipitation. Sensitivity simulations using the FN series scheme also have large impacts on radiations, T2, precipitation, and air quality (e.g., decreasing O3) through complex aerosol-radiation-cloud-chemistry feedbacks. The inclusion of adsorptive activation of dust particles in the FN series scheme has similar impacts on the meteorology and air quality but to lesser extent as compared to differences between the FN series and AG schemes. Compared to the overall differences between the FN series and AG schemes, impacts of adsorptive activation of dust particles can contribute significantly to the increase of total CDNC (∼45%) during dust storm events and indicate their importance in modulating regional climate over East Asia.

Are comets connected to the origin of life

NASA Technical Reports Server (NTRS)

Delsemme, A. H.

1981-01-01

Possible connections between comets and the origin of life on earth are discussed. The orbital evolution of comets and their origin are considered within a framework for the origin of the solar system, with particular attention given to the origin of the biosphere, and the origin of the Oort cloud. Evidence suggesting that cometary nuclei are undifferentiated throughout is considered, and a model of the average composition of a mean new comet is obtained from observational data which is similar to that of an interstellar frost. The chemistry of the model composition giving rise to the species observed in cometary spectra is considered, as well as the relations of cometary to cosmic abundances of oxygen, carbon and sulfur. The characteristics of possible sites for prebiotic chemistry, including interstellar clouds, the protosolar nebula, comets in the Oort cloud, periodic comets and the primitive earth, are examined, and a possible role of comets in bringing the interstellar prebiotic chemistry to earth is suggested.

Operational surface UV radiation product from GOME-2 and AVHRR/3 data

NASA Astrophysics Data System (ADS)

Kujanpää, J.; Kalakoski, N.

2015-05-01

The surface ultraviolet (UV) radiation product, version 1.20, generated operationally in the framework of the Satellite Application Facility on Ozone and Atmospheric Chemistry Monitoring (O3M SAF) of the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) is described. The product is based on the total ozone column derived from the measurements of the second Global Ozone Monitoring Experiment (GOME-2) instrument aboard EUMETSAT's polar orbiting meteorological operational (Metop) satellites. The input total ozone product is generated by the German Aerospace Center (DLR) also within the O3M SAF framework. Polar orbiting satellites provide global coverage but infrequent sampling of the diurnal cloud cover. The diurnal variation of the surface UV radiation is extremely strong due to modulation by solar elevation and rapidly changing cloud cover. At the minimum, one sample of the cloud cover in the morning and another in the afternoon are needed to derive daily maximum and daily integrated surface UV radiation quantities. This is achieved by retrieving cloud optical depth from the channel 1 reflectance of the third Advanced Very High Resolution Radiometer (AVHRR/3) instrument aboard both Metop in the morning orbit (daytime descending node around 09:30 LT) and Polar Orbiting Environmental Satellites (POES) of the National Oceanic and Atmospheric Administration (NOAA) in the afternoon orbit (daytime ascending node around 14:30 LT). In addition, more overpasses are used at high latitudes where the swaths of consecutive orbits overlap. The input satellite data are received from EUMETSAT's Multicast Distribution System (EUMETCast) using commercial telecommunication satellites for broadcasting the data to the user community. The surface UV product includes daily maximum dose rates and integrated daily doses with different biological weighting functions, integrated UVB and UVA radiation, solar noon UV Index and daily maximum photolysis frequencies of ozone and nitrogen dioxide at the surface level. The quantities are computed in a 0.5° × 0.5° regular latitude-longitude grid and stored as daily files in the hierarchical data format (HDF5) within two weeks from sensing. The product files are archived in the O3M SAF distributed archive and can be ordered via the EUMETSAT Data Centre.

The dynamical core, physical parameterizations, and basic simulation characteristics of the atmospheric component AM3 of the GFDL global coupled model CM3

USGS Publications Warehouse

Donner, L.J.; Wyman, B.L.; Hemler, R.S.; Horowitz, L.W.; Ming, Y.; Zhao, M.; Golaz, J.-C.; Ginoux, P.; Lin, S.-J.; Schwarzkopf, M.D.; Austin, J.; Alaka, G.; Cooke, W.F.; Delworth, T.L.; Freidenreich, S.M.; Gordon, C.T.; Griffies, S.M.; Held, I.M.; Hurlin, W.J.; Klein, S.A.; Knutson, T.R.; Langenhorst, A.R.; Lee, H.-C.; Lin, Y.; Magi, B.I.; Malyshev, S.L.; Milly, P.C.D.; Naik, V.; Nath, M.J.; Pincus, R.; Ploshay, J.J.; Ramaswamy, V.; Seman, C.J.; Shevliakova, E.; Sirutis, J.J.; Stern, W.F.; Stouffer, R.J.; Wilson, R.J.; Winton, M.; Wittenberg, A.T.; Zeng, F.

2011-01-01

The Geophysical Fluid Dynamics Laboratory (GFDL) has developed a coupled general circulation model (CM3) for the atmosphere, oceans, land, and sea ice. The goal of CM3 is to address emerging issues in climate change, including aerosol-cloud interactions, chemistry-climate interactions, and coupling between the troposphere and stratosphere. The model is also designed to serve as the physical system component of earth system models and models for decadal prediction in the near-term future-for example, through improved simulations in tropical land precipitation relative to earlier-generation GFDL models. This paper describes the dynamical core, physical parameterizations, and basic simulation characteristics of the atmospheric component (AM3) of this model. Relative to GFDL AM2, AM3 includes new treatments of deep and shallow cumulus convection, cloud droplet activation by aerosols, subgrid variability of stratiform vertical velocities for droplet activation, and atmospheric chemistry driven by emissions with advective, convective, and turbulent transport. AM3 employs a cubed-sphere implementation of a finite-volume dynamical core and is coupled to LM3, a new land model with ecosystem dynamics and hydrology. Its horizontal resolution is approximately 200 km, and its vertical resolution ranges approximately from 70 m near the earth's surface to 1 to 1.5 km near the tropopause and 3 to 4 km in much of the stratosphere. Most basic circulation features in AM3 are simulated as realistically, or more so, as in AM2. In particular, dry biases have been reduced over South America. In coupled mode, the simulation of Arctic sea ice concentration has improved. AM3 aerosol optical depths, scattering properties, and surface clear-sky downward shortwave radiation are more realistic than in AM2. The simulation of marine stratocumulus decks remains problematic, as in AM2. The most intense 0.2% of precipitation rates occur less frequently in AM3 than observed. The last two decades of the twentieth century warm in CM3 by 0.328C relative to 1881-1920. The Climate Research Unit (CRU) and Goddard Institute for Space Studies analyses of observations show warming of 0.568 and 0.528C, respectively, over this period. CM3 includes anthropogenic cooling by aerosol-cloud interactions, and its warming by the late twentieth century is somewhat less realistic than in CM2.1, which warmed 0.668C but did not include aerosol-cloud interactions. The improved simulation of the direct aerosol effect (apparent in surface clear-sky downward radiation) in CM3 evidently acts in concert with its simulation of cloud-aerosol interactions to limit greenhouse gas warming. ?? 2011 American Meteorological Society.

Assessing cloud radiative effects on tropospheric photolysis rates and key oxidants during aircraft campaigns using satellite cloud observations and a global chemical transport model

NASA Astrophysics Data System (ADS)

Zhang, B.; Liu, H.; Crawford, J. H.; Chen, G.; Voulgarakis, A.; Fairlie, T. D.; Duncan, B. N.; Ham, S. H.; Kato, S.; Payer Sulprizio, M.; Yantosca, R.

2017-12-01

Clouds affect tropospheric photochemistry through modifying solar radiation that determines photolysis rates. Observational and modeling studies have indicated that photolysis rates are enhanced above and in the upper portion of cloud layers and are reduced below optically thick clouds due to their dominant backscattering effect. However, large uncertainties exist in the representation of cloud spatiotemporal (especially vertical) distributions in global models, which makes understanding of cloud radiative effects on tropospheric chemistry challenging. Our previous study using a global 3-D chemical transport model (GEOS-Chem) driven by various meteorological data sets showed that the radiative effects of clouds on photochemistry are more sensitive to the differences in the vertical distribution of clouds than to those in the magnitude of column cloud optical depths. In this work, we evaluate monthly mean cloud optical properties and distributions in the MERRA-2 reanalysis with those in C3M, a 3-D cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We conduct tropospheric chemistry simulations for the periods of several aircraft campaigns, including ARCTAS (April, June-July, 2008), DC3 (May-June, 2012), and SEAC4RS (August-September, 2013) with GEOS-Chem driven by MERRA-2. We compare model simulations with and without constraints of cloud optical properties and distributions from C3M, and evaluate model photolysis rates (J[O1D] and J[NO2]) and key oxidants (e.g., OH and ozone) with aircraft profile measurements. We will assess whether the constraints provided by C3M improve model simulations of photolysis rates and oxidants as well as their variabilities.

Theoretical studies of the extraterrestrial chemistry of biogenic elements and compounds

NASA Technical Reports Server (NTRS)

Defrees, D. J.

1991-01-01

Organic compounds, molecules related to those in living systems, are found in many different extraterrestrial environments. The study of organic astrochemistry is important to exobiology both because it demonstrates the ubiquity of processes which led to life on Earth and because the dust clouds where molecules are found are analogs of the solar nebula from which the Earth formed. In the long chain of events leading from the Big Bang, and a universe composed of atomic hydrogen and helium, to the emergence of life on Earth, molecular interstellar clouds are an early link, the most primitive objects which display any significant organic chemistry. One such cloud was the direct precursor to the solar system and to all objects which it contains. Theoretical methods are ideally suited to studying interstellar cloud chemistry. They have been applied to determine spectroscopic constants of candidate interstellar molecules, mechanisms of ion-molecule reactions, and composition of dust grains. Accurate predictions of rotational constants and dipole moments of long-chain carbon molecules HC13N, HC15N, and C5O have been made to aid in determining the size limit of gas-phase interstellar molecules. Models of gas-phase interstellar chemistry use reaction rate constants measured at room temperature and extrapolated to interstellar temperatures. The temperature dependence of NH3(+)+H2 yields NH4(+)+H is anomalous, however, with a minimum rate at about 100K, casting doubt on the extrapolation procedures. The temperature dependence has now been explained.

Anthropogenic Sulfate, Clouds, and Climate Forcing

NASA Technical Reports Server (NTRS)

Ghan, Steven J.

1997-01-01

This research work is a joint effort between research groups at the Battelle Pacific Northwest Laboratory, Virginia Tech University, Georgia Institute of Technology, Brookhaven National Laboratory, and Texas A&M University. It has been jointly sponsored by the National Aeronautics and Space Administration, the U.S. Department of Energy, and the U.S. Environmental Protection Agency. In this research, a detailed tropospheric aerosol-chemistry model that predicts oxidant concentrations as well as concentrations of sulfur dioxide and sulfate aerosols has been coupled to a general circulation model that distinguishes between cloud water mass and cloud droplet number. The coupled model system has been first validated and then used to estimate the radiative impact of anthropogenic sulfur emissions. Both the direct radiative impact of the aerosols and their indirect impact through their influence on cloud droplet number are represented by distinguishing between sulfuric acid vapor and fresh and aged sulfate aerosols, and by parameterizing cloud droplet nucleation in terms of vertical velocity and the number concentration of aged sulfur aerosols. Natural sulfate aerosols, dust, and carbonaceous and nitrate aerosols and their influence on the radiative impact of anthropogenic sulfate aerosols, through competition as cloud condensation nuclei, will also be simulated. Parallel simulations with and without anthropogenic sulfur emissions are performed for a global domain. The objectives of the research are: To couple a state-of-the-art tropospheric aerosol-chemistry model with a global climate model. To use field and satellite measurements to evaluate the treatment of tropospheric chemistry and aerosol physics in the coupled model. To use the coupled model to simulate the radiative (and ultimately climatic) impacts of anthropogenic sulfur emissions.

The global impact of mineral dust on cloud droplet number concentration

NASA Astrophysics Data System (ADS)

Karydis, V.; Tsimpidi, A.; Bacer, S.; Pozzer, A.; Nenes, A.; Lelieveld, J.

2016-12-01

This study assesses the importance of mineral dust for cloud droplet formation by taking into account i) the adsorption of water on the surface of insoluble dust particles, ii) the coating of soluble material on the surface of mineral particles which augments their cloud condensation nuclei activity, and iii) the effect of dust on the inorganic aerosol concentrations through thermodynamic interactions with mineral cations. Simulations are carried out with the EMAC chemistry climate model that calculates the global atmospheric aerosol composition using the ISORROPIA-II thermodynamic equilibrium model and considers the gas phase interactions with K+-Ca2+-Mg2+-NH4+-Na+-SO42-NO3-Cl-H2O particle components. Emissions of the inert mineral dust and the reactive dust aerosol components are calculated online by taking into account the soil particle size distribution and chemical composition of different deserts worldwide (Karydis et al., 2016). We have implemented the "unified dust activation parameterization" (Kumar et al., 2011; Karydis et al., 2011) to calculate the droplet number concentration by taking into account the inherent hydrophilicity from adsorption and the acquired hygroscopicity from soluble salts by dust particles. Our simulations suggest that mineral dust significantly increases the cloud droplet number concentration (CDNC) over the main deserts and the adjacent oceans. However, over polluted areas the CDNC decreases significantly in the presence of dust. Furthermore, we investigate the role of adsorption activation of insoluble aerosols and the mineral dust thermodynamic interactions with inorganic anions on the cloud droplet formation. The CDNC sensitivity to the emission load, chemical composition, and inherent hydrophilicity of mineral dust is also tested. ReferencesKarydis, et al. (2011). "On the effect of dust particles on global cloud condensation nuclei and cloud droplet number." J. Geophys. Res. Atmos. 116. Karydis, et al. (2016). "Effects of mineral dust on global atmospheric nitrate concentrations." Atmos. Chem. Phys. 16(3): 1491-1509. Kumar, et al. (2011). "Measurements of cloud condensation nuclei activity and droplet activation kinetics of wet processed regional dust samples and minerals." Atmos. Chem. Phys. Discuss. 11(4): 12561-12605.

Anthropogenic influence on the distribution of tropospheric sulphate aerosol

NASA Astrophysics Data System (ADS)

Langner, J.; Rodhe, H.; Crutzen, P. J.; Zimmermann, P.

1992-10-01

HUMAN activities have increased global emissions of sulphur gases by about a factor of three during the past century, leading to increased sulphate aerosol concentrations, mainly in the Northern Hemisphere. Sulphate aerosols can affect the climate directly, by increasing the backscattering of solar radiation in cloud-free air, and indirectly, by providing additional cloud condensation nuclei1-4. Here we use a global transport-chemistry model to estimate the changes in the distribution of tropospheric sulphate aerosol and deposition of non-seasalt sulphur that have occurred since pre-industrial times. The increase in sulphate aerosol concentration is small over the Southern Hemisphere oceans, but reaches a factor of 100 over northern Europe in winter. Our calculations indicate, however, that at most 6% of the anthropogenic sulphur emissions is available for the formation of new aerosol particles. This is because about one-half of the sulphur dioxide is deposited on the Earth's surface, and most of the remainder is oxidized in cloud droplets so that the sulphate becomes associated with pre-existing particles. Even so, the rate of formation of new sulphate particles may have doubled since pre-industrial times.

Evaluation of the Cloud Fields in the UK Met Office HadGEM3-UKCA Model Using the CCCM Satellite Data Product to Advance Our Understanding of the Influence of Clouds on Tropospheric Composition and Chemistry

NASA Technical Reports Server (NTRS)

Varma, Sunil; Voulgarakis, Apostolos; Liu, Hongyu; Crawford, James H.; White, James

2016-01-01

To determine the role of clouds in driving inter-annual and inter-seasonal variability of trace gases in the troposphere and lower stratosphere with a particular focus on the importance of cloud modification of photolysis. To evaluate the cloud fields and their vertical distribution in the HadGEM3 model utilizing CCCM, a unique 3-D cloud data product merged from multiple A-Train satellites (CERES, CloudSat, CALIPSO, and MODIS) developed at the NASA Langley Research Center.

Observations of high droplet number concentrations in Southern Ocean boundary layer clouds

NASA Astrophysics Data System (ADS)

Chubb, T.; Huang, Y.; Jensen, J.; Campos, T.; Siems, S.; Manton, M.

2015-09-01

Data from the standard cloud physics payload during the NSF/NCAR High-performance Instrumented Airborne Platform for Environmental Research (HIAPER) Pole-to-Pole Observations (HIPPO) campaigns provide a snapshot of unusual wintertime microphysical conditions in the boundary layer over the Southern Ocean. On 29 June 2011, the HIAPER sampled the boundary layer in a region of pre-frontal warm air advection between 58 and 48° S to the south of Tasmania. Cloud droplet number concentrations were consistent with climatological values in the northernmost profiles but were exceptionally high for wintertime in the Southern Ocean at 100-200 cm-3 in the southernmost profiles. Sub-micron (0.0625 m s-1) were most likely responsible for production of sea spray aerosol which influenced the microphysical properties of the boundary layer clouds. The smaller size and higher number concentration of cloud droplets is inferred to increase the albedo of these clouds, and these conditions occur regularly, and are expected to increase in frequency, over windy parts of the Southern Ocean.

Atmospheric CO2 Concentration Measurements with Clouds from an Airborne Lidar

NASA Astrophysics Data System (ADS)

Mao, J.; Abshire, J. B.; Kawa, S. R.; Riris, H.; Allan, G. R.; Hasselbrack, W. E.; Numata, K.; Chen, J. R.; Sun, X.; DiGangi, J. P.; Choi, Y.

2017-12-01

Globally distributed atmospheric CO2 concentration measurements with high precision, low bias and full seasonal sampling are crucial to advance carbon cycle sciences. However, two thirds of the Earth's surface is typically covered by clouds, and passive remote sensing approaches from space are limited to cloud-free scenes. NASA Goddard is developing a pulsed, integrated-path differential absorption (IPDA) lidar approach to measure atmospheric column CO2 concentrations, XCO2, from space as a candidate for NASA's ASCENDS mission. Measurements of time-resolved laser backscatter profiles from the atmosphere also allow this technique to estimate XCO2 and range to cloud tops in addition to those to the ground with precise knowledge of the photon path-length. We demonstrate this measurement capability using airborne lidar measurements from summer 2017 ASCENDS airborne science campaign in Alaska. We show retrievals of XCO2 to ground and to a variety of cloud tops. We will also demonstrate how the partial column XCO2 to cloud tops and cloud slicing approach help resolving vertical and horizontal gradient of CO2 in cloudy conditions. The XCO2 retrievals from the lidar are validated against in situ measurements and compared to the Goddard Parameterized Chemistry Transport Model (PCTM) simulations. Adding this measurement capability to the future lidar mission for XCO2 will provide full global and seasonal data coverage and some information about vertical structure of CO2. This unique facility is expected to benefit atmospheric transport process studies, carbon data assimilation in models, and global and regional carbon flux estimation.

Multiple Paths of Deuterium Fractionation in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Aikawa, Yuri; Furuya, Kenji; Hincelin, Ugo; Herbst, Eric

2018-03-01

We investigate deuterium chemistry coupled with the nuclear spin-state chemistry of H2 and {{{H}}}3+ in protoplanetary disks. Multiple paths of deuterium fractionation are found; exchange reactions with D atoms, such as HCO+ + D, are effective in addition to those with HD. In a disk model with grain sizes appropriate for dark clouds, the freeze-out of molecules is severe in the outer midplane, while the disk surface is shielded from UV radiation. Gaseous molecules, including DCO+, thus become abundant at the disk surface, which tends to make their column density distribution relatively flat. If the dust grains have grown to millimeter size, the freeze-out rate of neutral species is reduced and the abundances of gaseous molecules, including DCO+ and N2D+, are enhanced in the cold midplane. Turbulent diffusion transports D atoms and radicals at the disk surface to the midplane, and stable ice species in the midplane to the disk surface. The effects of turbulence on chemistry are thus multifold; while DCO+ and N2D+ abundances increase or decrease depending on the regions, HCN and DCN in the gas and ice are greatly reduced at the innermost radii, compared to the model without turbulence. When cosmic rays penetrate the disk, the ortho-to-para ratio (OPR) of H2 is found to be thermal in the disk, except in the cold (≲10 K) midplane. We also analyze the OPR of {{{H}}}3+ and H2D+, as well as the main reactions of H2D+, DCO+, and N2D+, in order to analytically derive their abundances in the cold midplane.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust

NASA Astrophysics Data System (ADS)

Gaston, C.; Pratt, K.; Suski, K. J.; May, N.; Gill, T. E.; Prather, K. A.

2016-12-01

Saline playas (dried lake beds) emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dust for cloud formation, several models assume that dust is non-hygroscopic highlighting the need for measurements to clarify the role of dust from multiple sources in aerosol-cloud-climate interactions. Here we present water uptake measurements onto playa dust represented by the hygroscopicity parameter κ, which ranged from 0.002 ± 0.001 to 0.818 ± 0.094. Single-particle measurements made using an aircraft-aerosol time-of-flight mass spectrometer (A-ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that dust composition plays in water uptake. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values; however, several samples were poorly predicted using bulk particle composition. The lack of measurements/model agreement using this method and the strong correlations between κ and single-particle data are suggestive of chemical heterogeneities as a function of particle size and/or chemically distinct particle surfaces that dictate the water uptake properties of playa dust particles. Overall, our results highlight the ability of playa dust particles to act as cloud condensation nuclei that should be accounted for in models.

Radiative Effect of Clouds on Tropospheric Chemistry in a Global Three-Dimensional Chemical Transport Model

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James H.; Pierce, Robert B.; Norris, Peter; Platnick, Steven E.; Chen, Gao; Logan, Jennifer A.; Yantosca, Robert M.; Evans, Mat J.; Kittaka, Chieko;

Prebiotic chemical evolution in the astrophysical context.

PubMed

Ziurys, L M; Adande, G R; Edwards, J L; Schmidt, D R; Halfen, D T; Woolf, N J

2015-06-01

An ever increasing amount of molecular material is being discovered in the interstellar medium, associated with the birth and death of stars and planetary systems. Radio and millimeter-wave astronomical observations, made possible by high-resolution laboratory spectroscopy, uniquely trace the history of gas-phase molecules with biogenic elements. Using a combination of both disciplines, the full extent of the cycling of molecular matter, from circumstellar ejecta of dying stars - objects which expel large amounts of carbon - to nascent solar systems, has been investigated. Such stellar ejecta have been found to exhibit a rich and varied chemical content. Observations demonstrate that this molecular material is passed onto planetary nebulae, the final phase of stellar evolution. Here the star sheds almost its entire original mass, becoming an ultraviolet-emitting white dwarf. Molecules such as H2CO, HCN, HCO(+), and CCH are present in significant concentrations across the entire age span of such nebulae. These data suggest that gas-phase polyatomic, carbon-containing molecules survive the planetary nebula phase and subsequently are transported into the interstellar medium, seeding the chemistry of diffuse and then dense clouds. The extent of the chemical complexity in dense clouds is unknown, hindered by the high spectral line density. Organic species such as acetamide and methyl amine are present in such objects, and NH2CHO has a wide Galactic distribution. However, organophosphorus compounds have not yet been detected in dense clouds. Based on carbon and nitrogen isotope ratios, molecular material from the ISM appears to become incorporated into solar system planetesimals. It is therefore likely that interstellar synthesis influences prebiotic chemistry on planet surfaces.

Assessing regional scale predictions of aerosols, marine stratocumulus, and their interactions during VOCALS-REx using WRF-Chem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang Q.; Lee Y.; Gustafson Jr., W. I.

2011-12-02

This study assesses the ability of the recent chemistry version (v3.3) of the Weather Research and Forecasting (WRF-Chem) model to simulate boundary layer structure, aerosols, stratocumulus clouds, and energy fluxes over the Southeast Pacific Ocean. Measurements from the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) and satellite retrievals (i.e., products from the MODerate resolution Imaging Spectroradiometer (MODIS), Clouds and Earth's Radiant Energy System (CERES), and GOES-10) are used for this assessment. The Morrison double-moment microphysics scheme is newly coupled with interactive aerosols in the model. The 31-day (15 October-16 November 2008) WRF-Chem simulation with aerosol-cloud interactions (AERO hereafter) is also comparedmore » to a simulation (MET hereafter) with fixed cloud droplet number concentrations in the microphysics scheme and simplified cloud and aerosol treatments in the radiation scheme. The well-simulated aerosol quantities (aerosol number, mass composition and optical properties), and the inclusion of full aerosol-cloud couplings lead to significant improvements in many features of the simulated stratocumulus clouds: cloud optical properties and microphysical properties such as cloud top effective radius, cloud water path, and cloud optical thickness. In addition to accounting for the aerosol direct and semi-direct effects, these improvements feed back to the simulation of boundary-layer characteristics and energy budgets. Particularly, inclusion of interactive aerosols in AERO strengthens the temperature and humidity gradients within the capping inversion layer and lowers the marine boundary layer (MBL) depth by 130 m from that of the MET simulation. These differences are associated with weaker entrainment and stronger mean subsidence at the top of the MBL in AERO. Mean top-of-atmosphere outgoing shortwave fluxes, surface latent heat, and surface downwelling longwave fluxes are in better agreement with observations in AERO, compared to the MET simulation. Nevertheless, biases in some of the simulated meteorological quantities (e.g., MBL temperature and humidity) and aerosol quantities (e.g., underestimations of accumulation mode aerosol number) might affect simulated stratocumulus and energy fluxes over the Southeastern Pacific, and require further investigation. The well-simulated timing and outflow patterns of polluted and clean episodes demonstrate the model's ability to capture daily/synoptic scale variations of aerosol and cloud properties, and suggest that the model is suitable for studying atmospheric processes associated with pollution outflow over the ocean. The overall performance of the regional model in simulating mesoscale clouds and boundary layer properties is encouraging and suggests that reproducing gradients of aerosol and cloud droplet concentrations and coupling cloud-aerosol-radiation processes are important when simulating marine stratocumulus over the Southeast Pacific.« less

A survey of bimolecular ion-molecule reactions for use in modeling the chemistry of planetary atmospheres, cometary comae, and interstellar clouds

NASA Technical Reports Server (NTRS)

Anicich, V. G.; Huntress, W. T., Jr.

1986-01-01

All bimolecular positive ion-molecule reactions reported from 1965 to 1985 for temperatures below 1000 K are included in the present survey of those ion-molecule reactions pertinent to the chemistries of planetary atmospheres, cometary comae, and interstellar clouds. This survey is intended as an update of the first, by Huntress (1977). The tabular presentation is organized according to reactant ion, with cross-references for both the ionic and the neutral reactants as well as the ionic and neutral products.

Dissociative recombination in interstellar clouds

NASA Technical Reports Server (NTRS)

Black, John H.; Van Dishoeck, Ewine F.

1989-01-01

Molecular ions play a significant role in the chemistry and evolution of interstellar molecular clouds, even though these regions are overwhelmingly neutral. The dissociative recombination (DR) process governs the abundances of many of these ions and of related neutral species. The gas-phase ion-molecule chemistry of the simplest species is summarized, with emphasis on those problems which are most sensitive to uncertain rates or product branching ratios of DR processes. Examples of the kinds of information needed about DR processes are presented. The importance of the H3(+) ion and prospects for its direct observation are discussed.

SOA FROM ISOPRENE OXIDATION PRODUCTS: MODEL SIMULATION OF CLOUD CHEMISTRY

EPA Science Inventory

Recent laboratory evidence supports the hypothesis that secondary organic aerosol (SOA) is formed in the atmosphere through aqueous-phase reactions in clouds. The results of batch photochemical reactions of glyoxal, methylglyoxal and hydrogen peroxide are presented. These labor...

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1998-01-01

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where pH (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as pH increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Proceedings of a Workshop on Polar Stratospheric Clouds: Their Role in Atmospheric Processes

NASA Technical Reports Server (NTRS)

Hamill, P. (Editor); Mcmaster, L. R. (Editor)

1984-01-01

The potential role of polar stratospheric clouds in atmospheric processes was assessed. The observations of polar stratospheric clouds with the Nimbus 7 SAM II satellite experiment were reviewed and a preliminary analysis of their formation, impact on other remote sensing experiments, and potential impact on climate were presented. The potential effect of polar stratospheric clouds on climate, radiation balance, atmospheric dynamics, stratospheric chemistry and water vapor budget, and cloud microphysics was assessed. Conclusions and recommendations, a synopsis of materials and complementary material to support those conclusions and recommendations are presented.

Atmospheric Retrieval Analysis of the Directly Imaged Exoplanet HR 8799b

NASA Astrophysics Data System (ADS)

Lee, Jae-Min; Heng, Kevin; Irwin, Patrick G. J.

2013-12-01

Directly imaged exoplanets are unexplored laboratories for the application of the spectral and temperature retrieval method, where the chemistry and composition of their atmospheres are inferred from inverse modeling of the available data. As a pilot study, we focus on the extrasolar gas giant HR 8799b, for which more than 50 data points are available. We upgrade our non-linear optimal estimation retrieval method to include a phenomenological model of clouds that requires the cloud optical depth and monodisperse particle size to be specified. Previous studies have focused on forward models with assumed values of the exoplanetary properties; there is no consensus on the best-fit values of the radius, mass, surface gravity, and effective temperature of HR 8799b. We show that cloud-free models produce reasonable fits to the data if the atmosphere is of super-solar metallicity and non-solar elemental abundances. Intermediate cloudy models with moderate values of the cloud optical depth and micron-sized particles provide an equally reasonable fit to the data and require a lower mean molecular weight. We report our best-fit values for the radius, mass, surface gravity, and effective temperature of HR 8799b. The mean molecular weight is about 3.8, while the carbon-to-oxygen ratio is about unity due to the prevalence of carbon monoxide. Our study emphasizes the need for robust claims about the nature of an exoplanetary atmosphere to be based on analyses involving both photometry and spectroscopy and inferred from beyond a few photometric data points, such as are typically reported for hot Jupiters.

Pissible Habitats in the Venusian Environment? How Can the Venus Payload Contribute?

NASA Astrophysics Data System (ADS)

Muller, C. L.; Schulze-Makuch, D.

2005-12-01

The Venusian conditions are unique in the solar system. Venus has a dense CO2 atmosphere, is volcanically active, and has plenty of energy sources such as light, UV radiation, volcanic activity, and chemical energy from atmospheric disequilibria conditions. Its surface conditions are sufficiently hot for sterilization and volcanism injects highly toxic gases which in the absence of unbound water can accumulate in the atmosphere. The Venusian surface is constantly regenerated by volcanism and any possible fossil record from early Venus history in which oceans existed on its surface is almost certainly destroyed. Its upper atmosphere lays bare to solar radiation with only carbon dioxide to act as a confirmed EUV filter. Any possibility of life was considered irrational before extremophile bacteria were discovered in dark undersea hot sulphur rich volcanic vents on Earth. However, some regions of the Venusian clouds might show conditions similar to the earth surface and could be a habitat of thermophilic microbial life similar to the one observed on Earth. A synergy between different instruments of the VENUS-Express payload, the SPICAV spectrometer and the VMC camera in a first step, and the spectrometers VIRTIS and PFS in a second step, will probe the actual environmental conditions of the cloud region. The SPICAV spectrometer, in particular, has three channels including, two infrared AOTF channels and could give access to organic signatures in both the UV and infrared. Given these observations we will be able to analyze whether the environmental conditions of the cloud layer would make it a possible habitat for extant microbial life. The instruments will shed answers to the availability of nutrients, water, types of energy sources, atmospheric dynamics, and organic chemistry.

Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

PubMed

Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

2009-12-31

Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

Development of Realistic Synthetic Data Products for the Tempo Geostationary Mission

NASA Astrophysics Data System (ADS)

Chan Miller, C.; Gonzalez Abad, G.; Zoogman, P.; Spurr, R. J. D.; Keller, C. A.; Liu, X.; Chance, K.

2017-12-01

TEMPO is a future geostationary satellite instrument designed to measure atmospheric pollution from solar backscatter over greater North America. Here we describe efforts to generate realistic synthetic level 1 (radiance) and level 2 (trace gas, aerosol and cloud) TEMPO observations, appropriate for retrieval algorithm validation and data assimilation observing system simulation experiments. The synthetic data are derived using a high resolution ( 12km x 12km) GEOS-5 GCM simulation with GEOS-Chem tropospheric chemistry combined with the VLIDORT radiative transfer model. The simulations include cloud and aerosol scattering, pressure- and temperature-dependent gas absorption, anisotropic surface reflectance derived from MODIS observations, solar-induced plant fluorescence derived from GOME-2 observations, and the Ring effect. We describe methods to speed up calculation of the synthetic level 2 products, and present a first validation of the TEMPO operational algorithms against the synthetic level 1 data.

Importance of formaldehyde in cloud chemistry

NASA Technical Reports Server (NTRS)

Adewuyi, Y. G.; Cho, S.-Y.; Tsay, R.-P.; Carmichael, G. R.

1984-01-01

A physical-chemical model which is an extension of that of Hong and Carmichael (1983) is used to investigate the role of formaldehyde in cloud chemistry. This model takes into account the mass transfer of SO2, O3, NH3, HNO3, H2O2, CO2, HCl, HCHO, O2, OH and HO2 into cloud droplets and their subsequent chemical reactions. The model is used to assess the importance of S(IV)-HCHO adduct formation, the reduction of H2O2 by HCHO, HCHO-free radical interactions, and the formation of HCOOH in the presence of HCHO in cloud droplets. Illustrative calculations indicate that the presence of HCHO inhibits sulfate production rate in cloud droplets. The direct inhibition of sulfate production rate in cloudwater due to nucleophilic addition of HSO3(-) to HCHO(aq) to form hydroxymethanesulfonate is generally low for concentrations of HCHO typical of ambient air. However, inhibition of sulfate production due to formaldehyde-free radical interactions in solution can be important. These formaldehyde-free radical reactions can also generate appreciable quantities of formic acid.

Chemistry and Evolution of Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wooden, D. H.; Charnley, S. B.; Ehrenfreund, P.

2003-01-01

In this chapter we describe how elements have been and are still being formed in the galaxy and how they are transformed into the reservoir of materials present at the time of formation of our protosolar nebula. We discuss the global cycle of matter, beginning at its formation site in stars, where it is ejected through winds and explosions into the diffuse interstellar medium. In the next stage of the global cycle occurs in cold, dense molecular clouds, where the complexity of molecules and ices increases relative to the diffuse ISM.. When a protostar forms in a dense core within a molecular cloud, it heats the surrounding infalling matter warms and releases molecules from the solid phase into the gas phase in a warm, dense core, sponsoring a rich gas-phase chemistry. Some material from the cold and warm regions within molecular clouds probably survives as interstellar matter in the protostellar disk. For the diffuse ISM, for cold, dense clouds, and for dense-warm cores, the physio-chemical processes that occur within the gas and solid phases are discussed in detail.

Effect of stochastic grain heating on cold dense clouds chemistry

NASA Astrophysics Data System (ADS)

Chen, Long-Fei; Chang, Qiang; Xi, Hong-Wei

2018-06-01

The temperatures of dust grains play important roles in the chemical evolution of molecular clouds. Unlike large grains, the temperature fluctuations of small grains induced by photons may be significant. Therefore, if the grain size distribution is included in astrochemical models, the temperatures of small dust grains may not be assumed to be constant. We simulate a full gas-grain reaction network with a set of dust grain radii using the classical MRN grain size distribution and include the temperature fluctuations of small dust grains. Monte Carlo method is used to simulate the real-time dust grain's temperature fluctuations which is caused by the external low energy photons and the internal cosmic ray induced secondary photons. The increase of dust grains radii as ice mantles accumulate on grain surfaces is also included in our models. We found that surface CO2 abundances in models with grain size distribution and temperature fluctuations are more than one order of magnitude larger than those with single grain size. Small amounts of terrestrial complex organic molecules (COMs) can also be formed on small grains due to the temperature spikes induced by external low energy photons. However, cosmic ray induced secondary photons overheat small grains so that surface CO sublime and less radicals are formed on grains surfaces, thus the production of surface CO2 and COMs decreases by about one order of magnitude. The overheating of small grains can be offset by grain growth so that the formation of surface CO2 and COMs becomes more efficient.

Is microbiolgy an alternative route to photochemistry in atmospheric chemistry?

NASA Astrophysics Data System (ADS)

Vaitilingom, M.; Parazols, M.; Sancelme, M.; Deguillaume, L.; Mailhot, G.; Delort, A.-M.

2009-04-01

Until very recently scientists from atmospheric sciences focussed their studies on physical and chemical phenomena taking place in cloud water phase neglecting the presence of active microorganisms in this medium. For instance, considering atmospheric chemistry, solar light is considered as the predominant catalyser for chemical reactions occurring in the atmosphere. However recent studies show that living and active microorganisms, including bacteria, yeasts and fungi, are present in the atmospheric water phase and could play an active role in chemistry of clouds. Indeed living microorganisms are clearly biocatalysts which could transform organic compounds as an alternative route to photochemistry. The objective of our project is to bring answers to this new scientific question by a multidisciplinary approach involving atmospheric physicists, photochemists and microbiologists. Microorganisms have been isolated and identified in cloud water sampled at the puy de Dôme summit which is an atmospheric observatory and a European referenced site. Laboratory experiments were carried out to evaluate the potential of organic species (carboxylic acids) degradation by the photochemical or microbiological ways. The project was centred on few carboxylic acids among them succinic, acetic, formic and oxalic acids (the most important organic acids in cloud water sampled at Puy de Dôme). Degradation rates were measured during biodegradation alone (Pseudomonas syringae), photochemistry alone (hydrogen peroxide + light) and combing both processed using artificial reconstituted cloud water. Our first results show that the obtained degradation rates are in the range of order.

Cloud vertical distribution from combined surface and space radar-lidar observations at two Arctic atmospheric observatories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yinghui; Shupe, Matthew D.; Wang, Zhien

Detailed and accurate vertical distributions of cloud properties (such as cloud fraction, cloud phase, and cloud water content) and their changes are essential to accurately calculate the surface radiative flux and to depict the mean climate state. Surface and space-based active sensors including radar and lidar are ideal to provide this information because of their superior capability to detect clouds and retrieve cloud microphysical properties. In this study, we compare the annual cycles of cloud property vertical distributions from space-based active sensors and surface-based active sensors at two Arctic atmospheric observatories, Barrow and Eureka. Based on the comparisons, we identifymore » the sensors' respective strengths and limitations, and develop a blended cloud property vertical distribution by combining both sets of observations. Results show that surface-based observations offer a more complete cloud property vertical distribution from the surface up to 11 km above mean sea level (a.m.s.l.) with limitations in the middle and high altitudes; the annual mean total cloud fraction from space-based observations shows 25-40 % fewer clouds below 0.5 km than from surface-based observations, and space-based observations also show much fewer ice clouds and mixed-phase clouds, and slightly more liquid clouds, from the surface to 1 km. In general, space-based observations show comparable cloud fractions between 1 and 2 km a.m.s.l., and larger cloud fractions above 2 km a.m.s.l. than from surface-based observations. A blended product combines the strengths of both products to provide a more reliable annual cycle of cloud property vertical distributions from the surface to 11 km a.m.s.l. This information can be valuable for deriving an accurate surface radiative budget in the Arctic and for cloud parameterization evaluation in weather and climate models. Cloud annual cycles show similar evolutions in total cloud fraction and ice cloud fraction, and lower liquid-containing cloud fraction at Eureka than at Barrow; the differences can be attributed to the generally colder and drier conditions at Eureka relative to Barrow.« less

Cloud vertical distribution from combined surface and space radar-lidar observations at two Arctic atmospheric observatories

DOE PAGES

Liu, Yinghui; Shupe, Matthew D.; Wang, Zhien; ...

2017-05-16

Detailed and accurate vertical distributions of cloud properties (such as cloud fraction, cloud phase, and cloud water content) and their changes are essential to accurately calculate the surface radiative flux and to depict the mean climate state. Surface and space-based active sensors including radar and lidar are ideal to provide this information because of their superior capability to detect clouds and retrieve cloud microphysical properties. In this study, we compare the annual cycles of cloud property vertical distributions from space-based active sensors and surface-based active sensors at two Arctic atmospheric observatories, Barrow and Eureka. Based on the comparisons, we identifymore » the sensors' respective strengths and limitations, and develop a blended cloud property vertical distribution by combining both sets of observations. Results show that surface-based observations offer a more complete cloud property vertical distribution from the surface up to 11 km above mean sea level (a.m.s.l.) with limitations in the middle and high altitudes; the annual mean total cloud fraction from space-based observations shows 25-40 % fewer clouds below 0.5 km than from surface-based observations, and space-based observations also show much fewer ice clouds and mixed-phase clouds, and slightly more liquid clouds, from the surface to 1 km. In general, space-based observations show comparable cloud fractions between 1 and 2 km a.m.s.l., and larger cloud fractions above 2 km a.m.s.l. than from surface-based observations. A blended product combines the strengths of both products to provide a more reliable annual cycle of cloud property vertical distributions from the surface to 11 km a.m.s.l. This information can be valuable for deriving an accurate surface radiative budget in the Arctic and for cloud parameterization evaluation in weather and climate models. Cloud annual cycles show similar evolutions in total cloud fraction and ice cloud fraction, and lower liquid-containing cloud fraction at Eureka than at Barrow; the differences can be attributed to the generally colder and drier conditions at Eureka relative to Barrow.« less

Impact constraints on the environment for chemical evolution and the continuity of life

NASA Technical Reports Server (NTRS)

Oberbeck, Verne R.; Fogleman, Guy

1990-01-01

The moon and the earth were bombarded heavily by planetesimals and asteroids that were capable of interfering with chemical evolution and the origin of life. This paper explores the frequency of giant terrestrial impacts able to stop prebiotic chemistry in the probable regions of chemical evolution. The limited time available between impacts disruptive to prebiotic chemistry at the time of the oldest evidence of life suggests the need for a rapid process for chemical evolution of life. On the other hand, rapid chemical evolution in cloud systems and lakes or other shallow evaporating water bodies would have been possible because reactants could have been concentrated and polymerized rapidly in this environment. Thus life probably could have originated near the surface between frequent surface-sterilizing impacts. There may not have been continuity of life depending on sunlight because there is evidence that life, existing as early as 3.8 Gyr ago, may have been destroyed by giant impacts. The first such organisms on earth were probably not the ancestors of present life.

An assessment of thin cloud detection by applying bidirectional reflectance distribution function model-based background surface reflectance using Geostationary Ocean Color Imager (GOCI): A case study for South Korea

NASA Astrophysics Data System (ADS)

Kim, Hye-Won; Yeom, Jong-Min; Shin, Daegeun; Choi, Sungwon; Han, Kyung-Soo; Roujean, Jean-Louis

2017-08-01

In this study, a new assessment of thin cloud detection with the application of bidirectional reflectance distribution function (BRDF) model-based background surface reflectance was undertaken by interpreting surface spectra characterized using the Geostationary Ocean Color Imager (GOCI) over a land surface area. Unlike cloud detection over the ocean, the detection of cloud over land surfaces is difficult due to the complicated surface scattering characteristics, which vary among land surface types. Furthermore, in the case of thin clouds, in which the surface and cloud radiation are mixed, it is difficult to detect the clouds in both land and atmospheric fields. Therefore, to interpret background surface reflectance, especially underneath cloud, the semiempirical BRDF model was used to simulate surface reflectance by reflecting solar angle-dependent geostationary sensor geometry. For quantitative validation, Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) data were used to make a comparison with the proposed cloud masking result. As a result, the new cloud masking scheme resulted in a high probability of detection (POD = 0.82) compared with the Moderate Resolution Imaging Spectroradiometer (MODIS) (POD = 0.808) for all cloud cases. In particular, the agreement between the CALIPSO cloud product and new GOCI cloud mask was over 94% when detecting thin cloud (e.g., altostratus and cirrus) from January 2014 to June 2015. This result is relatively high in comparison with the result from the MODIS Collection 6 cloud mask product (MYD35).

Impacts of Cosmic Dust on Planetary Atmospheres and Surfaces

NASA Astrophysics Data System (ADS)

Plane, John M. C.; Flynn, George J.; Määttänen, Anni; Moores, John E.; Poppe, Andrew R.; Carrillo-Sanchez, Juan Diego; Listowski, Constantino

2018-02-01

Recent advances in interplanetary dust modelling provide much improved estimates of the fluxes of cosmic dust particles into planetary (and lunar) atmospheres throughout the solar system. Combining the dust particle size and velocity distributions with new chemical ablation models enables the injection rates of individual elements to be predicted as a function of location and time. This information is essential for understanding a variety of atmospheric impacts, including: the formation of layers of metal atoms and ions; meteoric smoke particles and ice cloud nucleation; perturbations to atmospheric gas-phase chemistry; and the effects of the surface deposition of micrometeorites and cosmic spherules. There is discussion of impacts on all the planets, as well as on Pluto, Triton and Titan.

The chemical evolution of molecular clouds

NASA Technical Reports Server (NTRS)

Iglesias, E.

1977-01-01

The nonequilibrium chemistry of dense molecular clouds (10,000 to 1 million hydrogen molecules per cu cm) is studied in the framework of a model that includes the latest published chemical data and most of the recent theoretical advances. In this model the only important external source of ionization is assumed to be high-energy cosmic-ray bombardment; standard charge-transfer reactions are taken into account as well as reactions that transfer charge from molecular ions to trace-metal atoms. Schemes are proposed for the synthesis of such species as NCO, HNCO, and CN. The role played by adsorption and condensation of molecules on the surface of dust grains is investigated, and effects on the chemical evolution of a dense molecular cloud are considered which result from varying the total density or the elemental abundances and from assuming negligible or severe condensation of gaseous species on dust grains. It is shown that the chemical-equilibrium time scale is given approximately by the depletion times of oxygen and nitrogen when the condensation efficiency is negligible; that this time scale is probably in the range from 1 to 4 million years, depending on the elemental composition and initial conditions in the cloud; and that this time scale is insensitive to variations in the total density.

Shocks and Molecules in Protostellar Outflows

NASA Astrophysics Data System (ADS)

Arce, Héctor

2014-06-01

As protostars form through the gravitational infall of material from their parent molecular cloud, they power energetic bipolar outflows that interact with the surrounding medium. Protostellar outflows are important to the chemical evolution of star forming regions, as the shocks produced by the interaction of the high-velocity protostellar wind and the ambient cloud can heat the surrounding medium and trigger chemical and physical processes that would otherwise not take place in a quiescent molecular cloud. Protostellar outflows, are therefore a great laboratory to study shock physics and shock-induced chemistry. I will present results from millimeter-wave observations of a small sample of outflow shocks. The spectra show clear evidence of the existence of complex organic molecules (e.g., methyl formate, ethanol, acetaldehyde) and high abundance of certain simple molecules (e.g., HCO^+, HCN, H_2O) in outflows. Results indicate that, most likely, the complex species formed on the surface of grains and were then ejected from the grain mantles by the shock. Spectral surveys of shocked regions using ALMA could therefore be used to probe the composition of dust in molecular clouds. Our results demonstrate that outflows modify the chemical composition of the surrounding gaseous environment and that this needs to be considered when using certain species to study active star forming regions.

Effects of Implementing Subgrid-Scale Cloud-Radiation Interactions in a Regional Climate Model

NASA Astrophysics Data System (ADS)

Herwehe, J. A.; Alapaty, K.; Otte, T.; Nolte, C. G.

2012-12-01

Interactions between atmospheric radiation, clouds, and aerosols are the most important processes that determine the climate and its variability. In regional scale models, when used at relatively coarse spatial resolutions (e.g., larger than 1 km), convective cumulus clouds need to be parameterized as subgrid-scale clouds. Like many groups, our regional climate modeling group at the EPA uses the Weather Research & Forecasting model (WRF) as a regional climate model (RCM). One of the findings from our RCM studies is that the summertime convective systems simulated by the WRF model are highly energetic, leading to excessive surface precipitation. We also found that the WRF model does not consider the interactions between convective clouds and radiation, thereby omitting an important process that drives the climate. Thus, the subgrid-scale cloudiness associated with convective clouds (from shallow cumuli to thunderstorms) does not exist and radiation passes through the atmosphere nearly unimpeded, potentially leading to overly energetic convection. This also has implications for air quality modeling systems that are dependent upon cloud properties from the WRF model, as the failure to account for subgrid-scale cloudiness can lead to problems such as the underrepresentation of aqueous chemistry processes within clouds and the overprediction of ozone from overactive photolysis. In an effort to advance the climate science of the cloud-aerosol-radiation (CAR) interactions in RCM systems, as a first step we have focused on linking the cumulus clouds with the radiation processes. To this end, our research group has implemented into WRF's Kain-Fritsch (KF) cumulus parameterization a cloudiness formulation that is widely used in global earth system models (e.g., CESM/CAM5). Estimated grid-scale cloudiness and associated condensate are adjusted to account for the subgrid clouds and then passed to WRF's Rapid Radiative Transfer Model - Global (RRTMG) radiation schemes to affect the shortwave and longwave radiative processes. To evaluate the effects of implementing the subgrid-scale cloud-radiation interactions on WRF regional climate simulations, a three-year study period (1988-1990) was simulated over the CONUS using two-way nested domains with 108 km and 36 km horizontal grid spacing, without and with the cumulus feedbacks to radiation, and without and with some form of four dimensional data assimilation (FDDA). Initial and lateral boundary conditions (as well as data for the FDDA, when enabled) were supplied from downscaled NCEP-NCAR Reanalysis II (R2) data sets. Evaluation of the simulation results will be presented comparing regional surface precipitation and temperature statistics with North American Regional Reanalysis (NARR) data and Climate Forecast System Reanalysis (CFSR) data, respectively, as well as comparison with available surface radiation (SURFRAD) and satellite (CERES) observations. This research supports improvements in the EPA's WRF-CMAQ modeling system, leading to better predictions of present and future air quality and climate interactions in order to protect human health and the environment.

A Case Study of Ship Track Formation in a Polluted Marine Boundary Layer.

NASA Astrophysics Data System (ADS)

Noone, Kevin J.; Johnson, Doug W.; Taylor, Jonathan P.; Ferek, Ronald J.; Garrett, Tim; Hobbs, Peter V.; Durkee, Philip A.; Nielsen, Kurt; Öström, Elisabeth; O'Dowd, Colin; Smith, Michael H.; Russell, Lynn M.; Flagan, Richard C.; Seinfeld, John H.; de Bock, Lieve; van Grieken, René E.; Hudson, James G.; Brooks, Ian;  Gasparovic, Richard F.;  Pockalny, Robert A.

2000-08-01

A case study of the effects of ship emissions on the microphysical, radiative, and chemical properties of polluted marine boundary layer clouds is presented. Two ship tracks are discussed in detail. In situ measurements of cloud drop size distributions, liquid water content, and cloud radiative properties, as well as aerosol size distributions (outside-cloud, interstitial, and cloud droplet residual particles) and aerosol chemistry, are presented. These are related to remotely sensed measurements of cloud radiative properties.The authors examine the processes behind ship track formation in a polluted marine boundary layer as an example of the effects of anthropogenic particulate pollution on the albedo of marine stratiform clouds.

Gas-Grain Chemical Models: Inclusion of a Grain Size Distribution and a Study Of Young Stellar Objects in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Pauly, Tyler Andrew

2017-06-01

Computational models of interstellar gas-grain chemistry have aided in our understanding of star-forming regions. Chemical kinetics models rely on a network of chemical reactions and a set of physical conditions in which atomic and molecular species are allowed to form and react. We replace the canonical single grain-size in our chemical model MAGICKAL with a grain size distribution and analyze the effects on the chemical composition of the gas and grain surface in quiescent and collapsing dark cloud models. We find that a grain size distribution coupled with a temperature distribution across grain sizes can significantly affect the bulk ice composition when dust temperatures fall near critical values related to the surface binding energies of common interstellar chemical species. We then apply the updated model to a study of ice formation in the cold envelopes surrounding massive young stellar objects in the Magellanic Clouds. The Magellanic Clouds are local satellite galaxies of the Milky Way, and they provide nearby environments to study star formation at low metallicity. We expand the model calculation of dust temperature to include a treatment for increased interstellar radiation field intensity; we vary the radiation field to model the elevated dust temperatures observed in the Magellanic Clouds. We also adjust the initial elemental abundances used in the model, guided by observations of Magellanic Cloud HII regions. We are able to reproduce the relative ice fractions observed, indicating that metal depletion and elevated grain temperature are important drivers of the envelope ice composition. The observed shortfall in CO in Small Magellanic Cloud sources can be explained by a combination of reduced carbon abundance and increased grain temperatures. The models indicate that a large variation in radiation field strength is required to match the range of observed LMC abundances. CH 3OH abundance is found to be enhanced (relative to total carbon abundance) in low-metallicity models, providing seed material for complex organic molecule formation. We conclude with a preliminary study of the recently discovered hot core in the Large Magellanic Cloud; we create a grid of models to simulate hot core formation in Magellanic Cloud environments, comparing them to models and observations of well-characterized galactic counterparts.

The DACCIWA Project: Dynamics-Aerosol-Chemistry-Cloud interactions in West Africa

NASA Astrophysics Data System (ADS)

Knippertz, Peter

2014-05-01

Massive economic and population growth and urbanisation are expected to lead to a tripling of anthropogenic emissions from southern West Africa (SWA) between 2000 and 2030, the impacts of which on human health, ecosystems, food security and the regional climate are largely unknown. An assessment of these impacts is complicated by (a) a superposition with effects of global climate change, (b) the strong dependence of SWA on the sensitive West African monsoon, (c) incomplete scientific understanding of interactions between emissions, clouds, radiation, precipitation and regional circulations and (d) by a lack of observations to advance our understanding and improve predictions. The purpose of this contribution is to introduce the research consortium DACCIWA (Dynamics-Aerosol-Chemistry-Cloud interactions in West Africa), which comprises 16 partners in six European and West African countries. The interdisciplinary DACCIWA team will build on the scientific and logistical foundations established by the African Monsoon Multidisciplinary Analysis (AMMA) project and collaborate closely with operational centres. DACCIWA will receive funding of about M8.75€ from the European Commission as part of Framework Programme 7 from 2015 until 2018. The DACCIWA project will conduct extensive fieldwork in SWA to collect high-quality observations, spanning the entire process chain from surface-based natural and anthropogenic emissions to impacts on health, ecosystems and climate. This will include a major field campaign in summer 2015 with three research aircrafts and two ground-based supersites. Combining the resulting benchmark dataset with a wide range of modelling activities will allow us: (a) to assess all relevant physical and chemical processes, (b) to improve the monitoring of climate and compositional parameters from space, (c) to determine health impacts from air pollution, and (d) to develop the next generation of weather and climate models capable of representing coupled cloud-aerosol interactions, which will ultimately lead to reduced uncertainties in climate predictions. SWA with its rich mix of emissions and diverse clouds is ideal for such a study and many findings and technical developments will be applicable to other monsoon regions. Using a targeted dissemination strategy, DACCIWA will deliver a comprehensive scientific assessment and actively guide sustainable future planning and policy-making for West Africa and beyond.

Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

NASA Technical Reports Server (NTRS)

Parella, J. P.; Jacob, D. J.; Liang, Q.; Zhang, Y.; Mickley, L. J.; Miller, B.; Evans, M. J.; Yang, X.; Pyle, J. A.; Theys, N.;

A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

NASA Astrophysics Data System (ADS)

Sareen, N.; McNeill, V. F.

2011-12-01

In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used. These compounds included (hemi)acetals, aldol condensation products, and oligomeric species up to 759 amu. Since these products are vulnerable to oxidants such as O3 and OH in the atmosphere, kinetic studies were conducted to study their affect upon exposure to O3 and OH. Custom-designed flow tube reactors were coupled with the Aerosol-CIMS to monitor aerosol composition, and consequently this data was used to determine reactive uptake coefficients (γO3~10-8 and γOH~ 10-6). Additionally, the lifetime of these SOA species in the atmosphere can be estimated and if these time scales are sufficiently long, they may affect aerosol optical properties. The effect of oxidation on the optical properties is also currently being tested by collecting aerosol particles before and after oxidation on a quartz window and testing changes in absorption using the UV-Vis spectrophotometer. The results of all these studies will be integrated to understand the role of methylglyoxal as a SOA precursor and the effect on various aerosol properties, and this will be used as a model system to predict the fate of similar organics in the atmosphere.

Stratospheric Ozone Response in Experiments G3 and G4 of the Geoengineering Model Intercomparison Project (GeoMIP)

NASA Technical Reports Server (NTRS)

Pitari, Giovanni; Aquila, Valentina; Kravitz, Ben; Watanabe, Shingo; Tilmes, Simone; Mancini, Eva; DeLuca, Natalia; DiGenova, Glauco

2013-01-01

Geoengineering with stratospheric sulfate aerosols has been proposed as a means of temporarily cooling the planet, alleviating some of the side effects of anthropogenic CO2 emissions. However, one of the known side effects of stratospheric injections of sulfate aerosols is a decrease in stratospheric ozone. Here we show results from two general circulation models and two coupled chemistry climate models that have simulated stratospheric sulfate aerosol geoengineering as part of the Geoengineering Model Intercomparison Project (GeoMIP). Changes in photolysis rates and upwelling of ozone-poor air in the tropics reduce stratospheric ozone, suppression of the NOx cycle increases stratospheric ozone, and an increase in available surfaces for heterogeneous chemistry modulates reductions in ozone. On average, the models show a factor 20-40 increase of the sulfate aerosol surface area density (SAD) at 50 hPa in the tropics with respect to unperturbed background conditions and a factor 3-10 increase at mid-high latitudes. The net effect for a tropical injection rate of 5 Tg SO2 per year is a decrease in globally averaged ozone by 1.1-2.1 DU in the years 2040-2050 for three models which include heterogeneous chemistry on the sulfate aerosol surfaces. GISS-E2-R, a fully coupled general circulation model, performed simulations with no heterogeneous chemistry and a smaller aerosol size; it showed a decrease in ozone by 9.7 DU. After the year 2050, suppression of the NOx cycle becomes more important than destruction of ozone by ClOx, causing an increase in total stratospheric ozone. Contribution of ozone changes in this experiment to radiative forcing is 0.23 W m-2 in GISS-E2-R and less than 0.1 W m-2 in the other three models. Polar ozone depletion, due to enhanced formation of both sulfate aerosol SAD and polar stratospheric clouds, results in an average 5 percent increase in calculated surface UV-B.

Modeling the partitioning of organic chemical species in cloud phases with CLEPS (1.1)

NASA Astrophysics Data System (ADS)

Rose, Clémence; Chaumerliac, Nadine; Deguillaume, Laurent; Perroux, Hélène; Mouchel-Vallon, Camille; Leriche, Maud; Patryl, Luc; Armand, Patrick

2018-02-01

The new detailed aqueous-phase mechanism Cloud Explicit Physico-chemical Scheme (CLEPS 1.0), which describes the oxidation of isoprene-derived water-soluble organic compounds, is coupled with a warm microphysical module simulating the activation of aerosol particles into cloud droplets. CLEPS 1.0 was then extended to CLEPS 1.1 to include the chemistry of the newly added dicarboxylic acids dissolved from the particulate phase. The resulting coupled model allows the prediction of the aqueous-phase concentrations of chemical compounds originating from particle scavenging, mass transfer from the gas-phase and in-cloud aqueous chemical reactivity. The aim of the present study was more particularly to investigate the effect of particle scavenging on cloud chemistry. Several simulations were performed to assess the influence of various parameters on model predictions and to interpret long-term measurements conducted at the top of Puy de Dôme (PUY, France) in marine air masses. Specific attention was paid to carboxylic acids, whose predicted concentrations are on average in the lower range of the observations, with the exception of formic acid, which is rather overestimated in the model. The different sensitivity runs highlight the fact that formic and acetic acids mainly originate from the gas phase and have highly variable aqueous-phase reactivity depending on the cloud acidity, whereas C3-C4 carboxylic acids mainly originate from the particulate phase and are supersaturated in the cloud.

A survey of bimolecular ion-molecule reactions for use in modeling the chemistry of planetary atmospheres, cometary comae, and interstellar clouds - 1993 supplement

NASA Technical Reports Server (NTRS)

Anicich, V. G.

1993-01-01

This is a supplement to a previous paper (Anicich & Huntress 1986). It is a survey of bimolecular positive ion-molecule reactions with potential importance to the chemistry of planetary atmospheres, cometary comae, and interstellar clouds. This supplement covers the literature from 1986 through 1991, with some additional citations missed in the original survey. Over 200 new citations are included. A table of reactions is listed by reactant ion, and cross-references are provided for both ionic and neutral reactants and also for both ionic and neutral products.

A New WRF-Chem Treatment for Studying Regional Scale Impacts of Cloud-Aerosol Interactions in Parameterized Cumuli

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, Larry K.; Shrivastava, ManishKumar B.; Easter, Richard C.

A new treatment of cloud-aerosol interactions within parameterized shallow and deep convection has been implemented in WRF-Chem that can be used to better understand the aerosol lifecycle over regional to synoptic scales. The modifications to the model to represent cloud-aerosol interactions include treatment of the cloud dropletnumber mixing ratio; key cloud microphysical and macrophysical parameters (including the updraft fractional area, updraft and downdraft mass fluxes, and entrainment) averaged over the population of shallow clouds, or a single deep convective cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. Thesechanges have beenmore » implemented in both the WRF-Chem chemistry packages as well as the Kain-Fritsch cumulus parameterization that has been modified to better represent shallow convective clouds. Preliminary testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS) as well as a high-resolution simulation that does not include parameterized convection. The simulation results are used to investigate the impact of cloud-aerosol interactions on the regional scale transport of black carbon (BC), organic aerosol (OA), and sulfate aerosol. Based on the simulations presented here, changes in the column integrated BC can be as large as -50% when cloud-aerosol interactions are considered (due largely to wet removal), or as large as +35% for sulfate in non-precipitating conditions due to the sulfate production in the parameterized clouds. The modifications to WRF-Chem version 3.2.1 are found to account for changes in the cloud drop number concentration (CDNC) and changes in the chemical composition of cloud-drop residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to WRF-Chem version 3.5, and it is anticipated that they will be included in a future public release of WRF-Chem.« less

Role of clouds, aerosols, and aerosol-cloud interaction in 20th century simulations with GISS ModelE2

NASA Astrophysics Data System (ADS)

Nazarenko, L.; Rind, D. H.; Bauer, S.; Del Genio, A. D.

2015-12-01

Simulations of aerosols, clouds and their interaction contribute to the major source of uncertainty in predicting the changing Earth's energy and in estimating future climate. Anthropogenic contribution of aerosols affects the properties of clouds through aerosol indirect effects. Three different versions of NASA GISS global climate model are presented for simulation of the twentieth century climate change. All versions have fully interactive tracers of aerosols and chemistry in both the troposphere and stratosphere. All chemical species are simulated prognostically consistent with atmospheric physics in the model and the emissions of short-lived precursors [Shindell et al., 2006]. One version does not include the aerosol indirect effect on clouds. The other two versions include a parameterization of the interactive first indirect aerosol effect on clouds following Menon et al. [2010]. One of these two models has the Multiconfiguration Aerosol Tracker of Mixing state (MATRIX) that permits detailed treatment of aerosol mixing state, size, and aerosol-cloud activation. The main purpose of this study is evaluation of aerosol-clouds interactions and feedbacks, as well as cloud and aerosol radiative forcings, for the twentieth century climate under different assumptions and parameterizations for aerosol, clouds and their interactions in the climate models. The change of global surface air temperature based on linear trend ranges from +0.8°C to +1.2°C between 1850 and 2012. Water cloud optical thickness increases with increasing temperature in all versions with the largest increase in models with interactive indirect effect of aerosols on clouds, which leads to the total (shortwave and longwave) cloud radiative cooling trend at the top of the atmosphere. Menon, S., D. Koch, G. Beig, S. Sahu, J. Fasullo, and D. Orlikowski (2010), Black carbon aerosols and the third polar ice cap, Atmos. Chem. Phys., 10,4559-4571, doi:10.5194/acp-10-4559-2010. Shindell, D., G. Faluvegi, N. Unger, E. Aguilar, G.A. Schmidt, D.M. Koch, S.E. Bauer, and J.R. Miller (2006), Simulations of preindustrial, present-day, and 2100 conditions in the NASA GISS composition and climate model G-PUCCINI, Atmos. Chem. Phys., 6, 4427-4459.

Scientific goals of the Cooperative Multiscale Experiment (CME)

NASA Technical Reports Server (NTRS)

Cotton, William

1993-01-01

Mesoscale Convective Systems (MCS) form the focus of CME. Recent developments in global climate models, the urgent need to improve the representation of the physics of convection, radiation, the boundary layer, and orography, and the surge of interest in coupling hydrologic, chemistry, and atmospheric models of various scales, have emphasized the need for a broad interdisciplinary and multi-scale approach to understanding and predicting MCS's and their interactions with processes at other scales. The role of mesoscale systems in the large-scale atmospheric circulation, the representation of organized convection and other mesoscale flux sources in terms of bulk properties, and the mutually consistent treatment of water vapor, clouds, radiation, and precipitation, are all key scientific issues concerning which CME will seek to increase understanding. The manner in which convective, mesoscale, and larger scale processes interact to produce and organize MCS's, the moisture cycling properties of MCS's, and the use of coupled cloud/mesoscale models to better understand these processes, are also major objectives of CME. Particular emphasis will be placed on the multi-scale role of MCS's in the hydrological cycle and in the production and transport of chemical trace constituents. The scientific goals of the CME consist of the following: understand how the large and small scales of motion influence the location, structure, intensity, and life cycles of MCS's; understand processes and conditions that determine the relative roles of balanced (slow manifold) and unbalanced (fast manifold) circulations in the dynamics of MCS's throughout their life cycles; assess the predictability of MCS's and improve the quantitative forecasting of precipitation and severe weather events; quantify the upscale feedback of MCS's to the large-scale environment and determine interrelationships between MCS occurrence and variations in the large-scale flow and surface forcing; provide a data base for initialization and verification of coupled regional, mesoscale/hydrologic, mesoscale/chemistry, and prototype mesoscale/cloud-resolving models for prediction of severe weather, ceilings, and visibility; provide a data base for initialization and validation of cloud-resolving models, and for assisting in the fabrication, calibration, and testing of cloud and MCS parameterization schemes; and provide a data base for validation of four dimensional data assimilation schemes and algorithms for retrieving cloud and state parameters from remote sensing instrumentation.

Potential Impact of Microbial Activity on the Oxidant Capacity and the Organic Carbon Budget in Clouds (Invited)

NASA Astrophysics Data System (ADS)

Delort, A.

2013-12-01

Within cloud water, microorganisms are metabolically active; so they are suspected to contribute to atmospheric chemistry. This paper is focused on the interactions between microorganisms and Reactive Oxygenated Species present in cloud water since these chemical compounds are driving the oxidant capacity of the cloud system. For this, real cloud waters with contrasting features (marine, continental, urban) were sampled at the puy de Dôme mountain (France). They exhibit high microbial biodiversity and complex chemical composition. These media were incubated in the dark and subjected to UV-light radiation in specifically designed photo-bio-reactors. The concentrations of hydrogen peroxide (H2O2), organic compounds and the ATP/ADP ratio were monitored during the incubation period. Microorganisms remained metabolically active in the presence of hydroxyl radicals photo-produced from H2O2. This oxidant and major carbon compounds (formaldehyde and carboxylic acids) were biodegraded by the endogenous microflora. This work suggests that microorganisms could play a double role in atmospheric chemistry: first, they could directly metabolize organic carbon species; second they could reduce the available source of radicals due to their oxidative metabolism. Consequently, molecules such as H2O2 would be no longer available for photochemical or other chemical reactions, decreasing the cloud oxidant capacity.

Potential impact of microbial activity on the oxidant capacity and organic carbon budget in clouds

NASA Astrophysics Data System (ADS)

Vaïtilingom, Mickael; Deguillaume, Laurent; Vinatier, Virginie; Sancelme, Martine; Amato, Pierre; Chaumerliac, Nadine; Delort, Anne-Marie

2013-01-01

Within cloud water, microorganisms are metabolically active and, thus, are expected to contribute to the atmospheric chemistry. This article investigates the interactions between microorganisms and the reactive oxygenated species that are present in cloud water because these chemical compounds drive the oxidant capacity of the cloud system. Real cloud water samples with contrasting features (marine, continental, and urban) were taken from the puy de Dôme mountain (France). The samples exhibited a high microbial biodiversity and complex chemical composition. The media were incubated in the dark and subjected to UV radiation in specifically designed photo-bioreactors. The concentrations of H2O2, organic compounds, and the ATP/ADP ratio were monitored during the incubation period. The microorganisms remained metabolically active in the presence of ●OH radicals that were photo-produced from H2O2. This oxidant and major carbon compounds (formaldehyde and carboxylic acids) were biodegraded by the endogenous microflora. This work suggests that microorganisms could play a double role in atmospheric chemistry; first, they could directly metabolize organic carbon species, and second, they could reduce the available source of radicals through their oxidative metabolism. Consequently, molecules such as H2O2 would no longer be available for photochemical or other chemical reactions, which would decrease the cloud oxidant capacity.

From Titan to the primitive Earth

NASA Astrophysics Data System (ADS)

Raulin, F.; Gpcos Team

Our knowledge of the conditions prevailing in the environment of the primitive Earth is still very limited, due to the lack of geological data. Fortunately, there are a few planetary objects in the solar system which present similarities with our planet, including during its early history. Titan is one of these. With a diameter of more than 5100 km, Titan, the largest moon of Saturn, is also the only one to have a dense atmosphere. This atmosphere, clearly evidenced by the presence of haze layers, extends to approximately 1500 km. Like the Earth, Titan's atmosphere is mainly composed of dinitrogen, N2 . The other main constituents are methane, CH4 , about 1.6% to 2.0% in the stratosphere, as measured by CIRS on Cassini and GC-MS on Huygens and dihydrogen (H2 , approximate 0.1%). With surface temperatures of approximately 94 K, and an average surface pressure of 1.5 bar, Titan's atmosphere is nearly five times denser than the Earth's. Despite of these differences between Titan and the Earth there are several analogies that can be drawn between the two planetary bodies. The first resemblances concern the vertical atmospheric structure. Although Titan is much colder, with a troposphere (˜94-˜70 K), a tropopause (70.4 K) and a stratosphere (˜70-175 K) its atmosphere presents a similar complex structure to that of the Earth. These analogies are linked to the presence in both atmospheres of greenhouse gases: CH4 and H2 on Titan, equivalent respectively to terrestrial condensable H2 O and non-condensable CO2 . In addition the haze particles and clouds in Titan's atmosphere play an antigreenhouse effect similar to that of the terrestrial atmospheric aerosols and clouds. Indeed, methane on Titan seems to play the role of water on the Earth, with a complex cycle, which still has to be understood. The possibility that Titan is covered with hydrocarbon oceans is now ruled out, but it is still possible that Titan's surface include lakes of methane and ethane. Moreover, the DISR instrument on Huygens has provided pictures of Titan's surface which clearly shows dentritic structures strongly suggesting recent liquid flow on the surface of Titan. In addition, the Huygens GCMS data show that methane mole fraction increases in the low troposphere (up to 5%) and reaches the saturation level at approximately 8 km altitude, allowing the possible formation of clouds and rain. Furthermore, GC-MS analyses recorded a 50% increase 1 in the methane mole fraction at Titan's surface, suggesting the presence of condensed methane on the surface near the lander. Other observations from the Cassini instruments clearly show the presence of various surface features of different origins indicative of volcanic, tectonic, sedimentological and meteorological processes.as we find on Earth .INMS on Cassini and GC-MS on Huygens have detected the presence of argon in the atmosphere. Similarly to the Earth atmosphere, the most abundant argon isotope is 40 Ar, which comes from the radioactive decay of 40 K. This strongly suggests that Titan's atmosphere is a secondary atmosphere, produced by the degassing of trapped gases. Analogies can also be made between the organic chemistry which is very active now on Titan and the prebiotic chemistry which was active on primitive Earth. In spite of the absence of permanent bodies of liquid water on Titan's surface, several of the organic processes which are occurring today on Titan imply some of the organic compounds which are considered as key molecules in the terrestrial prebiotic chemistry, such as hydrogen cyanide (HCN), cyanoacetylene (HC3 N) and cyanogen (C2 N2 ). A complex organic chemistry seems to be present in the three components of what one can call, always by analogy with our planet, the "geofluids" of Titan: air (gas atmosphere), aerosols (solid atmosphere) and surface (oceans). A recent study on the hydrogen escape from the primitive atmosphere of the Earth suggests that it may have been more reducing that we thought. If this is correct, the chemical processes involved in Titan's atmospheric chemistry may be even closer to those on the primitive Earth. References. Feng T., Owen B. T., Pavlov, A.A, and De Sterck, H. 2005. `A Hydrogen-Rich Early Earth Atmosphere'. Science 308, 1014-1017. Raulin, F. (2005), `Exo-Astrobiological Aspects of Europa and Titan: From Observations to Speculations', Space Science Review 116 (1-2), 471-496. Nature, (2005), `The Huygens probe on Titan', 8 News & Views, Articles and Letters 438, 756-802 2

ISCCP Cloud Properties Associated with Standard Cloud Types Identified in Individual Surface Observations

NASA Technical Reports Server (NTRS)

Hahn, Carole J.; Rossow, William B.; Warren, Stephen G.

1999-01-01

Individual surface weather observations from land stations and ships are compared with individual cloud retrievals of the International Satellite Cloud Climatology Project (ISCCP), Stage C1, for an 8-year period (1983-1991) to relate cloud optical thicknesses and cloud-top pressures obtained from satellite data to the standard cloud types reported in visual observations from the surface. Each surface report is matched to the corresponding ISCCP-C1 report for the time of observation for the 280x280-km grid-box containing that observation. Classes of the surface reports are identified in which a particular cloud type was reported present, either alone or in combination with other clouds. For each class, cloud amounts from both surface and C1 data, base heights from surface data, and the frequency-distributions of cloud-top pressure (p(sub c) and optical thickness (tau) from C1 data are averaged over 15-degree latitude zones, for land and ocean separately, for 3-month seasons. The frequency distribution of p(sub c) and tau is plotted for each of the surface-defined cloud types occurring both alone and with other clouds. The average cloud-top pressures within a grid-box do not always correspond well with values expected for a reported cloud type, particularly for the higher clouds Ci, Ac, and Cb. In many cases this is because the satellites also detect clouds within the grid-box that are outside the field of view of the surface observer. The highest average cloud tops are found for the most extensive cloud type, Ns, averaging 7 km globally and reaching 9 km in the ITCZ. Ns also has the greatest average retrieved optical thickness, tau approximately equal 20. Cumulonimbus clouds may actually attain far greater heights and depths, but do not fill the grid-box. The tau-p(sub c) distributions show features that distinguish the high, middle, and low clouds reported by the surface observers. However, the distribution patterns for the individual low cloud types (Cu, Sc, St) occurring alone overlap to such an extent that it is not possible to distinguish these cloud types from each other on the basis of tau-p(sub c) values alone. Other cloud types whose tau-p(sub c) distributions are indistinguishable are Cb, Ns, and thick As. However, the tau-p(sub c) distribution patterns for the different low cloud types are nevertheless distinguishable when all occurrences of a low cloud type are included, indicating that the different low types differ in their probabilities of co-occurrence with middle and high clouds.

An Investigation of the Effects of Black Carbon on Precipitation in the Western United States

NASA Astrophysics Data System (ADS)

Tseng, Hsien-Liang Rose

Black carbon (BC), the byproduct of incomplete combustion, is considered to be the second most important anthropogenic climate forcing agent after carbon dioxide. BC warms the atmosphere by absorbing solar radiation (direct effect), alters cloud and precipitation formation by acting as cloud condensation nuclei (indirect effect), and modifies cloud distribution via cloud burn-off (semi-direct effect). Currently, there are large discrepancies in general circulation model estimates of the influence of BC on precipitation. Even less known is how BC changes precipitation on regional scales. In the drought-stricken western United States (WUS), where BC emissions are known to affect the hydrological cycle, an investigation on how BC influences precipitation is warranted. In this study, we employ the Weather Research and Forecasting-Chemistry (WRF Chem) model (version 3.6.0) with the newly chemistry- and microphysics-coupled Fu-Liou-Gu radiation scheme to study how black carbon affects precipitation by separating BC-related effects into direct and semi-direct, and indirect effects. In this three-part study, we use a recent wet year (2005) to investigate black carbon effects. We first examine BC effects during a heavy wintertime heavy precipitation event (7-11 January 2005), a heavy summertime precipitation week for comparison to the wintertime event (20-24 July 2005), and finally, examine these same effects for the months of January to June 2005 to investigate month-long trends. We find that BC suppresses precipitation, predominantly through its direct and semi-direct effects. The direct and semi-direct effects warm the air aloft, and cool the lower levels of the atmosphere (surface dimming) through the reduction of downward shortwave radiation flux at the surface. These changes in vertical temperature increase the stability of the atmosphere and reduce convective precipitation. Convective precipitation reduction accounts for approximately 60 75% of the total precipitation reduction. Additionally, cooling in the lower levels reduces evaporation from the surface, which reduces the moisture needed for non-convective precipitation. Subsequently, reduced moisture in the atmosphere suppresses non-convective precipitation by approximately 10-40%. The indirect effects also reduce precipitation, but to a much smaller extent of 5-20%. Although we use an atypical BC emission dataset is used in this study, the resulting reduction of the different types of precipitation sheds light on the physical mechanisms of BC-cloud-radiation interactions by which the reductions follow. In particular, our results highlight the importance of the cumulus and surface layer parameterizations that house the triggering mechanism and surface moisture flux parameterizations in future studies. In this research we find the NEI 2005 emissions did not significantly change precipitation. This is likely due to the aggressive emission regulations that exist for the United States. Emission regulations, however, do not exist or are enforced equally across the globe. In the developing countries that rely on inefficient cook stoves and heating systems, the populations suffer the most due to black carbon emission. Along with respiratory and cardiovascular impacts from black carbon, they may suffer from reduced water resources from suppressed precipitation, as well. In a larger sense, findings from this research serve as a platform for understanding the wider-reaching effects of black carbon on regional precipitation and drought. In particular, in areas where there are no black carbon emission regulations, this would highlight health and potentially significant environmental benefits that could be achieved from a black carbon cap and trade.

Silicon chemistry in interstellar clouds

NASA Technical Reports Server (NTRS)

Langer, William D.; Glassgold, A. E.

1990-01-01

A new model of interstellar silicon chemistry is presented that explains the lack of SiO detections in cold clouds and contains an exponential temperature dependence for the SiO abundance. A key aspect of the model is the sensitivity of SiO production by neutral silicon reactions to density and temperature, which arises from the dependence of the rate coefficients on the population of the excited fine-structure levels of the silicon atom. As part of the explanation of the lack of SiO detections at low temperatures and densities, the model also emphasizes the small efficiencies of the production routes and the correspondingly long times needed to reach equilibrium. Measurements of the abundance of SiO, in conjunction with theory, can provide information on the physical properties of interstellar clouds such as the abundance of oxygen bearing molecules and the depletion of interstellar silicon.

Stratospheric ion and aerosol chemistry and possible links with cirrus cloud microphysics - A critical assessment

NASA Technical Reports Server (NTRS)

Mohnen, Volker A.

1990-01-01

Aspects of stratospheric ion chemistry and physics are assessed as they relate to aerosol formation and the transport of aerosols to upper tropospheric regions to create conditions favorable for cirrus cloud formation. It is found that ion-induced nucleation and other known phase transitions involving ions and sulfuric acid vapor are probably not efficient processes for stratospheric aerosol formation, and cannot compete with condensation of sulfuric acid on preexisting particles of volcanic or meteoritic origin which are larger than about 0.15 micron in radius. Thus, galactic cosmic rays cannot have a significant impact on stratospheric aerosol population. Changes in the stratospheric aerosol burden due to volcanos are up to two orders of magnitude larger than changes in ion densities. Thus, volcanic activity may modulate the radiative properties of cirrus clouds.

Comparison of cloud optical depth and cloud mask applying BRDF model-based background surface reflectance

NASA Astrophysics Data System (ADS)

Kim, H. W.; Yeom, J. M.; Woo, S. H.

2017-12-01

Over the thin cloud region, satellite can simultaneously detect the reflectance from thin clouds and land surface. Since the mixed reflectance is not the exact cloud information, the background surface reflectance should be eliminated to accurately distinguish thin cloud such as cirrus. In the previous research, Kim et al (2017) was developed the cloud masking algorithm using the Geostationary Ocean Color Imager (GOCI), which is one of significant instruments for Communication, Ocean, and Meteorology Satellite (COMS). Although GOCI has 8 spectral channels including visible and near infra-red spectral ranges, the cloud masking has quantitatively reasonable result when comparing with MODIS cloud mask (Collection 6 MYD35). Especially, we noticed that this cloud masking algorithm is more specialized in thin cloud detections through the validation with Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) data. Because this cloud masking method was concentrated on eliminating background surface effects from the top-of-atmosphere (TOA) reflectance. Applying the difference between TOA reflectance and the bi-directional reflectance distribution function (BRDF) model-based background surface reflectance, cloud areas both thick cloud and thin cloud can be discriminated without infra-red channels which were mostly used for detecting clouds. Moreover, when the cloud mask result was utilized as the input data when simulating BRDF model and the optimized BRDF model-based surface reflectance was used for the optimized cloud masking, the probability of detection (POD) has higher value than POD of the original cloud mask. In this study, we examine the correlation between cloud optical depth (COD) and its cloud mask result. Cloud optical depths mostly depend on the cloud thickness, the characteristic of contents, and the size of cloud contents. COD ranges from less than 0.1 for thin clouds to over 1000 for the huge cumulus due to scattering by droplets. With the cloud optical depth of CALIPSO, the cloud masking result can be more improved since we can figure out how deep cloud is. To validate the cloud mask and the correlation result, the atmospheric retrieval will be computed to compare the difference between TOA reflectance and the simulated surface reflectance.

OPTIMIZING MODEL PERFORMANCE: VARIABLE SIZE RESOLUTION IN CLOUD CHEMISTRY MODELING. (R826371C005)

EPA Science Inventory

Under many conditions size-resolved aqueous-phase chemistry models predict higher sulfate production rates than comparable bulk aqueous-phase models. However, there are special circumstances under which bulk and size-resolved models offer similar predictions. These special con...

The Chemistry of the Planets.

ERIC Educational Resources Information Center

Blake, Peter

1988-01-01

Introduces knowledge of planetary chemistry for possible use in teaching. Discusses the chemical composition of the planets; the atmosphere and clouds of Venus, Jupiter and its moons, and Titan. Includes diagrams of the greenhouse effects in the solar system, elemental abundances, and the chemical composition of Jupiter. (RT)

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Laboratory Studies of Atmospheric Heterogeneous Chemistry

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Leu, M-T.

1993-01-01

In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.

Chemical evolution of the gas in C-type shocks in dark clouds

NASA Astrophysics Data System (ADS)

Nesterenok, A. V.

2018-07-01

A magnetohydrodynamic model of a steady, transverse C-type shock in a dense molecular cloud is presented. A complete gas-grain chemical network is taken into account: the gas-phase chemistry, the adsorption of gas species on dust grains, various desorption mechanisms, the grain surface chemistry, the ion neutralization on dust grains, the sputtering of grain mantles. The population densities of energy levels of ions CI, CII and OI and molecules H2, CO, H2O are computed in parallel with the dynamical and chemical rate equations. The large velocity gradient approximation is used in the line radiative transfer calculations. The simulations consist of two steps: (i) modelling of the chemical and thermal evolution of a static molecular cloud and (ii) shock simulations. A comparison is made with the results of publicly available models of similar physical systems. The focus of the paper is on the chemical processing of gas material and ice mantles of dust grains by the shock. Sputtering of ice mantles takes place in the shock region close to the temperature peak of the neutral gas. At high shock speeds, molecules ejected from ice mantles are effectively destroyed in hot gas, and their survival time is low—of the order of dozens of years. After a passage of high-speed C-type shock, a zone of high abundance of atomic hydrogen appears in the cooling postshock gas that triggers formation of complex organic species such as methanol. It is shown that abundances of some complex organic molecules (COMs) in the postshock region can be much higher than in the preshock gas. These results are important for interpretation of observations of COMs in protostellar outflows.

Modeling the Relationships Between Aerosol Properties and the Direct and Indirect Effects of Aerosols on Climate

NASA Technical Reports Server (NTRS)

Toon, Owen B.

1994-01-01

Aerosols may affect climate directly by scattering and absorbing visible and infrared energy, They may also affect climate indirectly by modifying the properties of clouds through microphysical processes, and by altering abundances of radiatively important gases through heterogeneous chemistry. Researchers understand which aerosol properties control the direct effect of aerosols on the radiation budget. Unfortunately, despite an abundance of data on certain types of aerosols, much work remains to be done to determine the values of these properties. For instance we have little idea about the global distribution, seasonal variation, or interannual variability of the aerosol optical depth. Also we do not know the visible light absorption properties of tropical aerosols which may contain much debris from slash and burn agriculture. A positive correlation between aerosol concentrations and albedos of marine stratus clouds is observed, and the causative microphysics is understood. However, models suggest that it is difficult to produce new particles in the marine boundary layer. Some modelers have suggested that the particles in the marine boundary layer may originate in the free troposphere and be transported into the boundary layer. Others argue that the aerosols are created in the marine boundary layer. There are no data linking aerosol concentration and cirrus cloud albedo, and models suggest cirrus properties may not be very sensitive to aerosol abundance. There is clear evidence of a radiatively significant change in the global lower stratospheric ozone abundance during the past few decades. These changes are caused by heterogeneous chemical reactions occurring on the surfaces of particles. The rates of these reactions depend upon the chemical composition of the particles. Although rapid advances in understanding heterogeneous chemistry have been made, much remains to be done.

Laboratory and modeling studies of chemistry in dense molecular clouds

NASA Technical Reports Server (NTRS)

Huntress, W. T., Jr.; Prasad, S. S.; Mitchell, G. F.

1980-01-01

A chemical evolutionary model with a large number of species and a large chemical library is used to examine the principal chemical processes in interstellar clouds. Simple chemical equilibrium arguments show the potential for synthesis of very complex organic species by ion-molecule radiative association reactions.

Implementing marine organic aerosols into the GEOS-Chem model

DOE PAGES

Gantt, B.; Johnson, M. S.; Crippa, M.; ...

2015-03-17

Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Modelmore » predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.« less

Validation of the Archived CERES Surface and Atmosphere Radiation Budget (SARB) at SGP

NASA Technical Reports Server (NTRS)

Charlock, Thomas P.; Rose, Fred G.; Rutan, David A.

2003-01-01

The CERES Surface and Atmosphere Radiation Budget (SARB) product (Charlock et al, 2002) includes the vertical profile of broadband SW, broadband LW, and 8-12 micron window (WN) fluxes; upwelling and downwelling at TOA, 70 hPa, 200 hPa, 500 hPa, and the surface; and for all-sky and clear-sky conditions. We test the archived CERES TRMM record of SARB for January-August 1998 and focus on discrepancies with ground-based measurements at SGP. The CERES SARB is generated by a highly modified Fu-Liou radiative transfer code (Fu and Liou, 1993). The most critical inputs for this application are cloud optical properties (fractional area, optical depth, particle size and phase, height of top, and estimate of geometrical thickness Minnis et al., 2002) from the narrowband VIRS imager. Numerous VIRS pixels (approx. 2km resolution at nadir) are matched to each of the large (approx. 20km) CERES broadband footprints (Wielicki et al, 1996). Other inputs include temperature and humidity from ECMWF (Rabier et al, 1998) , NCEP ozone profiles from SBUV and TOVS (Yang et al, 2001), aerosol optical thickness (AOT) from the Model for Atmospheric Transport and Chemistry (MATCH) aerosol assimilation (Collins et al., 2001) or alternately from the VIRS imager (Ignatov and Stowe, 2000). VIRS AOT is available for clear and partly cloudy ocean footprints during daylight; and only when viewing geometry renders a contribution from sunglint as unlikely. For other footprints, AOT is taken from MATCH. AOT is apportioned into fractions of dust (Tegan and Lacis, 1996), sea salt, sulfate, dust, soluble organic, insoluble organic, and soot (Hess et al., 1996) using the 6-hourly MATCH output. Tuned fluxes are retrieved by adjusting inputs to nudge computed TOA fluxes toward CERES observations (Rose et al, 1997). In clear conditions, the fields of humidity, surface skin temperature, surface albedo and AOT are adjusted to produce a closer match of computed and observed fluxes at TOA. When CERES footprints have clouds, the cloud optical thickness, fractional area within the footprint, and temperature of cloud top are adjusted by the tuning algorithm. Both tuned and untuned fluxes are archived, as are the respective adjustments to any parameters at the surface or within the atmosphere.

GPI Spectroscopy of the Mass, Age, and Metallicity Benchmark Brown Dwarf HD 4747 B

NASA Astrophysics Data System (ADS)

Crepp, Justin R.; Principe, David A.; Wolff, Schuyler; Giorla Godfrey, Paige A.; Rice, Emily L.; Cieza, Lucas; Pueyo, Laurent; Bechter, Eric B.; Gonzales, Erica J.

2018-02-01

The physical properties of brown dwarf companions found to orbit nearby, solar-type stars can be benchmarked against independent measures of their mass, age, chemical composition, and other parameters, offering insights into the evolution of substellar objects. The TRENDS high-contrast imaging survey has recently discovered a (mass/age/metallicity) benchmark brown dwarf orbiting the nearby (d = 18.69 ± 0.19 pc), G8V/K0V star HD 4747. We have acquired follow-up spectroscopic measurements of HD 4747 B using the Gemini Planet Imager to study its spectral type, effective temperature, surface gravity, and cloud properties. Observations obtained in the H-band and K 1-band recover the companion and reveal that it is near the L/T transition (T1 ± 2). Fitting atmospheric models to the companion spectrum, we find strong evidence for the presence of clouds. However, spectral models cannot satisfactorily fit the complete data set: while the shape of the spectrum can be well-matched in individual filters, a joint fit across the full passband results in discrepancies that are a consequence of the inherent color of the brown dwarf. We also find a 2σ tension in the companion mass, age, and surface gravity when comparing to evolutionary models. These results highlight the importance of using benchmark objects to study “secondary effects” such as metallicity, non-equilibrium chemistry, cloud parameters, electron conduction, non-adiabatic cooling, and other subtleties affecting emergent spectra. As a new L/T transition benchmark, HD 4747 B warrants further investigation into the modeling of cloud physics using higher resolution spectroscopy across a broader range of wavelengths, polarimetric observations, and continued Doppler radial velocity and astrometric monitoring.

Modeling and observational constraints on the sulfur cycle in the marine troposphere: a focus on reactive halogens and multiphase chemistry

NASA Astrophysics Data System (ADS)

Chen, Q.; Breider, T.; Schmidt, J.; Sherwen, T.; Evans, M. J.; Xie, Z.; Quinn, P.; Bates, T. S.; Alexander, B.

2017-12-01

The radiative forcing from marine boundary layer clouds is still highly uncertain, which partly stems from our poor understanding of cloud condensation nuclei (CCN) formation. The oxidation of dimethyl sulfide (DMS) and subsequent chemical evolution of its products (e.g. DMSO) are key processes in CCN formation, but are generally very simplified in large-scale models. Recent research has pointed out the importance of reactive halogens (e.g. BrO and Cl) and multiphase chemistry in the tropospheric sulfur cycle. In this study, we implement a series of sulfur oxidation mechanisms into the GEOS-Chem global chemical transport model, involving both gas-phase and multiphase oxidation of DMS, DMSO, MSIA and MSA, to improve our understanding of the sulfur cycle in the marine troposphere. DMS observations from six locations around the globe and MSA/nssSO42- ratio observations from two ship cruises covering a wide range of latitudes and longitudes are used to assess the model. Preliminary results reveal the important role of BrO for DMS oxidation at high latitudes (up to 50% over Southern Ocean). Oxidation of DMS by Cl radicals is small in the model (within 10% in the marine troposphere), probably due to an underrepresentation of Cl sources. Multiphase chemistry (e.g. oxidation by OH and O3 in cloud droplets) is not important for DMS oxidation but is critical for DMSO oxidation and MSA production and removal. In our model, about half of the DMSO is oxidized in clouds, leading to the formation of MSIA, which is further oxidized to form MSA. Overall, with the addition of reactive halogens and multiphase chemistry, the model is able to better reproduce observations of seasonal variations of DMS and MSA/nssSO42- ratios.

Evaluating Clouds in Long-Term Cloud-Resolving Model Simulations with Observational Data

NASA Technical Reports Server (NTRS)

Zeng, Xiping; Tao, Wei-Kuo; Zhang, Minghua; Peters-Lidard, Christa; Lang, Stephen; Simpson, Joanne; Kumar, Sujay; Xie, Shaocheng; Eastman, Joseph L.; Shie, Chung-Lin;

Mesoscale Modeling of Smoke Particles Distribution and Their Radiative Feedback over Northern Sub-Saharan African Region

NASA Astrophysics Data System (ADS)

Yue, Y.; Wang, J.; Ichoku, C. M.; Ellison, L.

2015-12-01

Stretching from southern boundary of Sahara to the equator and expanding west to east from Atlantic Ocean coasts to the India Ocean coasts, the northern sub-Saharan African (NSSA) region has been subject to intense biomass burning. Comprised of savanna, shrub, tropical forest and a number of agricultural crops, the extensive fires burn belt covers central and south of NSSA during dry season (from October to March) contributes to one of the highest biomass burning rate per km2 in the world. Due to smoke particles' absorption effects of solar radiation, they can modify the surface and atmosphere temperature and thus change atmospheric stability, height of the boundary layer, regional atmospheric circulation, evaporation rate, cloud formation, and precipitation. Hence, smoke particles emitted from biomass burning over NSSA region has a significant influence to the air quality, weather and climate variability. In this study, the first version of this Fire Energetics and Emissions Research (FEER.v1) emissions of several smoke constituents including light-absorbing organic carbon (OC) and black carbon (BC) are applied to a state-of-science meteorology-chemistry model as NOAA Weather Research and Forecasting Model with Chemistry (WRF-Chem). We analyzed WRF-Chem simulations of surface and vertical distribution of various pollutants and their direct radiative effects in conjunction with satellite observation data from Moderate Resolution Imaging Spectroradiometer (MODIS) and Cloud-Aerosol Lidar data with Orthogonal Polarization (CALIPSO) to strengthen the importance of combining space measured emission products like FEER.v1 emission inventory with mesoscale model over intense biomass burning region, especially in area where ground-based air-quality and radiation-related observations are limited or absent.

Plume and wake dynamics, mixing, and chemistry behind an HSCT aircraft

NASA Technical Reports Server (NTRS)

Miake-Lye, R. C.; Martinez-Sanchez, M.; Brown, R. C.; Kolb, C. E.

1991-01-01

The chemical evolution and mixing and vortical motion of a High Speed Civil Transport's engine exhausts must be analyzed in order to track the gas and its speciation as emissions are mixed to atmospheric scales. Attention is presently given to an analytic model of the wake dynamical processes which accounts for the roll-up of the trailing vorticity, its breakup due to the Crow instability, and the subsequent evolution and motion of the reconnected vorticity. The concentrated vorticity is noted to wrap up the buoyant exhaust and suppress its continued mixing and dilution. The species tracked encompass those which could be heterogeneously reactive on the surfaces of the condensed ice particles, and those capable of reacting with exhaust soot particle surfaces to form active contrail and/or cloud condensation nuclei.

Influence of cloud fraction and snow cover to the variation of surface UV radiation at King Sejong station, Antarctica

NASA Astrophysics Data System (ADS)

Lee, Yun Gon; Koo, Ja-Ho; Kim, Jhoon

2015-10-01

This study investigated how cloud fraction and snow cover affect the variation of surface ultraviolet (UV) radiation by using surface Erythemal UV (EUV) and Near UV (NUV) observed at the King Sejong Station, Antarctica. First the Radiative Amplification Factor (RAF), the relative change of surface EUV according to the total-column ozone amount, is compared for different cloud fractions and solar zenith angles (SZAs). Generally, all cloudy conditions show that the increase of RAF as SZA becomes larger, showing the larger effects of vertical columnar ozone. For given SZA cases, the EUV transmission through mean cloud layer gradually decreases as cloud fraction increases, but sometimes the maximum of surface EUV appears under partly cloudy conditions. The high surface EUV transmittance under broken cloud conditions seems due to the re-radiation of scattered EUV by cloud particles. NUV transmission through mean cloud layer also decreases as cloud amount increases but the sensitivity to the cloud fraction is larger than EUV. Both EUV and NUV radiations at the surface are also enhanced by the snow cover, and their enhancement becomes higher as SZA increases implying the diurnal variation of surface albedo. This effect of snow cover seems large under the overcast sky because of the stronger interaction between snow surface and cloudy sky.

Chemical Processing of Organics within Clouds: Pilot Study at Whiteface Mountain in Upstate NY

NASA Astrophysics Data System (ADS)

Lance, S.; Carlton, A. G.; Barth, M. C.; Schwab, J. J.; Minder, J. R.; Freedman, J. M.; Zhang, J.; Brandt, R. E.; Casson, P.; Brewer, M.; Orlowski, D.; Christiansen, A.

2017-12-01

Aqueous chemical processing within cloud and fog water has been identified as a key process in the formation of secondary organic aerosol (SOA) mass, which is found abundantly throughout the troposphere. Yet, significant uncertainty remains regarding the organic chemical reactions taking place within clouds and the conditions under which those reactions occur. Routine longterm measurements from the Whiteface Mountain (WFM) Research Observatory in upstate NY provide a unique and broad view of regional air quality relevant to the formation of particulate matter within clouds, largely due to the fact that the summit of WFM is within non-precipitating clouds 30-50% in summertime and the site is undisturbed by local sources. An NSF-funded Cloud Chemistry Workshop in Sept 2016 brought together key researchers at WFM to lay out the most pertinent scientific questions relevant to heterogeneous chemistry occurring within fogs and clouds and to discuss preliminary model intercomparisons. The workshop culminated in a plan to coordinate chemical analyses of cloud water samples focused on chemical constituents thought to be most relevant for SOA formation. Workshop participants also recommended that a pilot study be conducted at WFM to better characterize the meteorological conditions, airflow patterns and clouds intercepting the site, in preparation for future intensive field operations focused on the chemical processing of organics within clouds. This presentation will highlight the experimental design and preliminary observations from the pilot study taking place at WFM in August 2017. Upwind below-cloud measurements of aerosol CCN activation efficiency, size distribution and chemical composition will be compared with similar measurements made at the summit. Under certain conditions, we anticipate that aerosols measured at the summit between cloud events will be representative of cloud droplet residuals recently detrained from the frequent shallow cumulus intercepting the summit. Wind LIDAR and radiosonde observations will be used to link the below-cloud and summit observations. These pre- and post- `cloud processed' aerosols will also be compared with the chemical composition of cloud water samples to evaluate changes to the organic partitioning in the aqueous and aerosol phases.

The case for a deep-atmospheric in situ mission to address the highest priority Decadal Survey questions for Venus (Invited)

NASA Astrophysics Data System (ADS)

Atreya, S. K.; Garvin, J. B.; Glaze, L. S.; Campbell, B. A.; Fisher, M. E.; Flores, A.; Gilmore, M. S.; Johnson, N.; Kiefer, W. S.; Lorenz, R. D.; Mahaffy, P. R.; Ravine, M. A.; Webster, C. R.; Zolotov, M. Y.

2013-12-01

Current understanding of Venus lags behind that for Mars, with a major disparity of information concerning noble and trace gases and the small scale surface processes needed for comparative studies of terrestrial planet evolution. Despite global surface mapping by Magellan, discoveries by Venera landers, and ongoing atmospheric observations by the Venus Express (VEx) orbiter, significant questions about Venus remain unanswered. To place Venus into its proper context with respect to Mars and Earth, it is necessary to obtain new measurements that address top issues identified in the National Research Council (NRC) Solar System Decadal Survey: (1) evolution of the atmosphere, history of climate, and evidence of past hydrologic cycles; (2) history of volatiles and sedimentary cycles; and (3) planetary surface evolution. To answer these questions, new measurements are needed. First and foremost, in situ noble gas measurements are needed to constrain solar system formation and Venus evolution. In particular, the isotopic ratios of Xe and Kr can provide unique insights into planetary accretion. Isotopic measurements of nitrogen (15N/14N) will place important constraints on atmospheric loss processes. Current knowledge of this ratio has a substantial uncertainty of ×20%. VEx observations of hydrogen isotopes indicate the D/H ratio above the clouds is substantially greater than measured by Pioneer Venus, and varies with height. High precision measurements of the vertical distribution of the D/H isotopic ratio below the cloud layers will provide constraints on models of the climate history of water on Venus. The majority of atmospheric mass is located below the clouds. Current data suggest intense interaction among atmospheric gases down to the surface. The haze within the cloud region of unknown composition plays a central role in the radiative balance. Photochemically-derived species (H2SO4, OCS, CO, Sn) are subjected to thermochemical reactions below the clouds, especially within 30 km of the surface. Competing temperature-pressure dependent reactions and atmospheric circulation may cause vertical and latitudinal gradients of chemically-active trace gases (e.g., SO2, H2S, OCS, CO). Measurements of the chemical composition of the near-surface atmosphere can be used to evaluate the stability of primary and secondary minerals and can help to understand chemistry of atmosphere-surface interactions. However, concentrations of many trace species have never been measured below ~30 km, and multiple in situ measurements are required to evaluate chemical processes and cycles of volatiles, which can only be accomplished with deep entry probes. Current lack of understanding about Venus not only limits our understanding of evolutionary pathways Earth could experience, but also suggests that we are ill-equipped to understand the evolution of star systems with similar-sized planets.

Mesoscale modeling of smoke transport over the Southeast Asian Maritime Continent: Coupling of smoke direct radiative feedbacks below and above the low-level clouds

NASA Astrophysics Data System (ADS)

Ge, C.; Wang, J.; Reid, J. S.

2013-12-01

The online-coupled Weather Research and Forecasting model with Chemistry (WRF-Chem) is used to simulate the direct and semi-direct radiative impacts of smoke particles over the southeast Asian Marine Continents (MC, 10°S - 10°N, 90°E-150°E) during October 2006 when a significant El Nino event caused the highest biomass burning activity since 1997. With the use of OC (Organic Carbon) /BC (Black Carbon) ratio of 10 in the smoke emission inventory, the baseline simulation shows that the low-level clouds amplifying effect on smoke absorption led to a warming effect at the top-of-atmosphere (TOA) with a domain/monthly average forcing value of ~20 Wm-2 over the islands of Borneo and Sumatra. The smoke-induced monthly average daytime heating (0.3K) that is largely confined above the low-level clouds results in the local convergence over the smoke source region. This heating-induced convergence coupled with daytime planetary boundary layer turbulent mixing, transports more smoke particles above the planetary boundary layer height (PBLH), hence rendering a positive feedback. This positive feedback contrasts with the decrease of cloud fraction resulted from the combined effects of smoke heating within the cloud layer and the more stability in the boundary layer; the latter can be considered as a negative feedback in which decrease of cloud fraction weakens the heating by smoke particles above the clouds. During nighttime, the elevated smoke layer (above clouds in daytime) is decoupled from boundary layer, and the reduction of PBLH due to the residual surface cooling from the daytime lead to the accumulation of smoke particles near the surface. Because of smoke radiative extinction, on monthly basis, the amount of the solar input at the surface is reduced as large as 60 Wm-2, which lead to the decrease of sensible heat, latent heat, 2-m air temperature, and PBLH by a maximum of 20 Wm-2, 20 Wm-2, 1K, 120 m, respectively. The cloud changes over continents are mostly occurred over the islands of Sumatra and Borneo during the daytime, where the low-level cloud fraction decreases more than 10%. However, the change of local wind (include sea breeze) induced by the smoke radiative feedback leads to more convergence over Karimata Strait and south coastal area of Kalimantan during both daytime and night time; consequently, cloud fraction is increased there up to 20%. The sensitivities with different OC/BC ratio show the importance of the smoke single scattering albedo for the smoke semi-direct effects. A case study on 31 October 2006 further demonstrated a much larger (more than twice of the monthly average) feedback induced by smoke aerosols. The decreased sea breeze during big events can lead to prominent increase (40%) of low-level cloud over coastal water. Lastly, the direct and semi-direct radiative impact of smoke particles over the Southeast Asian Marine Continents is summarized as a conceptual model.

Evaluation of a multi-scale WRF-CAM5 simulation during the 2010 East Asian Summer Monsoon

DOE PAGES

Campbell, Patrick; Zhang, Yang; Wang, Kai; ...

2017-09-08

The Weather Research and Forecasting model with Chemistry (WRF-Chem) with the physics package of the Community Atmosphere Model Version 5 (CAM5) has been applied at multiple scales over Eastern China (EC) and the Yangtze River Delta (YRD) to evaluate how increased horizontal resolution with physics designed for a coarser resolution climate model impacts aerosols and clouds, and the resulting precipitation characteristics and performance during the 2010 East Asian Summer Monsoon (EASM). Despite large underpredictions in surface aerosol concentrations and aerosol optical depth, there is good spatial agreement with surface observations of chemical predictions, and increasing spatial resolution tends to improvemore » performance. Model bias and normalized root mean square values for precipitation predictions are relatively small, but there are significant differences when comparing modeled and observed probability density functions for precipitation in EC and YRD. Increasing model horizontal resolution tends to reduce model bias and error for precipitation predictions. The surface and column aerosol loading is maximized between about 32°N and 42°N in early to mid-May during the 2010 EASM, and then shifts north while decreasing in magnitude during July and August. Changing model resolution moderately changes the spatiotemporal relationships between aerosols, cloud properties, and precipitation during the EASM, thus demonstrating the importance of model grid resolution in simulating EASM circulation and rainfall patterns over EC and the YRD. In conclusion, results from this work demonstrate the capability and limitations in the aerosol, cloud, and precipitation representation of WRF-CAM5 for regional-scale applications down to relatively fine horizontal resolutions. Further WRF-CAM5 model development and application in this area is needed.« less

Evaluation of a multi-scale WRF-CAM5 simulation during the 2010 East Asian Summer Monsoon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, Patrick; Zhang, Yang; Wang, Kai

The Weather Research and Forecasting model with Chemistry (WRF-Chem) with the physics package of the Community Atmosphere Model Version 5 (CAM5) has been applied at multiple scales over Eastern China (EC) and the Yangtze River Delta (YRD) to evaluate how increased horizontal resolution with physics designed for a coarser resolution climate model impacts aerosols and clouds, and the resulting precipitation characteristics and performance during the 2010 East Asian Summer Monsoon (EASM). Despite large underpredictions in surface aerosol concentrations and aerosol optical depth, there is good spatial agreement with surface observations of chemical predictions, and increasing spatial resolution tends to improvemore » performance. Model bias and normalized root mean square values for precipitation predictions are relatively small, but there are significant differences when comparing modeled and observed probability density functions for precipitation in EC and YRD. Increasing model horizontal resolution tends to reduce model bias and error for precipitation predictions. The surface and column aerosol loading is maximized between about 32N and 42N in early to mid-May during the 2010 EASM, and then shifts north while decreasing in magnitude during July and August. Changing model resolution moderately changes the spatiotemporal relationships between aerosols, cloud properties, and precipitation during the EASM, thus demonstrating the importance of model grid resolution in simulating EASM circulation and rainfall patterns over EC and the YRD. Results from this work demonstrate the capability and limitations in the aerosol, cloud, and precipitation representation of WRF-CAM5 for regional-scale applications down to relatively fine horizontal resolutions. Further WRF-CAM5 model development and application in this area is needed.« less

Evaluation of a multi-scale WRF-CAM5 simulation during the 2010 East Asian Summer Monsoon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, Patrick; Zhang, Yang; Wang, Kai

The Weather Research and Forecasting model with Chemistry (WRF-Chem) with the physics package of the Community Atmosphere Model Version 5 (CAM5) has been applied at multiple scales over Eastern China (EC) and the Yangtze River Delta (YRD) to evaluate how increased horizontal resolution with physics designed for a coarser resolution climate model impacts aerosols and clouds, and the resulting precipitation characteristics and performance during the 2010 East Asian Summer Monsoon (EASM). Despite large underpredictions in surface aerosol concentrations and aerosol optical depth, there is good spatial agreement with surface observations of chemical predictions, and increasing spatial resolution tends to improvemore » performance. Model bias and normalized root mean square values for precipitation predictions are relatively small, but there are significant differences when comparing modeled and observed probability density functions for precipitation in EC and YRD. Increasing model horizontal resolution tends to reduce model bias and error for precipitation predictions. The surface and column aerosol loading is maximized between about 32°N and 42°N in early to mid-May during the 2010 EASM, and then shifts north while decreasing in magnitude during July and August. Changing model resolution moderately changes the spatiotemporal relationships between aerosols, cloud properties, and precipitation during the EASM, thus demonstrating the importance of model grid resolution in simulating EASM circulation and rainfall patterns over EC and the YRD. In conclusion, results from this work demonstrate the capability and limitations in the aerosol, cloud, and precipitation representation of WRF-CAM5 for regional-scale applications down to relatively fine horizontal resolutions. Further WRF-CAM5 model development and application in this area is needed.« less

The astrochemistry of H+3

NASA Astrophysics Data System (ADS)

Herbst, E.

2000-09-01

The reactions of the molecular ion H3+ are pivotal to the chemistry of dense interstellar clouds. Produced by the cosmic-ray ionizati on of molecular hydrogen, H3+ reacts with a variety of a toms and molecules to produce species that are precursors to many of the detect ed molecules in dense clouds. For example, the reaction of H3+ with atomic O leads, eventually, to the production of water, while the re action with HD leads to the production of a wide variety of deuterated isotopom ers. In this article, the chemistry of H3+ and the produc ts derived from it are discussed in the larger context of interstellar chemistr y.

Time scales for molecule formation by ion-molecule reactions

NASA Technical Reports Server (NTRS)

Langer, W. D.; Glassgold, A. E.

1976-01-01

Analytical solutions are obtained for nonlinear differential equations governing the time-dependence of molecular abundances in interstellar clouds. Three gas-phase reaction schemes are considered separately for the regions where each dominates. The particular case of CO, and closely related members of the Oh and CH families of molecules, is studied for given values of temperature, density, and the radiation field. Nonlinear effects and couplings with particular ions are found to be important. The time scales for CO formation range from 100,000 to a few million years, depending on the chemistry and regime. The time required for essentially complete conversion of C(+) to CO in the region where the H3(+) chemistry dominates is several million years. Because this time is longer than or comparable to dynamical time scales for dense interstellar clouds, steady-state abundances may not be observed in such clouds.

Phosphorus-bearing molecules in the Galactic Center

NASA Astrophysics Data System (ADS)

Rivilla, V. M.; Jiménez-Serra, I.; Zeng, S.; Martín, S.; Martín-Pintado, J.; Armijos-Abendaño, J.; Viti, S.; Aladro, R.; Riquelme, D.; Requena-Torres, M.; Quénard, D.; Fontani, F.; Beltrán, M. T.

2018-03-01

Phosphorus (P) is one of the essential elements for life due to its central role in biochemical processes. Recent searches have shown that P-bearing molecules (in particular PN and PO) are present in star-forming regions, although their formation routes remain poorly understood. In this letter, we report observations of PN and PO towards seven molecular clouds located in the Galactic Center, which are characterized by different types of chemistry. PN is detected in five out of seven sources, whose chemistry is thought to be shock-dominated. The two sources with PN non-detections correspond to clouds exposed to intense UV/X-rays/cosmic ray (CR) radiation. PO is detected only towards the cloud G+0.693-0.03, with a PO/PN abundance ratio of ˜1.5. We conclude that P-bearing molecules likely form in shocked gas as a result of dust grain sputtering, while are destroyed by intense UV/X-ray/CR radiation.

The interstellar N2 abundance towards HD 124314 from far-ultraviolet observations.

PubMed

Knauth, David C; Andersson, B-G; McCandliss, Stephan R; Moos, H Warren

2004-06-10

The abundance of interstellar molecular nitrogen (N2) is of considerable importance: models of steady-state gas-phase interstellar chemistry, together with millimetre-wavelength observations of interstellar N2H+ in dense molecular clouds predict that N2 should be the most abundant nitrogen-bearing molecule in the interstellar medium. Previous attempts to detect N2 absorption in the far-ultraviolet or infrared (ice features) have hitherto been unsuccessful. Here we report the detection of interstellar N2 at far-ultraviolet wavelengths towards the moderately reddened star HD 124314 in the constellation of Centaurus. The N2 column density is larger than expected from models of diffuse clouds and significantly smaller than expected for dense molecular clouds. Moreover, the N2 abundance does not explain the observed variations in the abundance of atomic nitrogen (N I) towards high-column-density sightlines, implying that the models of nitrogen chemistry in the interstellar medium are incomplete.

Interferometric observations of large biologically interesting interstellar and cometary molecules

PubMed Central

Snyder, Lewis E.

2006-01-01

Interferometric observations of high-mass regions in interstellar molecular clouds have revealed hot molecular cores that have substantial column densities of large, partly hydrogen-saturated molecules. Many of these molecules are of interest to biology and thus are labeled “biomolecules.” Because the clouds containing these molecules provide the material for star formation, they may provide insight into presolar nebular chemistry, and the biomolecules may provide information about the potential of the associated interstellar chemistry for seeding newly formed planets with prebiotic organic chemistry. In this overview, events are outlined that led to the current interferometric array observations. Clues that connect this interstellar hot core chemistry to the solar system can be found in the cometary detection of methyl formate and the interferometric maps of cometary methanol. Major obstacles to understanding hot core chemistry remain because chemical models are not well developed and interferometric observations have not been very sensitive. Differentiation in the molecular isomers glycolaldehdye, methyl formate, and acetic acid has been observed, but not explained. The extended source structure for certain sugars, aldehydes, and alcohols may require nonthermal formation mechanisms such as shock heating of grains. Major advances in understanding the formation chemistry of hot core species can come from observations with the next generation of sensitive, high-resolution arrays. PMID:16894168

In situ observations of Arctic cloud properties across the Beaufort Sea marginal ice zone

NASA Astrophysics Data System (ADS)

Corr, C.; Moore, R.; Winstead, E.; Thornhill, K. L., II; Crosbie, E.; Ziemba, L. D.; Beyersdorf, A. J.; Chen, G.; Martin, R.; Shook, M.; Corbett, J.; Smith, W. L., Jr.; Anderson, B. E.

2016-12-01

Clouds play an important role in Arctic climate. This is particularly true over the Arctic Ocean where feedbacks between clouds and sea-ice impact the surface radiation budget through modifications of sea-ice extent, ice thickness, cloud base height, and cloud cover. This work summarizes measurements of Arctic cloud properties made aboard the NASA C-130 aircraft over the Beaufort Sea during ARISE (Arctic Radiation - IceBridge Sea&Ice Experiment) in September 2014. The influence of surface-type on cloud properties is also investigated. Specifically, liquid water content (LWC), droplet concentrations, and droplet size distributions are compared for clouds sampled over three distinct regimes in the Beaufort Sea: 1) open water, 2) the marginal ice zone, and 3) sea-ice. Regardless of surface type, nearly all clouds intercepted during ARISE were liquid-phase clouds. However, differences in droplet size distributions and concentrations were evident for the surface types; clouds over the MIZ and sea-ice generally had fewer and larger droplets compared to those over open water. The potential implication these results have for understanding cloud-surface albedo climate feedbacks in Arctic are discussed.

A Climatology of Surface Cloud Radiative Effects at the ARM Tropical Western Pacific Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

McFarlane, Sally A.; Long, Charles N.; Flaherty, Julia E.

Cloud radiative effects on surface downwelling fluxes are investigated using long-term datasets from the three Atmospheric Radiation Measurement (ARM) sites in the Tropical Western Pacific (TWP) region. The Nauru and Darwin sites show significant variability in sky cover, downwelling radiative fluxes, and surface cloud radiative effect (CRE) due to El Niño and the Australian monsoon, respectively, while the Manus site shows little intra-seasonal or interannual variability. Cloud radar measurement of cloud base and top heights are used to define cloud types so that the effect of cloud type on the surface CRE can be examined. Clouds with low bases contributemore » 71-75% of the surface shortwave (SW) CRE and 66-74% of the surface longwave (LW) CRE at the three TWP sites, while clouds with mid-level bases contribute 8-9% of the SW CRE and 12-14% of the LW CRE, and clouds with high bases contribute 16-19% of the SW CRE and 15-21% of the LW CRE.« less

Clouds and Water Vapor in the Climate System and Radiative Transfer in Clear Air and Cirrus Clouds in the Tropics

NASA Technical Reports Server (NTRS)

Anderson, James G.; DeSouza-Machado, Sergio; Strow, L. Larrabee

2002-01-01

Research supported under this grant was aimed at attacking unanswered scientific questions that lie at the intersection of radiation, dynamics, chemistry, and climate. Considerable emphasis was placed on scientific collaboration and the innovative development of instruments required to address these issues. Specific questions include water vapor distribution in the tropical troposphere, atmospheric radiation, thin cirrus clouds, stratosphere-troposphere exchange, and correlative science with satellite observations.

Cloud and boundary layer interactions over the Arctic sea-ice in late summer

NASA Astrophysics Data System (ADS)

Shupe, M. D.; Persson, P. O. G.; Brooks, I. M.; Tjernström, M.; Sedlar, J.; Mauritsen, T.; Sjogren, S.; Leck, C.

2013-05-01

Observations from the Arctic Summer Cloud Ocean Study (ASCOS), in the central Arctic sea-ice pack in late summer 2008, provide a detailed view of cloud-atmosphere-surface interactions and vertical mixing processes over the sea-ice environment. Measurements from a suite of ground-based remote sensors, near surface meteorological and aerosol instruments, and profiles from radiosondes and a helicopter are combined to characterize a week-long period dominated by low-level, mixed-phase, stratocumulus clouds. Detailed case studies and statistical analyses are used to develop a conceptual model for the cloud and atmosphere structure and their interactions in this environment. Clouds were persistent during the period of study, having qualities that suggest they were sustained through a combination of advective influences and in-cloud processes, with little contribution from the surface. Radiative cooling near cloud top produced buoyancy-driven, turbulent eddies that contributed to cloud formation and created a cloud-driven mixed layer. The depth of this mixed layer was related to the amount of turbulence and condensed cloud water. Coupling of this cloud-driven mixed layer to the surface boundary layer was primarily determined by proximity. For 75% of the period of study, the primary stratocumulus cloud-driven mixed layer was decoupled from the surface and typically at a warmer potential temperature. Since the near-surface temperature was constrained by the ocean-ice mixture, warm temperatures aloft suggest that these air masses had not significantly interacted with the sea-ice surface. Instead, back trajectory analyses suggest that these warm airmasses advected into the central Arctic Basin from lower latitudes. Moisture and aerosol particles likely accompanied these airmasses, providing necessary support for cloud formation. On the occasions when cloud-surface coupling did occur, back trajectories indicated that these air masses advected at low levels, while mixing processes kept the mixed layer in equilibrium with the near-surface environment. Rather than contributing buoyancy forcing for the mixed-layer dynamics, the surface instead simply appeared to respond to the mixed-layer processes aloft. Clouds in these cases often contained slightly higher condensed water amounts, potentially due to additional moisture sources from below.

Cloud and boundary layer interactions over the Arctic sea ice in late summer

NASA Astrophysics Data System (ADS)

Shupe, M. D.; Persson, P. O. G.; Brooks, I. M.; Tjernström, M.; Sedlar, J.; Mauritsen, T.; Sjogren, S.; Leck, C.

2013-09-01

Observations from the Arctic Summer Cloud Ocean Study (ASCOS), in the central Arctic sea-ice pack in late summer 2008, provide a detailed view of cloud-atmosphere-surface interactions and vertical mixing processes over the sea-ice environment. Measurements from a suite of ground-based remote sensors, near-surface meteorological and aerosol instruments, and profiles from radiosondes and a helicopter are combined to characterize a week-long period dominated by low-level, mixed-phase, stratocumulus clouds. Detailed case studies and statistical analyses are used to develop a conceptual model for the cloud and atmosphere structure and their interactions in this environment. Clouds were persistent during the period of study, having qualities that suggest they were sustained through a combination of advective influences and in-cloud processes, with little contribution from the surface. Radiative cooling near cloud top produced buoyancy-driven, turbulent eddies that contributed to cloud formation and created a cloud-driven mixed layer. The depth of this mixed layer was related to the amount of turbulence and condensed cloud water. Coupling of this cloud-driven mixed layer to the surface boundary layer was primarily determined by proximity. For 75% of the period of study, the primary stratocumulus cloud-driven mixed layer was decoupled from the surface and typically at a warmer potential temperature. Since the near-surface temperature was constrained by the ocean-ice mixture, warm temperatures aloft suggest that these air masses had not significantly interacted with the sea-ice surface. Instead, back-trajectory analyses suggest that these warm air masses advected into the central Arctic Basin from lower latitudes. Moisture and aerosol particles likely accompanied these air masses, providing necessary support for cloud formation. On the occasions when cloud-surface coupling did occur, back trajectories indicated that these air masses advected at low levels, while mixing processes kept the mixed layer in equilibrium with the near-surface environment. Rather than contributing buoyancy forcing for the mixed-layer dynamics, the surface instead simply appeared to respond to the mixed-layer processes aloft. Clouds in these cases often contained slightly higher condensed water amounts, potentially due to additional moisture sources from below.

In-cloud oxalate formation in the global troposphere: a 3-D modeling study

NASA Astrophysics Data System (ADS)

Myriokefalitakis, S.; Tsigaridis, K.; Mihalopoulos, N.; Sciare, J.; Nenes, A.; Kawamura, K.; Segers, A.; Kanakidou, M.

2011-06-01

Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21-37 Tg yr-1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2-0.3 Tg, i.e. 0.05-0.1 Tg-C that is about 5-9 % of model-calculated water soluble organic carbon burden.

Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface

PubMed Central

2016-01-01

Interfaces are ubiquitous in the environment and many atmospheric key processes, such as gas deposition, aerosol, and cloud formation are, at one stage or another, strongly impacted by physical and chemical processes occurring at interfaces. Here, the photoinduced chemistry of an air/water interface coated with nonanoic acid—a fatty acid surfactant we use as a proxy for chemically complex natural aqueous surface microlayers—was investigated as a source of volatile and semivolatile reactive organic species. The carboxylic acid coating significantly increased the propensity of photosensitizers, chosen to mimic those observed in real environmental waters, to partition to the interface and enhance reactivity there. Photochemical formation of functionalized and unsaturated compounds was systematically observed upon irradiation of these coated surfaces. The role of a coated interface appears to be critical in providing a concentrated medium allowing radical–radical reactions to occur in parallel with molecular oxygen additions. Mechanistic insights are provided from extensive analysis of products observed in both gas and aqueous phases by online switchable reagent ion-time of flight-mass spectrometry and by off-line ultraperformance liquid chromatography coupled to a Q Exactive high resolution mass spectrometer through heated electrospray ionization, respectively. PMID:27611489

Measurement Comparisons Towards Improving the Understanding of Aerosol-Cloud Processing

NASA Astrophysics Data System (ADS)

Noble, Stephen R.

Cloud processing of aerosol is an aerosol-cloud interaction that is not heavily researched but could have implications on climate. The three types of cloud processing are chemical processing, collision and coalescence processing, and Brownian capture of interstitial particles. All types improve cloud condensation nuclei (CCN) in size or hygroscopicity (kappa). These improved CCN affect subsequent clouds. This dissertation focuses on measurement comparisons to improve our observations and understanding of aerosol-cloud processing. Particle size distributions measured at the continental Southern Great Plains (SGP) site were compared with ground based measurements of cloud fraction (CF) and cloud base altitude (CBA). Particle size distributions were described by a new objective shape parameter to define bimodality rather than an old subjective one. Cloudy conditions at SGP were found to be correlated with lagged shape parameter. Horizontal wind speed and regional CF explained 42%+ of this lag time. Many of these surface particle size distributions were influenced by aerosol-cloud processing. Thus, cloud processing may be more widespread with more implications than previously thought. Particle size distributions measured during two aircraft field campaigns (MArine Stratus/stratocumulus Experiment; MASE; and Ice in Cloud Experiment-Tropical; ICE-T) were compared to CCN distributions. Tuning particle size to critical supersaturation revealed hygroscopicity expressed as ? when the distributions were overlain. Distributions near cumulus clouds (ICE-T) had a higher frequency of the same ?s (48% in ICE-T to 42% in MASE) between the accumulation (processed) and Aitken (unprocessed) modes. This suggested physical processing domination in ICE-T. More MASE (stratus cloud) kappa differences between modes pointed to chemical cloud processing. Chemistry measurements made in MASE showed increases in sulfates and nitrates with distributions that were more processed. This supported chemical cloud processing in MASE. This new method to determine kappa provides the needed information without interrupting ambient measurements. MODIS derived cloud optical thickness (COT), cloud liquid water path (LWP), and cloud effective radius (re) were compared to the same in situ derived variables from cloud probe measurements of two stratus/stratocumulus cloud campaigns (MASE and Physics Of Stratocumulus Tops; POST). In situ data were from complete vertical cloud penetrations, while MODIS data were from pixels along the aircraft penetration path. Comparisons were well correlated except that MODIS LWP (14-36%) and re (20-30%) were biased high. The LWP bias was from re bias and was not improved by using the vertically stratified assumption. MODIS re bias was almost removed when compared to cloud top maximum in situ re, but, that does not describe re for the full depth of the cloud. COT is validated by in situ COT. High correlations suggest that MODIS variables are useful in self-comparisons such as gradient changes in stratus cloud re during aerosol-cloud processing.

Heterogeneous Ice Nucleation by Soufriere Hills Volcanic Ash Immersed in Water Droplets.

PubMed

Mangan, T P; Atkinson, J D; Neuberg, J W; O'Sullivan, D; Wilson, T W; Whale, T F; Neve, L; Umo, N S; Malkin, T L; Murray, B J

2017-01-01

Fine particles of ash emitted during volcanic eruptions may sporadically influence cloud properties on a regional or global scale as well as influencing the dynamics of volcanic clouds and the subsequent dispersion of volcanic aerosol and gases. It has been shown that volcanic ash can trigger ice nucleation, but ash from relatively few volcanoes has been studied for its ice nucleating ability. In this study we quantify the efficiency with which ash from the Soufriere Hills volcano on Montserrat nucleates ice when immersed in supercooled water droplets. Using an ash sample from the 11th February 2010 eruption, we report ice nucleating efficiencies from 246 to 265 K. This wide range of temperatures was achieved using two separate droplet freezing instruments, one employing nanolitre droplets, the other using microlitre droplets. Soufriere Hills volcanic ash was significantly more efficient than all other ash samples that have been previously examined. At present the reasons for these differences are not understood, but may be related to mineralogy, amorphous content and surface chemistry.

Heterogeneous Ice Nucleation by Soufriere Hills Volcanic Ash Immersed in Water Droplets

PubMed Central

Atkinson, J. D.; Neuberg, J. W.; O’Sullivan, D.; Wilson, T. W.; Whale, T. F.; Neve, L.; Umo, N. S.; Malkin, T. L.; Murray, B. J.

2017-01-01

Fine particles of ash emitted during volcanic eruptions may sporadically influence cloud properties on a regional or global scale as well as influencing the dynamics of volcanic clouds and the subsequent dispersion of volcanic aerosol and gases. It has been shown that volcanic ash can trigger ice nucleation, but ash from relatively few volcanoes has been studied for its ice nucleating ability. In this study we quantify the efficiency with which ash from the Soufriere Hills volcano on Montserrat nucleates ice when immersed in supercooled water droplets. Using an ash sample from the 11th February 2010 eruption, we report ice nucleating efficiencies from 246 to 265 K. This wide range of temperatures was achieved using two separate droplet freezing instruments, one employing nanolitre droplets, the other using microlitre droplets. Soufriere Hills volcanic ash was significantly more efficient than all other ash samples that have been previously examined. At present the reasons for these differences are not understood, but may be related to mineralogy, amorphous content and surface chemistry. PMID:28056077

Solute deposition from cloud water to the canopy of a puerto rican montane forest

NASA Astrophysics Data System (ADS)

Asbury, Clyde E.; McDowell, William H.; Trinidad-Pizarro, Roberto; Berrios, Samuel

Deposition of cloud water and dissolved solutes onto vegetation was studied by sampling clouds, throughfall and stemflow during 12 cloud-only events at Pico Del Este, a tropical cloud forest in the Luquillo Mountains of Puerto Rico. Liquid water content of the sampled clouds was low (0.016 g m -3), but deposition of water (1.3 mm d -1)was comparable to other sites, apparently due to efficient capture of clouds by epiphyte-laden vegetation. Elemental deposition by cloud water was similar to that in other, more polluted sites, but was only 8-30% of total deposition (cloud-only plus rain) due to the high rainfall at the site (approximately 5 m). Na and CI from marine aerosols dominated cloud chemistry, with concentrations of 400 μeqδ -1. Sulfate and nitrate concentrations were 180 and 60 μedδ -1, respectively. After passage through the canopy, concentrations of base cations in deposited cloud water increased, and concentrations of nitrogen decreased.

Surface tension and quasi-emulsion of cavitation bubble cloud.

PubMed

Bai, Lixin; Chen, Xiaoguang; Zhu, Gang; Xu, Weilin; Lin, Weijun; Wu, Pengfei; Li, Chao; Xu, Delong; Yan, Jiuchun

2017-03-01

A quasi-emulsion phenomenon of cavitation structure in a thin liquid layer (the thin liquid layer is trapped between a radiating surface and a hard reflector) is investigated experimentally with high-speed photography. The transformation from cloud-in-water (c/w) emulsion to water-in-cloud (w/c) emulsion is related to the increase of cavitation bubble cloud. The acoustic field in the thin liquid layer is analyzed. It is found that the liquid region has higher acoustic pressure than the cloud region. The bubbles are pushed from liquid region to cloud region by the primary Bjerknes forces. The rate of change of CSF increased with the increase of CSF. The cavitation bubbles on the surface of cavitation cloud are attracted by the cavitation bubbles inside the cloud due to secondary Bjerknes forces. The existence of surface tension on the interface of liquid region and cloud region is proved. The formation mechanism of disc-shaped liquid region and cloud region are analysed by surface tension and incompressibility of cavitation bubble cloud. Copyright © 2016 Elsevier B.V. All rights reserved.

Insights Into Atmospheric Aqueous Organic Chemistry Through Controlled Experiments with Cloud Water Surrogates

NASA Astrophysics Data System (ADS)

Turpin, B. J.; Ramos, A.; Kirkland, J. R.; Lim, Y. B.; Seitzinger, S.

2011-12-01

There is considerable laboratory and field-based evidence that chemical processing in clouds and wet aerosols alters organic composition and contributes to the formation of secondary organic aerosol (SOA). Single-compound laboratory experiments have played an important role in developing aqueous-phase chemical mechanisms that aid prediction of SOA formation through multiphase chemistry. In this work we conduct similar experiments with cloud/fog water surrogates, to 1) evaluate to what extent the previously studied chemistry is observed in these more realistic atmospheric waters, and 2) to identify additional atmospherically-relevant precursors and products that require further study. We used filtered Camden and Pinelands, NJ rainwater as a surrogate for cloud water. OH radical (~10-12 M) was formed by photolysis of hydrogen peroxide and samples were analyzed in real-time by electrospray ionization mass spectroscopy (ESI-MS). Discrete samples were also analyzed by ion chromatography (IC) and ESI-MS after IC separation. All experiments were performed in duplicate. Standards of glyoxal, methylglyoxal and glycolaldehyde and their major aqueous oxidation products were also analyzed, and control experiments performed. Decreases in the ion abundance of many positive mode compounds and increases in the ion abundance of many negative mode compounds (e.g., organic acids) suggest that precursors are predominantly aldehydes, organic peroxides and/or alcohols. Real-time ESI mass spectra were consistent with the expected loss of methylglyoxal and subsequent formation of pyruvate, glyoxylate, and oxalate. New insights regarding other potential precursors and products will be provided.

Water in dense molecular clouds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wannier, P.G.; Kuiper, T.B.H.; Frerking, M.A.

1991-08-01

The G.P. Kuiper Airborne Observatory (KAO) was used to make initial observations of the half-millimeter ground-state transition of water in seven giant molecular clouds and in two late-type stars. No significant detections were made, and the resulting upper limits are significantly below those expected from other, indirect observations and from several theoretical models. The implied interstellar H2O/CO abundance is less than 0.003 in the cores of three giant molecular clouds. This value is less than expected from cloud chemistry models and also than estimates based on HDO and H3O(+) observations. 78 refs.

Hot electrons and radial transport in Saturn's inner magetosphere: Modeling the effects on ion chemistry

NASA Astrophysics Data System (ADS)

Fleshman, Bobby L.

The E-ring of Saturn, located just beyond the main rings at four Saturn radii, was known to be made mostly of water and its by-products before the Cassini spacecraft arrived at Saturn in 2005. Since then, Cassini has observed water geysers on the tiny moon of Enceladus ejecting ≈ 100 kg of water per second into orbit around Saturn, which most agree is the chief contributor to neutrals in the E-ring. Following several key reactions, many of these neutrals go on to populate large, tenuous structures, known as neutral clouds, extending 10s of Saturn radii. The other side of the story are the ions, which are largely created by the ionization of same neutrals sourced from Enceladus. A key distinction between the neutrals and ions is that ions are carried along by Saturn's magnetic field, and revolve around Saturn at the rotation rate of the planet, while neutrals generally have much slower Keplerian speeds. It is the study of the chemical interaction of these separate, but related populations that is the subject of this thesis. We have developed a series of models to study how the coupling of these systems affect details of the other, such as composition. The first step (Chapter 2) was the development of a water-group physical chemistry model, which includes suprathermal electrons and the effect of radial ion transport. With this "one-box" model, we are able to reproduce observed water and hydrogen ion densities in Enceladus's orbit, but only when the hot electron density is ≈ 0.5% of the total plasma density. Radial transport is found to be slow, requiring 26 days to remove ions from the orbit of Enceladus. Moving toward the development of a radial model of ion chemistry, in Chapter 4 we present a model of Saturn's neutral clouds, which are made of material outgassing from Enceladus. The effects of dissociation and charge exchange are considered, where the details of the latter prove to be of great consequence on neutral cloud morphology. The oxygen cloud is found to the most extended, followed by H2O, and finally OH. The above efforts are combined in Chapter 5, where a neutral cloud model is used to construct a radial model of ion chemistry. It is shown that neutral H2O requires more spreading than yet modeled in order to recover observed water and hydrogen ion abundances near Enceladus. The relative abundance of water-group ion species presented will be useful for analyses of CAPS-IMS data, while loss rates derived from the model can be used to improve neutral cloud models. The case is made that ion chemistry models and neutral cloud models must be developed alongside one another in order to improve understanding of these interrelated populations at Saturn.

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James H.; Considine, David B.; Platnick, Steven; Norris, Peter M.; Duncan, Bryan N.; Pierce, Robert B.; Chen, Gao; Yantosca, Robert M.

2009-01-01

Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH3 concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the ultraviolet wavelengths.

Locally driven interannual variability of near-surface pH and ΩA in the Strait of Georgia

NASA Astrophysics Data System (ADS)

Moore-Maley, Ben L.; Allen, Susan E.; Ianson, Debby

2016-03-01

Declines in mean ocean pH and aragonite saturation state (ΩA) driven by anthropogenic CO2 emissions have raised concerns regarding the trends of pH and ΩA in estuaries. Low pH and ΩA can be harmful to a variety of marine organisms, especially those with calcium carbonate shells, and so may threaten the productive ecosystems and commercial fisheries found in many estuarine environments. The Strait of Georgia is a large, temperate, productive estuarine system with numerous wild and aquaculture shellfish and finfish populations. We determine the seasonality and variability of near-surface pH and ΩA in the Strait using a one-dimensional, biophysical, mixing layer model. We further evaluate the sensitivity of these quantities to local wind, freshwater, and cloud forcing by running the model over a wide range of scenarios using 12 years of observations. Near-surface pH and ΩA demonstrate strong seasonal cycles characterized by low pH, aragonite-undersaturated waters in winter and high pH, aragonite-supersaturated waters in summer. The aragonite saturation horizon generally lies at ˜20 m depth except in winter and during strong Fraser River freshets when it shoals to the surface. Periods of strong interannual variability in pH and aragonite saturation horizon depth arise in spring and summer. We determine that at different times of year, each of wind speed, freshwater flux, and cloud fraction are the dominant drivers of this variability. These results establish the mechanisms behind the emerging observations of highly variable near-surface carbonate chemistry in the Strait.

10-Year Observations of Cloud and Surface Longwave Radiation at Ny-Ålesund, Svalbard

NASA Astrophysics Data System (ADS)

Yeo, H.; Kim, S. W.; Kim, B. M.; Kim, J. H.; Shiobara, M.; Choi, T. J.; Son, S. W.; Kim, M. H.; Jeong, J. H.; Kim, S. J.

2015-12-01

Arctic clouds play a key role in surface radiation budget and may influence sea ice and snow melting. In this study, 10-year (2004-2013) observations of cloud from Micro-Pulse Lidar (MPL) and surface longwave (LW) radiation at Ny-Ålesund, Svalbard are analyzed to investigate cloud radiative effect. The cloud fraction (CF) derived from MPL shows distinct monthly variation, having higher CF (0.90) in summer and lower CF (0.79) in winter. Downward longwave radiation (DLW) during wintertime (Nov., Dec., Jan., and Feb.) decreases as cloud base height (CBH) increases. The DLW for CBH < 1km (264.7±35.4 W m-2) is approximately 1.46 times larger than that for cloud-free (181.8±25.8 W m-2) conditions. The temperature difference (ΔT) and DLW difference (ΔDLW), which are calculated as the difference of monthly mean temperature and DLW between all-sky and cloud-free conditions, are positively correlated (R2 = 0.83). This implies that an increase of DLW may influence surface warming, which can result in snow and sea ice melting. However, dramatic changes in surface temperature, cloud and DLW are observed with a time scale of a few days. The averaged surface temperature on the presence of low-level clouds (CBH < 2km) and under cloud-free conditions are estimated to be -6.9±6.1°C and -14.5±5.7°C, respectively. The duration of low-level clouds, showing relatively high DLW and high surface temperature, is about 2.5 days. This suggests that DLW induced by low-level clouds may not have a critical effect on surface temperature rising and sea ice melting.

Deuteration of ammonia in the starless core Ophiuchus/H-MM1

NASA Astrophysics Data System (ADS)

Harju, J.; Daniel, F.; Sipilä, O.; Caselli, P.; Pineda, J. E.; Friesen, R. K.; Punanova, A.; Güsten, R.; Wiesenfeld, L.; Myers, P. C.; Faure, A.; Hily-Blant, P.; Rist, C.; Rosolowsky, E.; Schlemmer, S.; Shirley, Y. L.

2017-04-01

Context. Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. The time-dependence of deuterium fractionation and the relative abundances of different nuclear spin modifications are supposed to provide a means of determining the evolutionary stages of these objects. Aims: We aim to test the current understanding of spin-state chemistry of deuterated species by determining the abundances and spin ratios of NH2D, NHD2 and ND3 in a quiescent, dense cloud. Methods: Spectral lines of NH3, NH2D, NHD2, ND3 and N2D+ were observed towards a dense, starless core in Ophiuchus with the APEX, GBT and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia and their deuterated forms. Different desorption schemes can be considered. Results: High deuterium fractionation ratios with NH2D/NH3 0.4, NHD2/ NH2D 0.2 and ND3/ NHD2 0.06 are found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but consistently predicts too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N2 on grain surfaces. Conclusions: The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of ammonia changes with physical conditions and time, the nuclear spin ratios of ammonia isotopologues do not probe the evolutionary stage of a cloud. Based on observations carried out with The Atacama Pathfinder Experiment (APEX), the Robert C. Byrd Green Bank Telescope (GBT), and the IRAM 30 m Telescope. APEX is a collaboration between Max-Planck Institut für Radioastronomie (MPIfR), Onsala Space Observatory (OSO), and the European Southern Observatory (ESO). GBT is managed by the National Radio Astronomy Observatory, which is a facility of the National Science Foundation operated under cooperative agreement by Associated Universities, Inc. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).

Interaction of acidic trace gases with ice from a surface science perspective

NASA Astrophysics Data System (ADS)

Waldner, A.; Kong, X.; Ammann, M.; Orlando, F.; Birrer, M.; Artiglia, L.; Bartels-Rausch, T.

2016-12-01

Acidic trace gases, such as HCOOH, HCl and HONO, play important roles in atmospheric chemistry. The presence of ice is known to have the capability to modify this chemistry (Neu et al. 2012). The molecular level processes of the interaction of acidic trace gases with ice are still a matter of debate and a quantification of the uptake is difficult (Dash et al. 2006, Bartels-Rausch et al. 2014, Huthwelker et al. 2006). This hampers a proper inclusion of ice as a substrate in models of various scales as for example in global chemistry climate models that would among others allow predicting large-scale effects of ice clouds. So far, direct observations of the ice surface and of the interaction with trace gases at temperatures and concentrations relevant to the environment are very limited. In this study, we take advantage of the surface and analytical sensitivity as well as the chemical selectivity of photoemission and absorption spectroscopy performed at ambient pressure using the near ambient pressure photoemission endstation (NAPP) at Swiss Light Source to overcome this limitation in environmental science (Orlando et al. 2016). Specifically, ambient pressure X-ray Photoelectron Spectroscopy (XPS) allows us to get information about chemical state and concentration depth profiles of dopants. The combination of XPS with auger electron yield Near-Edge X-ray Absorption Fine Structure (NEXAFS) enables us to locate the dopant and analyse wheather the interaction leads to enhanced surface disorder and to what extent different disorders influences the uptake of the trace gas. For the first time, this study looks directly at the interaction of HCOOH, the strongest organic acid, with ice at 2 different temperatures (233 and 253 K) relevant for environmental science by means of electron spectroscopy. XPS depth profiles indicate that the HCOOH basically remains within the topmost ice layers and O K-edge NEXAFS analysis show that the interaction ice-HCOOH does not lead to enhanced surface disorder at environmentally relevant conditions.

West Antarctic Ice Sheet cloud cover and surface radiation budget from NASA A-Train satellites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, Ryan C.; Lubin, Dan; Vogelmann, Andrew M.

Clouds are an essential parameter of the surface energy budget influencing the West Antarctic Ice Sheet (WAIS) response to atmospheric warming and net contribution to global sea-level rise. A four-year record of NASA A-Train cloud observations is combined with surface radiation measurements to quantify the WAIS radiation budget and constrain the three-dimensional occurrence frequency, thermodynamic phase partitioning, and surface radiative effect of clouds over West Antarctica (WA). The skill of satellite-modeled radiative fluxes is confirmed through evaluation against measurements at four Antarctic sites (WAIS Divide Ice Camp, Neumayer, Syowa, and Concordia Stations). And due to perennial high-albedo snow and icemore » cover, cloud infrared emission dominates over cloud solar reflection/absorption leading to a positive net all-wave cloud radiative effect (CRE) at the surface, with all monthly means and 99.15% of instantaneous CRE values exceeding zero. The annual-mean CRE at theWAIS surface is 34 W m -2, representing a significant cloud-induced warming of the ice sheet. Low-level liquid-containing clouds, including thin liquid water clouds implicated in radiative contributions to surface melting, are widespread and most frequent in WA during the austral summer. Clouds warm the WAIS by 26 W m -2, in summer, on average, despite maximum offsetting shortwave CRE. Glaciated cloud systems are strongly linked to orographic forcing, with maximum incidence on the WAIS continuing downstream along the Transantarctic Mountains.« less

West Antarctic Ice Sheet cloud cover and surface radiation budget from NASA A-Train satellites

DOE PAGES

Scott, Ryan C.; Lubin, Dan; Vogelmann, Andrew M.; ...

2017-04-26

Clouds are an essential parameter of the surface energy budget influencing the West Antarctic Ice Sheet (WAIS) response to atmospheric warming and net contribution to global sea-level rise. A four-year record of NASA A-Train cloud observations is combined with surface radiation measurements to quantify the WAIS radiation budget and constrain the three-dimensional occurrence frequency, thermodynamic phase partitioning, and surface radiative effect of clouds over West Antarctica (WA). The skill of satellite-modeled radiative fluxes is confirmed through evaluation against measurements at four Antarctic sites (WAIS Divide Ice Camp, Neumayer, Syowa, and Concordia Stations). And due to perennial high-albedo snow and icemore » cover, cloud infrared emission dominates over cloud solar reflection/absorption leading to a positive net all-wave cloud radiative effect (CRE) at the surface, with all monthly means and 99.15% of instantaneous CRE values exceeding zero. The annual-mean CRE at theWAIS surface is 34 W m -2, representing a significant cloud-induced warming of the ice sheet. Low-level liquid-containing clouds, including thin liquid water clouds implicated in radiative contributions to surface melting, are widespread and most frequent in WA during the austral summer. Clouds warm the WAIS by 26 W m -2, in summer, on average, despite maximum offsetting shortwave CRE. Glaciated cloud systems are strongly linked to orographic forcing, with maximum incidence on the WAIS continuing downstream along the Transantarctic Mountains.« less

Improvements of top-of-atmosphere and surface irradiance computations with CALIPSO-, CloudSat-, and MODIS-derived cloud and aerosol properties

NASA Astrophysics Data System (ADS)

Kato, Seiji; Rose, Fred G.; Sun-Mack, Sunny; Miller, Walter F.; Chen, Yan; Rutan, David A.; Stephens, Graeme L.; Loeb, Norman G.; Minnis, Patrick; Wielicki, Bruce A.; Winker, David M.; Charlock, Thomas P.; Stackhouse, Paul W., Jr.; Xu, Kuan-Man; Collins, William D.

2011-10-01

One year of instantaneous top-of-atmosphere (TOA) and surface shortwave and longwave irradiances are computed using cloud and aerosol properties derived from instruments on the A-Train Constellation: the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) on the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite, the CloudSat Cloud Profiling Radar (CPR), and the Aqua Moderate Resolution Imaging Spectrometer (MODIS). When modeled irradiances are compared with those computed with cloud properties derived from MODIS radiances by a Clouds and the Earth's Radiant Energy System (CERES) cloud algorithm, the global and annual mean of modeled instantaneous TOA irradiances decreases by 12.5 W m-2 (5.0%) for reflected shortwave and 2.5 W m-2 (1.1%) for longwave irradiances. As a result, the global annual mean of instantaneous TOA irradiances agrees better with CERES-derived irradiances to within 0.5W m-2 (out of 237.8 W m-2) for reflected shortwave and 2.6W m-2 (out of 240.1 W m-2) for longwave irradiances. In addition, the global annual mean of instantaneous surface downward longwave irradiances increases by 3.6 W m-2 (1.0%) when CALIOP- and CPR-derived cloud properties are used. The global annual mean of instantaneous surface downward shortwave irradiances also increases by 8.6 W m-2 (1.6%), indicating that the net surface irradiance increases when CALIOP- and CPR-derived cloud properties are used. Increasing the surface downward longwave irradiance is caused by larger cloud fractions (the global annual mean by 0.11, 0.04 excluding clouds with optical thickness less than 0.3) and lower cloud base heights (the global annual mean by 1.6 km). The increase of the surface downward longwave irradiance in the Arctic exceeds 10 W m-2 (˜4%) in winter because CALIOP and CPR detect more clouds in comparison with the cloud detection by the CERES cloud algorithm during polar night. The global annual mean surface downward longwave irradiance of 345.4 W m-2 is estimated by combining the modeled instantaneous surface longwave irradiance computed with CALIOP and CPR cloud profiles with the global annual mean longwave irradiance from the CERES product (AVG), which includes the diurnal variation of the irradiance. The estimated bias error is -1.5 W m-2 and the uncertainty is 6.9 W m-2. The uncertainty is predominately caused by the near-surface temperature and column water vapor amount uncertainties.

Exploring the Production of NOx by Lightning and Its Impact on Tropospheric Ozone

NASA Technical Reports Server (NTRS)

Gillani, Noor; Koshak, William; Biazar, Arastoo; Doty, Kevin; Mahon, Robert; Newchurch, Michael; Byun, Daewon; Emmons, Louisa

2006-01-01

Our quantitative understanding of free tropospheric (FT) chemistry is quite poor. State-of-the-art regional air quality models (e.g., US EPA's CMAQ) perform very poorly in simulating FT chemistry, with Uniform ozone around 70 ppb throughout the FT in summer, while ozonesonde data show much higher levels of ozone and much spatial-temporal structure. Such models completely neglect lightning-NOx (LNOx) emissions (the most significant source of NOx in the FT), and also contain large uncertainties in the specifications of intercontinental transport, stratosphere-troposphere exchange (STE) and PBLFT exchange (PFTE). Global air chemistry models include LNOx, but in very crude fashion, with the frequency and distribution of lightning being based on modeled cloud parameters (hence large uncertainty), lightning energetics being assumed to be constant for all flashes (literature value, while in reality there is at least a two-orders of magnitude variability from flash-to-flash), and the production of NOx in the surrounding heated air, per Joule of heating, being assumed to be constant also (literature value, while in fact it is a non-linear function of the dissipated heat and local air density, p). This situation is commonly blamed on paucity of pertinent observational data, but for the USA, there is now a wealth of surface- and satellite-based data of lightning available to permit much improved observation-based estimation of LNOx emissions. In the FT, such NOx has a long residence time, and also the ozone production efficiency from NOx there is considerably higher than in the PBL. It is, therefore, of critical importance in FT chemistry. This paper will describe the approach and data products of an ongoing NSSTC project aimed at a much-improved quantification of not only LNOx production on the scale of continental USA based on local and regional lightning observations, but also of intercontinental transport, STE and PFTE, all in upgraded simulations of tropospheric transport and chemistry. In our approach for LNOx, (a) we utilize continuous observed lightning information from the NLDN ground network and from satellite imagers (OTD and LIS) to quantify lightning frequency and distribution at the spatial-temporal scales of models such as CMAQ; (b) we develop new methodologies to quantify flash-specific lightning energy dissipation as heat (epsilon) using data from the research-grade lightning measurement facility at NASA-KSC, and to parameterize epsilon based on regional lightning monitoring data (ground- and satellite-based); and, (c) we develop a new parameterization of NOx production as a function of epsilon and rho. Based on such observation-based information, we are working to develop a gridded, episodic LNOx emissions inventory for the USA for use in models like CMAQ. We are also developing approaches for global(MOZART)- regional(CMAQ) chemistry coupling to improve intercontinental transport and STE. Finally, we are developing new methodologies for assimilation of satellite-observed (GOES) clouds into meteorological modeling (MM5), to improve PFTE and to optimize co-location of cloud convection and observed lightning. We will incorporate these improvements in CMAQ simulations over the USA to better understand FT processes and chemistry, and its impact on ground-level ozone.

Using Presentation Software to Flip an Undergraduate Analytical Chemistry Course

ERIC Educational Resources Information Center

Fitzgerald, Neil; Li, Luisa

2015-01-01

An undergraduate analytical chemistry course has been adapted to a flipped course format. Course content was provided by video clips, text, graphics, audio, and simple animations organized as concept maps using the cloud-based presentation platform, Prezi. The advantages of using Prezi to present course content in a flipped course format are…

The performance of low-cost commercial cloud computing as an alternative in computational chemistry.

PubMed

Thackston, Russell; Fortenberry, Ryan C

2015-05-05

The growth of commercial cloud computing (CCC) as a viable means of computational infrastructure is largely unexplored for the purposes of quantum chemistry. In this work, the PSI4 suite of computational chemistry programs is installed on five different types of Amazon World Services CCC platforms. The performance for a set of electronically excited state single-point energies is compared between these CCC platforms and typical, "in-house" physical machines. Further considerations are made for the number of cores or virtual CPUs (vCPUs, for the CCC platforms), but no considerations are made for full parallelization of the program (even though parallelization of the BLAS library is implemented), complete high-performance computing cluster utilization, or steal time. Even with this most pessimistic view of the computations, CCC resources are shown to be more cost effective for significant numbers of typical quantum chemistry computations. Large numbers of large computations are still best utilized by more traditional means, but smaller-scale research may be more effectively undertaken through CCC services. © 2015 Wiley Periodicals, Inc.

How Well Can Infrared Sounders Observe the Atmosphere and Surface Through Clouds?

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Larar, Allen M.; Liu, Xu; Smith, William L.; Strow, L. Larrabee; Yang, Ping

2010-01-01

Infrared sounders, such as the Atmospheric Infrared Sounder (AIRS), the Infrared Atmospheric Sounding Interferometer (IASI), and the Cross-track Infrared sounder (CrIS), have a cloud-impenetrable disadvantage in observing the atmosphere and surface under opaque cloudy conditions. However, recent studies indicate that hyperspectral, infrared sounders have the ability to detect cloud effective-optical and microphysical properties and to penetrate optically thin clouds in observing the atmosphere and surface to a certain degree. We have developed a retrieval scheme dealing with atmospheric conditions with cloud presence. This scheme can be used to analyze the retrieval accuracy of atmospheric and surface parameters under clear and cloudy conditions. In this paper, we present the surface emissivity results derived from IASI global measurements under both clear and cloudy conditions. The accuracy of surface emissivity derived under cloudy conditions is statistically estimated in comparison with those derived under clear sky conditions. The retrieval error caused by the clouds is shown as a function of cloud optical depth, which helps us to understand how well infrared sounders can observe the atmosphere and surface through clouds.

CLOUD CHEMISTRY IN THE EASTERN UNITED STATES, AS SAMPLED FROM THREE HIGH-ELEVATION SITES ALONG THE APPALACHIAN MOUNTAINS

EPA Science Inventory

Atmospheric deposition of acidic cloud water is thought to be one of the causes for the recent forest decline in industrialized areas of the world. The present paper presents results from the Mountain Acid Deposition Program (MADPro), a part of EPA's Clean Air Status and Trends ...

Multi-year application of WRF-CAM5 over East Asia-Part I: Comprehensive evaluation and formation regimes of O 3 and PM 2.5

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jian; Zhang, Yang; Wang, Kai

Accurate simulations of air quality and climate require robust model parameterizations on regional and global scales. The Weather Research and Forecasting model with Chemistry version 3.4.1 has been coupled with physics packages from the Community Atmosphere Model version 5 (CAM5) (WRF-CAM5) to assess the robustness of the CAM5 physics package for regional modeling at higher grid resolutions than typical grid resolutions used in global modeling. In this two-part study, Part I describes the application and evaluation of WRF-CAM5 over East Asia at a horizontal resolution of 36-km for six years: 2001, 2005, 2006, 2008, 2010, and 2011. The simulations aremore » evaluated comprehensively with a variety of datasets from surface networks, satellites, and aircraft. The results show that meteorology is relatively well simulated by WRF-CAM5. However, cloud variables are largely or moderately underpredicted, indicating uncertainties in the model treatments of dynamics, thermodynamics, and microphysics of clouds/ices as well as aerosol-cloud interactions. For chemical predictions, the tropospheric column abundances of CO, NO2, and O3 are well simulated, but those of SO2 and HCHO are moderately overpredicted, and the column HCHO/NO2 indicator is underpredicted. Large biases exist in the surface concentrations of CO, NO2, and PM10 due to uncertainties in the emissions as well as vertical mixing. The underpredictions of NO lead to insufficient O3 titration, thus O3 overpredictions. The model can generally reproduce the observed O3 and PM indicators. These indicators suggest to control NOx emissions throughout the year, and VOCs emissions in summer in big cities and in winter over North China Plain, North/South Korea, and Japan to reduce surface O3, and to control SO2, NH3, and NOx throughout the year to reduce inorganic surface PM.« less

Sensitivity simulations of superparameterised convection in a general circulation model

NASA Astrophysics Data System (ADS)

Rybka, Harald; Tost, Holger

2015-04-01

Cloud Resolving Models (CRMs) covering a horizontal grid spacing from a few hundred meters up to a few kilometers have been used to explicitly resolve small-scale and mesoscale processes. Special attention has been paid to realistically represent cloud dynamics and cloud microphysics involving cloud droplets, ice crystals, graupel and aerosols. The entire variety of physical processes on the small-scale interacts with the larger-scale circulation and has to be parameterised on the coarse grid of a general circulation model (GCM). Since more than a decade an approach to connect these two types of models which act on different scales has been developed to resolve cloud processes and their interactions with the large-scale flow. The concept is to use an ensemble of CRM grid cells in a 2D or 3D configuration in each grid cell of the GCM to explicitly represent small-scale processes avoiding the use of convection and large-scale cloud parameterisations which are a major source for uncertainties regarding clouds. The idea is commonly known as superparameterisation or cloud-resolving convection parameterisation. This study presents different simulations of an adapted Earth System Model (ESM) connected to a CRM which acts as a superparameterisation. Simulations have been performed with the ECHAM/MESSy atmospheric chemistry (EMAC) model comparing conventional GCM runs (including convection and large-scale cloud parameterisations) with the improved superparameterised EMAC (SP-EMAC) modeling one year with prescribed sea surface temperatures and sea ice content. The sensitivity of atmospheric temperature, precipiation patterns, cloud amount and types is observed changing the embedded CRM represenation (orientation, width, no. of CRM cells, 2D vs. 3D). Additionally, we also evaluate the radiation balance with the new model configuration, and systematically analyse the impact of tunable parameters on the radiation budget and hydrological cycle. Furthermore, the subgrid variability (individual CRM cell output) is analysed in order to illustrate the importance of a highly varying atmospheric structure inside a single GCM grid box. Finally, the convective transport of Radon is observed comparing different transport procedures and their influence on the vertical tracer distribution.

Decadal evaluation of regional climate, air quality, and their interactions using WRF/Chem Version 3.6.1

NASA Astrophysics Data System (ADS)

Yahya, K.; Wang, K.; Campbell, P.; Glotfelty, T.; He, J.; Zhang, Y.

2015-08-01

The Weather Research and Forecasting model with Chemistry (WRF/Chem) v3.6.1 with the Carbon Bond 2005 (CB05) gas-phase mechanism is evaluated for its first decadal application during 2001-2010 using the Representative Concentration Pathway (RCP 8.5) emissions to assess its capability and appropriateness for long-term climatological simulations. The initial and boundary conditions are downscaled from the modified Community Earth System Model/Community Atmosphere Model (CESM/CAM5) v1.2.2. The meteorological initial and boundary conditions are bias-corrected using the National Center for Environmental Protection's Final (FNL) Operational Global Analysis data. Climatological evaluations are carried out for meteorological, chemical, and aerosol-cloud-radiation variables against data from surface networks and satellite retrievals. The model performs very well for the 2 m temperature (T2) for the 10 year period with only a small cold bias of -0.3 °C. Biases in other meteorological variables including relative humidity at 2 m, wind speed at 10 m, and precipitation tend to be site- and season-specific; however, with the exception of T2, consistent annual biases exist for most of the years from 2001 to 2010. Ozone mixing ratios are slightly overpredicted at both urban and rural locations but underpredicted at rural locations. PM2.5 concentrations are slightly overpredicted at rural sites, but slightly underpredicted at urban/suburban sites. In general, the model performs relatively well for chemical and meteorological variables, and not as well for aerosol-cloud-radiation variables. Cloud-aerosol variables including aerosol optical depth, cloud water path, cloud optical thickness, and cloud droplet number concentration are generally underpredicted on average across the continental US. Overpredictions of several cloud variables over eastern US result in underpredictions of radiation variables and overpredictions of shortwave and longwave cloud forcing which are important climate variables. While the current performance is deemed to be acceptable, improvements to the bias-correction method for CESM downscaling and the model parameterizations of cloud dynamics and thermodynamics, as well as aerosol-cloud interactions can potentially improve model performance for long-term climate simulations.

The 1991 Eruption of Mt. Pinatubo: Changes in Climate and Atmospheric Chemistry- Lesson Learned and Questions Left Unanswered

NASA Astrophysics Data System (ADS)

Toon, O. B.

2016-12-01

Mt. Pinatubo injected the largest amount of SO2 into the stratosphere of any 20th Century eruption. I will survey what we learned, and point out issues that require more data, or further analysis. Beautiful purple twilight glows, hazy gray skies, and sunsets so bright they caused traffic accidents made the volcanic cloud evident to even casual observers for more than a year. High altitude aircraft, balloons, satellites and ground-based instruments measured many properties of the cloud and its impact on the Earth. Scattering of sunlight to space created a temporary negative radiative forcing, larger than the positive forcing from greenhouse gases in the previous century. As a result the surface cooled, but the cloud faded before the cooling reached its full potential. Absorption of near infrared sunlight, and of upwelling mid-infrared radiation heated the stratosphere. The heating was unequal, which may have induced local dynamical changes that sped the movement of the cloud into the Southern Hemisphere. The ascending motion in the tropical branch of the Brewer-Dobson circulation sped up, leading to tropical ozone reductions. Mid-latitude declines in ozone were caused by heterogeneous chemical reactions on the volcanic cloud. Polar ozone loss was enhanced by increased heterogeneous reactions due to the increased surface area provided by the volcanic particles. A number of important microphysical insights were gained that are not always recognized. Stratospheric particle sizes increase with the addition of SO2, and even Pinatubo particles did not have a constant or uniform particle size distribution. The optical depth was not uniform over the globe, or even one hemisphere. In fact, the maximum optical depth moved from the tropics to high northern latitudes over the first year. Many questions have been left unanswered. Theory suggests the optical depth of volcanic clouds increases less than linearly with the mass of SO2 injected, is this correct? Observations did not show injections of water or halogens, will other eruptions have significant injections? Do large eruptions have an effect on El Nino or winter warming in the Northern Hemisphere, and if so what is the mechanism? Other large eruptions are inevitable, but rare. How can we prepare to measure the properties and effects of their clouds?

Feedbacks between Air-Quality, Meteorology, and the Forest Environment

NASA Astrophysics Data System (ADS)

Makar, Paul; Akingunola, Ayodeji; Stroud, Craig; Zhang, Junhua; Gong, Wanmin; Moran, Michael; Zheng, Qiong; Brook, Jeffrey; Sills, David

2017-04-01

The outcome of air quality forecasts depend in part on how the local environment surrounding the emissions regions influences chemical reaction rates and transport from those regions to the larger spatial scales. Forested areas alter atmospheric chemistry through reducing photolysis rates and vertical diffusivities within the forest canopy. The emitted pollutants, and their reaction products, are in turn capable of altering meteorology, through the well-known direct and indirect effects of particulate matter on radiative transfer. The combination of these factors was examined using version 2 of the Global Environmental Multiscale - Modelling Air-quality and CHemistry (GEM-MACH) on-line air pollution model. The model configuration used for this study included 12 aerosol size bins, eight aerosol species, homogeneous core Mie scattering, the Milbrandt-Yao two-moment cloud microphysics scheme with cloud condensation nuclei generated from model aerosols using the scheme of Abdul-Razzak and Ghan, and a new parameterization for forest canopy shading and turbulence. The model was nested to 2.5km resolution for a domain encompassing the lower Great Lakes, for simulations of a period in August of 2015 during the Pan American Games, held in Toronto, Canada. Four scenarios were carried out: (1) a "Base Case" scenario (the original model, in which coupling between chemistry and weather is not permitted; instead, the meteorological model's internal climatologies for aerosol optical and cloud condensation properties are used for direct and indirect effect calculations); (2) a "Feedback" scenario (the aerosol properties were derived from the internally simulated chemistry, and coupled to the meteorological model's radiative transfer and cloud formation modules); (3) a "Forest" scenario (canopy shading and turbulence were added to the Base Case); (4) a "Combined" scenario (including both direct and indirect effect coupling between meteorology and chemistry, as well as the forest canopy parameterization). The simulations suggest that the feedbacks between simulated aerosols and meteorology may strengthen the existing lake breeze circulation, modifying the resulting meteorological and air-quality forecasts, while the forest canopy's influence may extend throughout the planetary boundary layer, and may also influence the weather. The simulations will be compared to available observations, in order to determine their relative impact on model performance.

Theoretical Investigations of Clouds and Aerosols in the Stratosphere and Upper Troposphere

NASA Technical Reports Server (NTRS)

Toon, Owen B.

2005-01-01

support of the Atmospheric Chemistry Modeling and Data Analysis Program. We investigated a wide variety of issues involving ambient stratospheric aerosols, polar stratospheric clouds or heterogeneous chemistry, analysis of laboratory data, and particles in the upper troposphere. The papers resulting from these studies are listed below. In addition, I participated in the 1999-2000 SOLVE mission as one of the project scientists and in the 2002 CRYSTAL field mission as one of the project scientists. Several CU graduate students and research associates also participated in these mission, under support from the ACMAP program, and worked to interpret data. During the past few years my group has completed a number of projects under the

Dust Production and Mass Loss in Cool Evolved Stars

NASA Technical Reports Server (NTRS)

Boyer, M. L.

2013-01-01

Following the red giant branch phase and the subsequent core He-burning phase, the low- to intermediate-mass stars (0.8

Chemical transitions for interstellar C2 and CN in cloud envelopes

NASA Technical Reports Server (NTRS)

Federman, S. R.; Strom, C. J.; Lambert, D. L.; Cardelli, Jason A.; Smith, V. V.; Joseph, C. L.

1994-01-01

Observations were made of absorption from CH, C2, and CN toward moderately reddened stars in Sco, OB2, Ceo OB3, and Taurus/Auriga. For these directions, most of the reddening is associated with a single cloud complex, for example, the rho Ophiuchus molecular cloud, and as a result, the observations probe moderately dense material. When combined with avaliable data for nearby directions, the survey provides the basis for a comprehensive analysis of the chemistry for these species. The chemical transitions affecting C2 and CN in cloud envelopes were analyzed. The depth into a cloud at which a transition takes place was characterized by tau(sub uv), the grain optical depth at 1000 A. One transition at tau(sub uv) approx. = 2, which arises from, the conversion of C(+) into CO, affects the chemistries for both molecules because of the key role this ion plays. A second one involving production terms in the CN chemistry occurs at tau(sub uv) of approx. = 3; neutral reactions which C2 and CH is more important at larger values for tau(sub uv). The transition from photodissociation to chemical destruction takes place at tau(sub uv) approx. = 4.5 for C2 and CN. The observational data for stars in Sco OB2, Cep OB3, and Taurus/Auriga were studied with chemical rate equations containing the most important production and destruction mechanisms. Because the sample of stars in Sco OB2 includes sight lines with A(sub v) ranging from 1-4 mag, sight lines dominated by photochemistry could be analyzed separately from those controlled by gas-phase destruction. The analysis yielded values for two poorly known rate constants for reactions involved in the production of CN; the reactions are C2 + N yields CN + C and C(+) + NH yields all products. The other directions were analyzed with the inferred values. The predicted column densities for C2 and CN agree with the observed values to better than 50%, and in most instances 20%. When combining the estimates for density and temperature derived from chemical modeling and molecular excitation for a specific cloud, such as the rho Ophiuchus molecular cloud, the portion of the cloud envelope probed by C2 and CN absorption was found to be in pressure equilibrium.

Biological aerosol effects on clouds and precipitation

NASA Astrophysics Data System (ADS)

Hallar, A. Gannet; Huffman, J. Alex; Fridlind, Ann

2012-12-01

Bioaerosol Effects on Clouds Workshop;Steamboat Springs, Colorado, 5-6August 2012 Bioaerosols such as bacteria have been proposed as significant contributors to cloud ice nucleation, but too little is known about the properties and impacts of bioaerosol and other ice nuclei to make reliable conclusions about their wide-scale impact on clouds and precipitation. During late summer an international group of 40 participants met at a Steamboat Springs ski resort to share perspectives on bioaerosol sources, activity, and influence on clouds. Participants who were invited collectively spanned a broad range of expertise, including atmospheric chemistry, microbiology, micrometeorology, and cloud physics, as well as a broad range of research approaches, including laboratory measurement, field measurement, and modeling. Tours of Storm Peak Laboratory (http://www.stormpeak.dri.edu) were offered before and after the workshop.

The Impact of Cloud Properties on Young Sea Ice during Three Winter Storms at N-ICE2015

NASA Astrophysics Data System (ADS)

Murphy, S. Y.; Walden, V. P.; Cohen, L.; Hudson, S. R.

2017-12-01

The impact of clouds on sea ice varies significantly as cloud properties change. Instruments deployed during the Norwegian Young Sea Ice field campaign (N-ICE2015) are used to study how differing cloud properties influence the cloud radiative forcing at the sea ice surface. N-ICE2015 was the first campaign in the Arctic winter since SHEBA (1997/1998) to study the surface energy budget of sea ice and the associated effects of cloud properties. Cloud characteristics, surface radiative and turbulent fluxes, and meteorological properties were measured throughout the field campaign. Here we explore how cloud macrophysical and microphysical properties affect young, thin sea ice during three winter storms from 31 January to 15 February 2015. This time period is of interest due to the varying surface and atmospheric conditions, which showcase the variety of conditions the newly-formed sea ice can experience during the winter. This period was characterized by large variations in the ice surface and near-surface air temperatures, with highs near 0°C when warm, moist air was advected into the area and lows reaching -40°C during clear, calm periods between storms. The advection of warm, moist air into the area influenced the cloud properties and enhanced the downwelling longwave flux. For most of the period, downwelling longwave flux correlates closely with the air temperature. However, at the end of the first storm, a drop in downwelling longwave flux of about 50 Wm-2 was observed, independent of any change in surface or air temperature or cloud fraction, indicating a change in cloud properties. Lidar data show an increase in cloud height during this period and a potential shift in cloud phase from ice to mixed-phase. This study will describe the cloud properties during the three winter storms and discuss their impacts on surface energy budget.

The relationship between interannual and long-term cloud feedbacks

DOE PAGES

Zhou, Chen; Zelinka, Mark D.; Dessler, Andrew E.; ...

2015-12-11

The analyses of Coupled Model Intercomparison Project phase 5 simulations suggest that climate models with more positive cloud feedback in response to interannual climate fluctuations also have more positive cloud feedback in response to long-term global warming. Ensemble mean vertical profiles of cloud change in response to interannual and long-term surface warming are similar, and the ensemble mean cloud feedback is positive on both timescales. However, the average long-term cloud feedback is smaller than the interannual cloud feedback, likely due to differences in surface warming pattern on the two timescales. Low cloud cover (LCC) change in response to interannual andmore » long-term global surface warming is found to be well correlated across models and explains over half of the covariance between interannual and long-term cloud feedback. In conclusion, the intermodel correlation of LCC across timescales likely results from model-specific sensitivities of LCC to sea surface warming.« less

Primitive bodies - Molecular abundances in Comet Halley as probes of cometary formation environments

NASA Technical Reports Server (NTRS)

Lunine, Jonathan I.

1989-01-01

The most recent results on abundances of molecules in Halley's comet are examined in the context of various models for the environment in which comets formed. These environments include molecular clouds associated with star-forming regions, the solar nebula, gaseous disks around proto-planets, and combinations of these. Of all constituents in a cometary nucleus, the highly volatile molecules such as methane, ammonia, molecular nitrogen, and carbon monoxide are most sensitive to the final episode of cometary grain formation and incorporation in the comet's nucleus; hence they likely reflect at least some chemical processing in the solar nebula. Proper interpretation requires modeling of a number of physical processes including gas phase chemistry, chemistry on grain surfaces, and fractionation effects resulting from preferential incorporation of certain gases in proto-cometary grains. The abundance of methane in Halley's comet could be a key indicator of where that comet formed, provided the methane abundance on grains in star-forming regions can be observationally constrained.

CAUSES: Attribution of Surface Radiation Biases in NWP and Climate Models near the U.S. Southern Great Plains

DOE PAGES

Van Weverberg, K.; Morcrette, C. J.; Petch, J.; ...

2018-02-28

Many Numerical Weather Prediction (NWP) and climate models exhibit too warm lower tropospheres near the midlatitude continents. The warm bias has been shown to coincide with important surface radiation biases that likely play a critical role in the inception or the growth of the warm bias. This paper presents an attribution study on the net radiation biases in nine model simulations, performed in the framework of the CAUSES project (Clouds Above the United States and Errors at the Surface). Contributions from deficiencies in the surface properties, clouds, water vapor, and aerosols are quantified, using an array of radiation measurement stationsmore » near the Atmospheric Radiation Measurement Southern Great Plains site. Furthermore, an in-depth analysis is shown to attribute the radiation errors to specific cloud regimes. The net surface shortwave radiation is overestimated in all models throughout most of the simulation period. Cloud errors are shown to contribute most to this overestimation, although nonnegligible contributions from the surface albedo exist in most models. Missing deep cloud events and/or simulating deep clouds with too weak cloud radiative effects dominate in the cloud-related radiation errors. Some models have compensating errors between excessive occurrence of deep cloud but largely underestimating their radiative effect, while other models miss deep cloud events altogether. Surprisingly, even the latter models tend to produce too much and too frequent afternoon surface precipitation. This suggests that rather than issues with the triggering of deep convection, cloud radiative deficiencies are related to too weak convective cloud detrainment and too large precipitation efficiencies.« less

CAUSES: Attribution of Surface Radiation Biases in NWP and Climate Models near the U.S. Southern Great Plains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Weverberg, K.; Morcrette, C. J.; Petch, J.

Many Numerical Weather Prediction (NWP) and climate models exhibit too warm lower tropospheres near the midlatitude continents. The warm bias has been shown to coincide with important surface radiation biases that likely play a critical role in the inception or the growth of the warm bias. This paper presents an attribution study on the net radiation biases in nine model simulations, performed in the framework of the CAUSES project (Clouds Above the United States and Errors at the Surface). Contributions from deficiencies in the surface properties, clouds, water vapor, and aerosols are quantified, using an array of radiation measurement stationsmore » near the Atmospheric Radiation Measurement Southern Great Plains site. Furthermore, an in-depth analysis is shown to attribute the radiation errors to specific cloud regimes. The net surface shortwave radiation is overestimated in all models throughout most of the simulation period. Cloud errors are shown to contribute most to this overestimation, although nonnegligible contributions from the surface albedo exist in most models. Missing deep cloud events and/or simulating deep clouds with too weak cloud radiative effects dominate in the cloud-related radiation errors. Some models have compensating errors between excessive occurrence of deep cloud but largely underestimating their radiative effect, while other models miss deep cloud events altogether. Surprisingly, even the latter models tend to produce too much and too frequent afternoon surface precipitation. This suggests that rather than issues with the triggering of deep convection, cloud radiative deficiencies are related to too weak convective cloud detrainment and too large precipitation efficiencies.« less

CAUSES: Attribution of Surface Radiation Biases in NWP and Climate Models near the U.S. Southern Great Plains

NASA Astrophysics Data System (ADS)

Van Weverberg, K.; Morcrette, C. J.; Petch, J.; Klein, S. A.; Ma, H.-Y.; Zhang, C.; Xie, S.; Tang, Q.; Gustafson, W. I.; Qian, Y.; Berg, L. K.; Liu, Y.; Huang, M.; Ahlgrimm, M.; Forbes, R.; Bazile, E.; Roehrig, R.; Cole, J.; Merryfield, W.; Lee, W.-S.; Cheruy, F.; Mellul, L.; Wang, Y.-C.; Johnson, K.; Thieman, M. M.

2018-04-01

Many Numerical Weather Prediction (NWP) and climate models exhibit too warm lower tropospheres near the midlatitude continents. The warm bias has been shown to coincide with important surface radiation biases that likely play a critical role in the inception or the growth of the warm bias. This paper presents an attribution study on the net radiation biases in nine model simulations, performed in the framework of the CAUSES project (Clouds Above the United States and Errors at the Surface). Contributions from deficiencies in the surface properties, clouds, water vapor, and aerosols are quantified, using an array of radiation measurement stations near the Atmospheric Radiation Measurement Southern Great Plains site. Furthermore, an in-depth analysis is shown to attribute the radiation errors to specific cloud regimes. The net surface shortwave radiation is overestimated in all models throughout most of the simulation period. Cloud errors are shown to contribute most to this overestimation, although nonnegligible contributions from the surface albedo exist in most models. Missing deep cloud events and/or simulating deep clouds with too weak cloud radiative effects dominate in the cloud-related radiation errors. Some models have compensating errors between excessive occurrence of deep cloud but largely underestimating their radiative effect, while other models miss deep cloud events altogether. Surprisingly, even the latter models tend to produce too much and too frequent afternoon surface precipitation. This suggests that rather than issues with the triggering of deep convection, cloud radiative deficiencies are related to too weak convective cloud detrainment and too large precipitation efficiencies.

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3c

DOE PAGES

Prather, M. J.

2015-08-14

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and is implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observations of the vertical correlation of cloud layers, Cloud-J 7.3c provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations by four quadrature atmospheres produces mean J values in an atmospheric column with root mean square (rms) errors of 4 % or less compared with 10–20 %more » errors using simpler approximations. Cloud-J is practical for chemistry–climate models, requiring only an average of 2.8 Fast-J calls per atmosphere vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections, is also incorporated into Cloud-J.« less

Large-eddy simulation of subtropical cloud-topped boundary layers: 1. A forcing framework with closed surface energy balance

NASA Astrophysics Data System (ADS)

Tan, Zhihong; Schneider, Tapio; Teixeira, João.; Pressel, Kyle G.

2016-12-01

Large-eddy simulation (LES) of clouds has the potential to resolve a central question in climate dynamics, namely, how subtropical marine boundary layer (MBL) clouds respond to global warming. However, large-scale processes need to be prescribed or represented parameterically in the limited-area LES domains. It is important that the representation of large-scale processes satisfies constraints such as a closed energy balance in a manner that is realizable under climate change. For example, LES with fixed sea surface temperatures usually do not close the surface energy balance, potentially leading to spurious surface fluxes and cloud responses to climate change. Here a framework of forcing LES of subtropical MBL clouds is presented that enforces a closed surface energy balance by coupling atmospheric LES to an ocean mixed layer with a sea surface temperature (SST) that depends on radiative fluxes and sensible and latent heat fluxes at the surface. A variety of subtropical MBL cloud regimes (stratocumulus, cumulus, and stratocumulus over cumulus) are simulated successfully within this framework. However, unlike in conventional frameworks with fixed SST, feedbacks between cloud cover and SST arise, which can lead to sudden transitions between cloud regimes (e.g., stratocumulus to cumulus) as forcing parameters are varied. The simulations validate this framework for studies of MBL clouds and establish its usefulness for studies of how the clouds respond to climate change.

The variability of California summertime marine stratus: impacts on surface air temperatures

USGS Publications Warehouse

Iacobellis, Sam F.; Cayan, Daniel R.

2013-01-01

This study investigates the variability of clouds, primarily marine stratus clouds, and how they are associated with surface temperature anomalies over California, especially along the coastal margin. We focus on the summer months of June to September when marine stratus are the dominant cloud type. Data used include satellite cloud reflectivity (cloud albedo) measurements, hourly surface observations of cloud cover and air temperature at coastal airports, and observed values of daily surface temperature at stations throughout California and Nevada. Much of the anomalous variability of summer clouds is organized over regional patterns that affect considerable portions of the coast, often extend hundreds of kilometers to the west and southwest over the North Pacific, and are bounded to the east by coastal mountains. The occurrence of marine stratus is positively correlated with both the strength and height of the thermal inversion that caps the marine boundary layer, with inversion base height being a key factor in determining their inland penetration. Cloud cover is strongly associated with surface temperature variations. In general, increased presence of cloud (higher cloud albedo) produces cooler daytime temperatures and warmer nighttime temperatures. Summer daytime temperature fluctuations associated with cloud cover variations typically exceed 1°C. The inversion-cloud albedo-temperature associations that occur at daily timescales are also found at seasonal timescales.

Surface Emissivity Retrieved with Satellite Ultraspectral IR Measurements for Monitoring Global Change

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Larar, Allen M.; Liu, Xu; Smith, William L.; Schluessel, Peter

2009-01-01

Surface and atmospheric thermodynamic parameters retrieved with advanced ultraspectral remote sensors aboard Earth observing satellites are critical to general atmospheric and Earth science research, climate monitoring, and weather prediction. Ultraspectral resolution infrared radiance obtained from nadir observations provide atmospheric, surface, and cloud information. Presented here is the global surface IR emissivity retrieved from Infrared Atmospheric Sounding Interferometer (IASI) measurements under "clear-sky" conditions. Fast radiative transfer models, applied to the cloud-free (or clouded) atmosphere, are used for atmospheric profile and surface parameter (or cloud parameter) retrieval. The inversion scheme, dealing with cloudy as well as cloud-free radiances observed with ultraspectral infrared sounders, has been developed to simultaneously retrieve atmospheric thermodynamic and surface (or cloud microphysical) parameters. Rapidly produced surface emissivity is initially evaluated through quality control checks on the retrievals of other impacted atmospheric and surface parameters. Surface emissivity and surface skin temperature from the current and future operational satellites can and will reveal critical information on the Earth s ecosystem and land surface type properties, which can be utilized as part of long-term monitoring for the Earth s environment and global climate change.

A 10-Year Climatology of Cloud Cover and Vertical Distribution Derived from Both Surface and GOES Observations Over the DOE ARM SGP Site

NASA Technical Reports Server (NTRS)

Xi, Baike; Dong, Xiquan; Minnis, P.; Khaiyer, M.

2010-01-01

Analysis of a decade of ARM radar-lidar and GOES observations at the SGP site reveal that 0.5 and 4-hr averages of the surface cloud fraction correspond closely to 0.5deg and 2.5deg averages of GOES cloudiness, respectively. The long-term averaged surface and GOES cloud fractions agree to within 0.5%. Cloud frequency increases and cloud amount decreases as the temporal and spatial averaging scales increase. Clouds occurred most often during winter and spring. Single-layered clouds account for 61.5% of the total cloud frequency. There are distinct bimodal vertical distributions of clouds with a lower peak around 1 km and an upper one that varies from 7.5 to 10.8 km between winter and summer, respectively. The frequency of occurrence for nighttime GOES high-cloud tops agree well with the surface observations, but are underestimated during the day.

The climate impacts of absorbing aerosols on and within the Arctic

NASA Astrophysics Data System (ADS)

Rasch, P.; Wang, H.; Ma, P.; Fast, J. D.; Wang, M.; Easter, R. C.; Liu, X.; Qian, Y.; Flanner, M. G.; Ghan, S.; Singh, B.

2011-12-01

Absorbing aerosols are receiving increasing attention as forcing agents in the climate system. By scattering and absorbing light they can reduce planetary albedo, particularly over bright surfaces (clouds, snow and ice). They also act as cloud condensation and/or ice nuclei, influencing the brightness, lifetime and precipitation properties of clouds. Atmospheric stability and primary circulation features respond to the changing vertical and horizontal patterns of heating, cooling, and surface fluxes produced by the aerosols, clouds and surface properties. These changes in meteorology have further impacts on aerosols and clouds producing a complex interplay between transport, forcings, and feedbacks involving absorbing aerosols and climate. The complexity of the processes and the interactions between them make it very challenging to represent aerosols realistically in large scale (global and regional) climate models. Simulations of important features of aerosols still contain easily identifiable biases. I will describe our efforts to identify the processes responsible for some of those biases and the deficiencies in model formulations that impede progress in treating aerosols and understanding their role in polar climate. I plan to summarize some studies performed with the NCAR CESM (global) and WRF-Chem (regional) Community models that examine the simulation sensitivity to treatments of physics, chemistry, and meteorology. Some of these simulations were allowed to evolve freely; others were strongly constrained to agree with observed meteorological fields. We have also altered the formulation of a number of the processes in the model to improve fidelity in the aerosol distributions. The parameterizations used in our global model have also been transferred to the regional model, allowing comparisons to be made between the simpler formulations used in the global model with more elaborate and costly formulations available in the regional model. The regional model can be run at higher resolution in order to explore the resolution dependence of the parameterizations and make comparisons to field experiments more straightforward. Aerosols sources have also been tagged by sector and geographic region to help in attribution and interpretation. The many variations mentioned here help in understanding how aerosols reach the arctic and how they produce changes in radiative forcing and Arctic climate. I will provide a brief overview of these studies, with more detail available in presentations submitted to this session and elsewhere.

“Towards building better linkages between aqueous phase ...

EPA Pesticide Factsheets

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and employing a bisection method to calculate H+ concentrations. With potentially hundreds of reactions that may be important in cloud water and only seven reactions in the current model, expansion of the existing mechanism is an important area of investigation. However, with the current mechanism hardwired into the solver code, the module is difficult to expand with additional chemistry. It also ignores the impacts of mass transfer limitations on cloud chemistry which may be significant. Here, the Kinetic PreProcessor has been applied to generate a Rosenbrock solver for the CMAQ v5.0.1 aqueous phase chemistry mechanism. The module has been updated to simultaneously solve kinetic mass transfer between the phases, dissociation/association, chemical kinetics, Aitken scavenging, and wet deposition. This will allow for easier expansion of the chemical mechanism in the future and a better link between aqueous phase chemistry and droplet microphysics. The National Exposure Research Laboratory (NERL) Atmospheric Modeling and Analysis Division (AMAD) conducts research in support of EPA mission to protect human health and the environment. AMAD research program is engaged in developing and evaluating pre

Ozone Research with Advanced Cooperative Lidar Experiment (ORACLE) Implementation Study

NASA Technical Reports Server (NTRS)

Stadler, John H.; Browell, Edward V.; Ismail, Syed; Dudelzak, Alexander E.; Ball, Donald J.

1998-01-01

New technological advances have made possible new active remote sensing capabilities from space. Utilizing these technologies, the Ozone Research with Advanced Cooperative Lidar Experiment (ORACLE) will provide high spatial resolution measurements of ozone, clouds and aerosols in the stratosphere and lower troposphere. Simultaneous measurements of ozone, clouds and aerosols will assist in the understanding of global change, atmospheric chemistry and meteorology.

Search for molecular absorptions with the Fourier Transform Spectrometer

NASA Technical Reports Server (NTRS)

Knacke, Roger F.

1995-01-01

The objective of this research was a search for water molecules in the gas phase in molecular clouds. Water should be among the most abundant gases in the clouds and is of fundamental importance in gas chemistry, cloud cooling, shock wave chemistry, and gas-grain interactions of interstellar dust. Detection of water in Comet Halley in the 2.7 micron v(3) band in 1986 had shown that airborne H2O observations are feasible (ground-based observations of H2O are impossible because of the massive water content of the atmosphere). We planned to observe the v(3) band in interstellar clouds where a number of lines of this band should be in absorption. The search for H2O commenced in 1988 with a two flight program on the KAO. this resulted in a detection of interstellar H2O with S/N of 2-4 in the v(3) 1(01)-2(02) line at 3801.42/cm. A subsequent flight series of two flights in 1989 resulted in confirmation to the 3801.42/cm line detection and the detection of altogether four strong lines in the 000-001 v(3) vibration-rotation band of H2O.

Gemini Planet Imager Spectroscopy of the HR 8799 Planets c and d

DOE PAGES

Ingraham, Patrick; Marley, Mark S.; Saumon, Didier; ...

2014-09-30

During the first-light run of the Gemini Planet Imager we obtained K-band spectra of exoplanets HR 8799 c and d. Analysis of the spectra indicates that planet d may be warmer than planet c. Comparisons to recent patchy cloud models and previously obtained observations over multiple wavelengths confirm that thick clouds combined with horizontal variation in the cloud cover generally reproduce the planets’ spectral energy distributions.When combined with the 3 to 4μm photometric data points, the observations provide strong constraints on the atmospheric methane content for both planets. Lastly, the data also provide further evidence that future modeling efforts mustmore » include cloud opacity, possibly including cloud holes, disequilibrium chemistry, and super-solar metallicity.« less

Directly Imaged L-T Transition Exoplanets in the Mid-infrared

NASA Astrophysics Data System (ADS)

Skemer, Andrew J.; Marley, Mark S.; Hinz, Philip M.; Morzinski, Katie M.; Skrutskie, Michael F.; Leisenring, Jarron M.; Close, Laird M.; Saumon, Didier; Bailey, Vanessa P.; Briguglio, Runa; Defrere, Denis; Esposito, Simone; Follette, Katherine B.; Hill, John M.; Males, Jared R.; Puglisi, Alfio; Rodigas, Timothy J.; Xompero, Marco

2014-09-01

Gas-giant planets emit a large fraction of their light in the mid-infrared (gsim3 μm), where photometry and spectroscopy are critical to our understanding of the bulk properties of extrasolar planets. Of particular importance are the L- and M-band atmospheric windows (3-5 μm), which are the longest wavelengths currently accessible to ground-based, high-contrast imagers. We present binocular LBT adaptive optics (AO) images of the HR 8799 planetary system in six narrow-band filters from 3 to 4 μm, and a Magellan AO image of the 2M1207 planetary system in a broader 3.3 μm band. These systems encompass the five known exoplanets with luminosities consistent with L → T transition brown dwarfs. Our results show that the exoplanets are brighter and have shallower spectral slopes than equivalent temperature brown dwarfs in a wavelength range that contains the methane fundamental absorption feature (spanned by the narrow-band filters and encompassed by the broader 3.3 μm filter). For 2M1207 b, we find that thick clouds and non-equilibrium chemistry caused by vertical mixing can explain the object's appearance. For the HR 8799 planets, we present new models that suggest the atmospheres must have patchy clouds, along with non-equilibrium chemistry. Together, the presence of a heterogeneous surface and vertical mixing presents a picture of dynamic planetary atmospheres in which both horizontal and vertical motions influence the chemical and condensate profiles.

Directly imaged L-T transition exoplanets in the mid-infrared {sup ,}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skemer, Andrew J.; Hinz, Philip M.; Morzinski, Katie M.

2014-09-01

Gas-giant planets emit a large fraction of their light in the mid-infrared (≳3 μm), where photometry and spectroscopy are critical to our understanding of the bulk properties of extrasolar planets. Of particular importance are the L- and M-band atmospheric windows (3-5 μm), which are the longest wavelengths currently accessible to ground-based, high-contrast imagers. We present binocular LBT adaptive optics (AO) images of the HR 8799 planetary system in six narrow-band filters from 3 to 4 μm, and a Magellan AO image of the 2M1207 planetary system in a broader 3.3 μm band. These systems encompass the five known exoplanets withmore » luminosities consistent with L → T transition brown dwarfs. Our results show that the exoplanets are brighter and have shallower spectral slopes than equivalent temperature brown dwarfs in a wavelength range that contains the methane fundamental absorption feature (spanned by the narrow-band filters and encompassed by the broader 3.3 μm filter). For 2M1207 b, we find that thick clouds and non-equilibrium chemistry caused by vertical mixing can explain the object's appearance. For the HR 8799 planets, we present new models that suggest the atmospheres must have patchy clouds, along with non-equilibrium chemistry. Together, the presence of a heterogeneous surface and vertical mixing presents a picture of dynamic planetary atmospheres in which both horizontal and vertical motions influence the chemical and condensate profiles.« less

Cloud characterization and clear-sky correction from Landsat-7

USGS Publications Warehouse

Cahalan, Robert F.; Oreopoulos, L.; Wen, G.; Marshak, S.; Tsay, S. -C.; DeFelice, Tom

2001-01-01

Landsat, with its wide swath and high resolution, fills an important mesoscale gap between atmospheric variations seen on a few kilometer scale by local surface instrumentation and the global view of coarser resolution satellites such as MODIS. In this important scale range, Landsat reveals radiative effects on the few hundred-meter scale of common photon mean-free-paths, typical of scattering in clouds at conservative (visible) wavelengths, and even shorter mean-free-paths of absorptive (near-infrared) wavelengths. Landsat also reveals shadowing effects caused by both cloud and vegetation that impact both cloudy and clear-sky radiances. As a result, Landsat has been useful in development of new cloud retrieval methods and new aerosol and surface retrievals that account for photon diffusion and shadowing effects. This paper discusses two new cloud retrieval methods: the nonlocal independent pixel approximation (NIPA) and the normalized difference nadir radiance method (NDNR). We illustrate the improvements in cloud property retrieval enabled by the new low gain settings of Landsat-7 and difficulties found at high gains. Then, we review the recently developed “path radiance” method of aerosol retrieval and clear-sky correction using data from the Department of Energy Atmospheric Radiation Measurement (ARM) site in Oklahoma. Nearby clouds change the solar radiation incident on the surface and atmosphere due to indirect illumination from cloud sides. As a result, if clouds are nearby, this extra side-illumination causes clear pixels to appear brighter, which can be mistaken for extra aerosol or higher surface albedo. Thus, cloud properties must be known in order to derive accurate aerosol and surface properties. A three-dimensional (3D) Monte Carlo (MC) radiative transfer simulation illustrates this point and suggests a method to subtract the cloud effect from aerosol and surface retrievals. The main conclusion is that cloud, aerosol, and surface retrievals are linked and must be treated as a combined system. Landsat provides the range of scales necessary to observe the 3D cloud radiative effects that influence joint surface-atmospheric retrievals.

Hyperspectrally-Resolved Surface Emissivity Derived Under Optically Thin Clouds

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Larar, Allen M.; Liu, Xu; Smith, William L.; Strow, L. Larrabee; Yang, Ping

2010-01-01

Surface spectral emissivity derived from current and future satellites can and will reveal critical information about the Earth s ecosystem and land surface type properties, which can be utilized as a means of long-term monitoring of global environment and climate change. Hyperspectrally-resolved surface emissivities are derived with an algorithm utilizes a combined fast radiative transfer model (RTM) with a molecular RTM and a cloud RTM accounting for both atmospheric absorption and cloud absorption/scattering. Clouds are automatically detected and cloud microphysical parameters are retrieved; and emissivity is retrieved under clear and optically thin cloud conditions. This technique separates surface emissivity from skin temperature by representing the emissivity spectrum with eigenvectors derived from a laboratory measured emissivity database; in other words, using the constraint as a means for the emissivity to vary smoothly across atmospheric absorption lines. Here we present the emissivity derived under optically thin clouds in comparison with that under clear conditions.

Influence of the Surface and Cloud Nonuniformities in the Solar Energy Fluxes in the Arctic

NASA Technical Reports Server (NTRS)

Rozwadowska, A.; Cahalan, R. F.; Einaudi, Franco (Technical Monitor)

2000-01-01

Solar energy fluxes reaching the surface and absorbed by it are basic components of the energy balance of the Arctic. They depend mainly on the solar zenith angle, a state of the atmosphere, especially the cloudiness, and the surface albedo. However, they can also be modified by variabilities in the surface albedo and cloud optical thickness. The surface of the Arctic can be highly nonuniform. The surface of the Arctic Ocean, which covers the huge part of the Arctic can be view as a mosaic of sea water, sea ice, snow and, in the melting period, melting ponds. In our paper, results are presented of Monte Carlo simulations of the expected influence of nonuniform cloud structure and nonuniform surface albedo on radiative fluxes at the Arctic surface. In particular, the plane parallel biases in the surface absorptance and atmospheric transmittance are studied. The bias is defined as the difference between the real absorptance or transmittance (i.e. nonuniform conditions) averaged over a given area, and the uniform or plane parallel case with the same mean cloud optical thickness and the same mean surface albedo. The dependence of the biases is analysed with respect to the following: domain averaged values of the cloud optical thickness and surface albedo, scales of their spatial variabilities, correlation between cloud optical thickness and cloud albedo variabilities, cloud height, and the solar zenith angle. Ranges of means and standard deviations of the input parameters typical of Arctic conditions are obtained from the SHEBA experiment.

Impact of cloud timing on surface temperature and related hydroclimatic dynamics

NASA Astrophysics Data System (ADS)

Porporato, A. M.; Yin, J.

2015-12-01

Cloud feedbacks have long been identified as one of the largest source of uncertainty in climate change predictions. Differences in the spatial distribution of clouds and the related impact on surface temperature and climate dynamics have been recently emphasized in quasi-equilibrium General Circulation Models (GCM). However, much less attention has been paid to the temporal variation of cloud presence and thickness. Clouds in fact shade the solar radiation during the daytime, but also acts as greenhouse gas to reduce the emission of longwave radiation to the outer space anytime of the day. Thus it is logical to expect that even small differences in timing and thickness of clouds could result in very different predictions in GCMs. In this study, these two effects of cloud dynamics are analyzed by tracking the cloud impacts on longwave and shortwave radiation in a minimalist transient thermal balance model of the land surface. The marked changes in surface temperature due to alterations in the timing of onset of clouds demonstrate that capturing temporal variation of cloud at sub-daily scale should be a priority in cloud parameterization schemes in GCMs.

Revised models of interstellar nitrogen isotopic fractionation

NASA Astrophysics Data System (ADS)

Wirström, E. S.; Charnley, S. B.

2018-03-01

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

Stratospheric Heterogeneous Chemistry and Microphysics: Model Development, Validation and Applications

NASA Technical Reports Server (NTRS)

Turco, Richard P.

1996-01-01

The objectives of this project are to: define the chemical and physical processes leading to stratospheric ozone change that involve polar stratospheric clouds (PSCS) and the reactions occurring on the surfaces of PSC particles; study the formation processes, and the physical and chemical properties of PSCS, that are relevant to atmospheric chemistry and to the interpretation of field measurements taken during polar stratosphere missions; develop quantitative models describing PSC microphysics and heterogeneous chemical processes; assimilate laboratory and field data into these models; and calculate the extent of chemical processing on PSCs and the impact of specific microphysical processes on polar composition and ozone depletion. During the course of the project, a new coupled microphysics/physical-chemistry/ photochemistry model for stratospheric sulfate aerosols and nitric acid and ice PSCs was developed and applied to analyze data collected during NASA's Arctic Airborne Stratospheric Expedition-II (AASE-II) and other missions. In this model, detailed treatments of multicomponent sulfate aerosol physical chemistry, sulfate aerosol microphysics, polar stratospheric cloud microphysics, PSC ice surface chemistry, as well as homogeneous gas-phase chemistry were included for the first time. In recent studies focusing on AASE measurements, the PSC model was used to analyze specific measurements from an aircraft deployment of an aerosol impactor, FSSP, and NO(y) detector. The calculated results are in excellent agreement with observations for particle volumes as well as NO(y) concentrations, thus confirming the importance of supercooled sulfate/nitrate droplets in PSC formation. The same model has been applied to perform a statistical study of PSC properties in the Northern Hemisphere using several hundred high-latitude air parcel trajectories obtained from Goddard. The rates of ozone depletion along trajectories with different meteorological histories are presently being systematically evaluated to identify the principal relationships between ozone loss and aerosol state. Under this project, we formulated a detailed quantitative model that predicts the multicomponent composition of sulfate aerosols under stratospheric conditions, including sulfuric, nitric, hydrochloric, hydrofluoric and hydrobromic acids. This work defined for the first time the behavior of liquid ternary-system type-1b PSCS. The model also allows the compositions and reactivities of sulfate aerosols to be calculated over the entire range of environmental conditions encountered in the stratosphere (and has been incorporated into a trajectory/microphysics model-see above). Important conclusions that derived from this work over the last few years include the following: the HNO3 content of liquid-state aerosols dominate PSCs below about 195 K; the freezing of nitric acid ice from sulfate aerosol solutions is likely to occur within a few degrees K of the water vapor frost point; the uptake and reactions of HCl in liquid aerosols is a critical component of PSC heterogeneous chemistry. In a related application of this work, the inefficiency of chlorine injection into the stratosphere during major volcanic eruptions was explained on the basis of nucleation of sulfuric acid aerosols in rising volcanic plumes leading to the formation of supercooled water droplets on these aerosols, which efficiently scavenges HCl via precipitation.

Satellite Estimation of Spectral Surface UV Irradiance. 2; Effect of Horizontally Homogeneous Clouds

NASA Technical Reports Server (NTRS)

Krothov, N.; Herman, J. R.; Bhartia, P. K.; Ahmad, Z.a; Fioletov, V.

1998-01-01

The local variability of UV irradiance at the Earth's surface is mostly caused by clouds in addition to the seasonal variability. Parametric representations of radiative transfer RT calculations are presented for the convenient solution of the transmission T of ultraviolet radiation through plane parallel clouds over a surface with reflectivity R(sub s). The calculations are intended for use with the Total Ozone Mapping Spectrometer (TOMS) measured radiances to obtain the calculated Lambert equivalent scene reflectivity R for scenes with and without clouds. The purpose is to extend the theoretical analysis of the estimation of UV irradiance from satellite data for a cloudy atmosphere. Results are presented for a range of cloud optical depths and solar zenith angles for the cases of clouds over a low reflectivity surface R(sub s) less than 0.1, over a snow or ice surface R(sub s) greater than 0.3, and for transmission through a non-conservative scattering cloud with single scattering albedo omega(sub 0) = 0.999. The key finding for conservative scattering is that the cloud-transmission function C(sub T), the ratio of cloudy-to clear-sky transmission, is roughly C(sub T) = 1 - R(sub c) with an error of less than 20% for nearly overhead sun and snow-free surfaces. For TOMS estimates of UV irradiance in the presence of both snow and clouds, independent information about snow albedo is needed for conservative cloud scattering. For non-conservative scattering with R(sub s) greater than 0.5 (snow) the satellite measured scene reflectance cannot be used to estimate surface irradiance. The cloud transmission function has been applied to the calculation of UV irradiance at the Earth's surface and compared with ground-based measurements.

The Sensitivity of Arctic Ozone Loss to Polar Stratospheric Cloud Volume and Chlorine and Bromine Loading in a Chemistry and Transport Model

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Stolarski, R. S.; Strahan, S. E.; Polansky, B. C.

2006-01-01

The sensitivity of Arctic ozone loss to polar stratospheric cloud volume (V(sub PSC)) and chlorine and bromine loading is explored using chemistry and transport models (CTMs). A simulation using multi-decadal output from a general circulation model (GCM) in the Goddard Space Flight Center (GSFC) CTM complements one recycling a single year s GCM output in the Global Modeling Initiative (GMI) CTM. Winter polar ozone loss in the GSFC CTM depends on equivalent effective stratospheric chlorine (EESC) and polar vortex characteristics (temperatures, descent, isolation, polar stratospheric cloud amount). Polar ozone loss in the GMI CTM depends only on changes in EESC as the dynamics repeat annually. The GSFC CTM simulation reproduces a linear relationship between ozone loss and Vpsc derived from observations for 1992 - 2003 which holds for EESC within approx.85% of its maximum (approx.1990 - 2020). The GMI simulation shows that ozone loss varies linearly with EESC for constant, high V(sub PSC).

Impacts of cloud water droplets on the OH production rate from peroxide photolysis.

PubMed

Martins-Costa, M T C; Anglada, J M; Francisco, J S; Ruiz-López, Manuel F

2017-12-06

Understanding the difference between observed and modeled concentrations of HO x radicals in the troposphere is a current major issue in atmospheric chemistry. It is widely believed that existing atmospheric models miss a source of such radicals and several potential new sources have been proposed. In recent years, interest has increased on the role played by cloud droplets and organic aerosols. Computer modeling of ozone photolysis, for instance, has shown that atmospheric aqueous interfaces accelerate the associated OH production rate by as much as 3-4 orders of magnitude. Since methylhydroperoxide is a main source and sink of HO x radicals, especially at low NO x concentrations, it is fundamental to assess what is the influence of clouds on its chemistry and photochemistry. In this study, computer simulations for the photolysis of methylhydroperoxide at the air-water interface have been carried out showing that the OH production rate is severely enhanced, reaching a comparable level to ozone photolysis.

Cloud chemistry on Jupiter

NASA Technical Reports Server (NTRS)

Carlson, Barbara E.; Prather, Michael J.; Rossow, William B.

1987-01-01

Chemical equilibrium models used currently to interpret observations of Jupiter are reexamined using new data defining thermal profiles, which are substantially different from those used in the previous models. A model is developed for the chemical reactions controlling the composition of the upper troposphere on Jupiter, specifically the cloud-forming region from 10 bar to 0.1 bar, which includes, for the first time, the effects of aqueous chemistry on the composition and the vertical distribution of many measurable species in the atmosphere, identifying the factors influencing their abundances above the H2O cloud. The thermodynamic data for potential condensates on Jupiter, i.e., NH3(s), NH4SH(s), (NH4)2S(s), and H2S(s), are reexamined, recognizing the lack of data on sulfides for the temperature range of interest on Jupiter. Vertical profiles of mixing ratios for CO2, H2S, NH3, and H2, obtained for several assumed bulk abundances with respect to solar, are presented.

Aerosol Complexity and Implications for Predictability and Short-Term Forecasting

NASA Technical Reports Server (NTRS)

Colarco, Peter

2016-01-01

There are clear NWP and climate impacts from including aerosol radiative and cloud interactions. Changes in dynamics and cloud fields affect aerosol lifecycle, plume height, long-range transport, overall forcing of the climate system, etc. Inclusion of aerosols in NWP systems has benefit to surface field biases (e.g., T2m, U10m). Including aerosol affects has impact on analysis increments and can have statistically significant impacts on, e.g., tropical cyclogenesis. Above points are made especially with respect to aerosol radiative interactions, but aerosol-cloud interaction is a bigger signal on the global system. Many of these impacts are realized even in models with relatively simple (bulk) aerosol schemes (approx.10 -20 tracers). Simple schemes though imply simple representation of aerosol absorption and importantly for aerosol-cloud interaction particle-size distribution. Even so, more complex schemes exhibit a lot of diversity between different models, with issues such as size selection both for emitted particles and for modes. Prospects for complex sectional schemes to tune modal (and even bulk) schemes toward better selection of size representation. I think this is a ripe topic for more research -Systematic documentation of benefits of no vs. climatological vs. interactive (direct and then direct+indirect) aerosols. Document aerosol impact on analysis increments, inclusion in NWP data assimilation operator -Further refinement of baseline assumptions in model design (e.g., absorption, particle size distribution). Did not get into model resolution and interplay of other physical processes with aerosols (e.g., moist physics, obviously important), chemistry

Diagnosing causes of cloud parameterization deficiencies using ARM measurements over SGP site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, W.; Liu, Y.; Betts, A. K.

2010-03-15

Decade-long continuous surface-based measurements at Great Southern Plains (SGP) collected by the US Department of Energy’s Atmospheric Radiation Measurement (ARM) Climate Research Facility are first used to evaluate the three major reanalyses (i.e., ERA-Interim, NCEP/NCAR Reanalysis I and NCEP/DOE Reanalysis II) to identify model biases in simulating surface shortwave cloud forcing and total cloud fraction. The results show large systematic lower biases in the modeled surface shortwave cloud forcing and cloud fraction from all the three reanalysis datasets. Then we focus on diagnosing the causes of these model biases using the Active Remote Sensing of Clouds (ARSCL) products (e.g., verticalmore » distribution of cloud fraction, cloud-base and cloud-top heights, and cloud optical depth) and meteorological measurements (temperature, humidity and stability). Efforts are made to couple cloud properties with boundary processes in the diagnosis.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Chen; Zelinka, Mark D.; Dessler, Andrew E.

The analyses of Coupled Model Intercomparison Project phase 5 simulations suggest that climate models with more positive cloud feedback in response to interannual climate fluctuations also have more positive cloud feedback in response to long-term global warming. Ensemble mean vertical profiles of cloud change in response to interannual and long-term surface warming are similar, and the ensemble mean cloud feedback is positive on both timescales. However, the average long-term cloud feedback is smaller than the interannual cloud feedback, likely due to differences in surface warming pattern on the two timescales. Low cloud cover (LCC) change in response to interannual andmore » long-term global surface warming is found to be well correlated across models and explains over half of the covariance between interannual and long-term cloud feedback. In conclusion, the intermodel correlation of LCC across timescales likely results from model-specific sensitivities of LCC to sea surface warming.« less

Improving volcanic sulfur dioxide cloud dispersal forecasts by progressive assimilation of satellite observations

NASA Astrophysics Data System (ADS)

Boichu, Marie; Clarisse, Lieven; Khvorostyanov, Dmitry; Clerbaux, Cathy

2014-04-01

Forecasting the dispersal of volcanic clouds during an eruption is of primary importance, especially for ensuring aviation safety. As volcanic emissions are characterized by rapid variations of emission rate and height, the (generally) high level of uncertainty in the emission parameters represents a critical issue that limits the robustness of volcanic cloud dispersal forecasts. An inverse modeling scheme, combining satellite observations of the volcanic cloud with a regional chemistry-transport model, allows reconstructing this source term at high temporal resolution. We demonstrate here how a progressive assimilation of freshly acquired satellite observations, via such an inverse modeling procedure, allows for delivering robust sulfur dioxide (SO2) cloud dispersal forecasts during the eruption. This approach provides a computationally cheap estimate of the expected location and mass loading of volcanic clouds, including the identification of SO2-rich parts.

Carbon Dioxide Clouds at High Altitude in the Tropics and in an Early Dense Martian Atmosphere

NASA Technical Reports Server (NTRS)

Colaprete, Anthony; Toon, Owen B.

2001-01-01

We use a time dependent, microphysical cloud model to study the formation of carbon dioxide clouds in the Martian atmosphere. Laboratory studies by Glandor et al. show that high critical supersaturations are required for cloud particle nucleation and that surface kinetic growth is not limited. These conditions, which are similar to those for cirrus clouds on Earth, lead to the formation of carbon dioxide ice particles with radii greater than 500 micrometers and concentrations of less than 0.1 cm(exp -3) for typical atmospheric conditions. Within the current Martian atmosphere, CO2 cloud formation is possible at the poles during winter and at high altitudes in the tropics during periods of increased atmospheric dust loading. In both cases, temperature perturbations of several degrees below the CO2 saturation temperature are required to nucleate new cloud particles suggesting that dynamical processes are the most common initiators of carbon dioxide clouds rather than diabatic cooling. The microphysical cloud model, coupled to a two-stream radiative transfer model, is used to reexamine the impact of CO2 clouds on the surface temperature within a dense CO2 atmosphere. The formation of carbon dioxide clouds leads to a warmer surface than what would be expected for clear sky conditions. The amount of warming is sensitive to the presence of dust and water vapor in the atmosphere, both of which act to dampen cloud effects. The radiative warming associated with cloud formation, as well as latent heating, work to dissipate the clouds when present. Thus, clouds never last for periods much longer than several days, limiting their overall effectiveness for warming the surface. The time average cloud optical depth is approximately unity leading to a 5-10 K warming, depending on the surface pressure. However, the surface temperature does not rise about the freezing point of liquid water even for pressures as high as 5 bars, at a solar luminosity of 75% the current value.

Three-dimensional modelling of trace species in the Arctic lower stratosphere

NASA Technical Reports Server (NTRS)

Chipperfield, Martyn; Cariolle, Daniel; Simon, Pascal; Ramaroson, Richard

1994-01-01

A three-dimensional radiative-dynamical-chemical model has been developed and used to study some aspects of modeling the polar lower stratosphere. The model includes a comprehensive gas-phase chemistry scheme as well as a treatment of heterogeneous reactions occurring on the surface of polar stratospheric clouds. Tracer transport is treated by an accurate, nondispersive scheme with little diffusion suited to the representation of strong gradients. Results from a model simulation of early February 1990 are presented and used to illustrate the importance of the model transport scheme. The model simulation is also used to examine the potential for Arctic ozone destruction and the relative contributions of the chemical cycles responsible.

Cloud chemistry in eastern China: Observations from Mt. Tai

NASA Astrophysics Data System (ADS)

Collett, J. L.; Shen, X.; Lee, T.; Wang, X.; Li, Y.; Wang, W.; Wang, T.

2010-07-01

Until recently, studies of fog and cloud chemistry in China have been rare - even though the fate of China’s large sulfur dioxide emissions depends, in part, on the ability of regional clouds to support rapid aqueous oxidation to sulfate. Sulfur dioxide oxidized in regional clouds is more likely to be removed by wet deposition while sulfur dioxide that undergoes slower gas phase oxidation is expected to survive longer in the atmosphere and be transported over a much broader spatial scale. Two 2008 field campaigns conducted at Mt. Tai, an isolated peak on the NE China plain, provide insight into the chemical composition of regional clouds and the importance of various aqueous phase sulfur oxidation pathways. Single and two-stage Caltech Active Strand Cloudwater Collectors were used to collect bulk and drop size-resolved samples of cloudwater. Collected cloudwater was analyzed for key species that influence in-cloud sulfate production, including pH, S(IV), H2O2, Fe and Mn. Other major cloud solutes, including inorganic ions, total organic carbon (TOC), formaldehyde, and organic acids were also analyzed, as were gas phase concentrations of SO2, O3, and H2O2. A wide range of cloud pH was observed, from below 3 to above 6. High concentrations of cloudwater sulfate were consistent with abundant sulfur dioxide emissions in the region. Sampled clouds were also found to contain high concentrations of ammonium, nitrate, and organic carbon. Peak TOC concentrations reached approximately 200 ppmC, among the highest concentrations ever measured in cloudwater. Hydrogen peroxide was found to be the dominant aqueous phase S(IV) oxidant when cloud pH was less than approximately 5.4. Despite its fast reaction with sulfur dioxide in cloud droplets, high concentrations of residual hydrogen peroxide were measured in some clouds implying a substantial additional capacity for sulfate production. Ozone was found to be an important S(IV) oxidant when cloud pH was high. Oxidation of S(IV) by oxygen, catalyzed by Fe (III) and Mn(II) was generally the second or third fastest pathway for sulfate production. Differences between the pH and trace metal concentrations of small and large cloud droplets were observed, giving rise to aqueous phase sulfate production rates that were drop size-dependent for the ozone and metal-catalyzed pathways.

Isotopic Fractionation in Primitive Material: Quantifying the Contribution of Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Charnley, Steven

2010-01-01

Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets. It is thought, in some cases, to trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. We will present the results of models of the nitrogen, oxygen, and carbon fractionation chemistry in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred. The range of fractionation ratios expected in different interstellar molecules will be discussed and compared to the ratios measured in molecular clouds, comets and meteoritic material. These models make several predictions that can be tested in the near future by molecular line observations, particularly with ALMA.

The effects of cloud inhomogeneities upon radiative fluxes, and the supply of a cloud truth validation dataset

NASA Technical Reports Server (NTRS)

Welch, Ronald M.

1993-01-01

A series of cloud and sea ice retrieval algorithms are being developed in support of the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) Science Team objectives. These retrievals include the following: cloud fractional area, cloud optical thickness, cloud phase (water or ice), cloud particle effective radius, cloud top heights, cloud base height, cloud top temperature, cloud emissivity, cloud 3-D structure, cloud field scales of organization, sea ice fractional area, sea ice temperature, sea ice albedo, and sea surface temperature. Due to the problems of accurately retrieving cloud properties over bright surfaces, an advanced cloud classification method was developed which is based upon spectral and textural features and artificial intelligence classifiers.

POLECAT: Preparatory and modelling studies

NASA Astrophysics Data System (ADS)

Peter, T.; Müller, R.; Pawson, S.; Volkert, H.

1995-02-01

“POLECAT” is the acronym for a mission to polar stratospheric clouds, lee waves, chemistry, aerosols and transport. It constitutes a lead project of the German ozone research program sponsored by the Federal Ministry of Education and Research (BMBF). It focusses on the investigation of polar stratospheric clouds (PSCs) in the northern hemisphere with special emphasis on mesoscale effects, in particular lee waves, and their effects on polar stratospheric chemistry. The project comprises two phases. Phase 1 will support laboratory studies on PSC microphysics and heterogeneous chemistry, modelling studies on all scales, and selected field experiments concerning particle measurements as well as characterization of the direct chemical products of heterogeneous reactions. Phase 2 will cover a mission of the high-altitude aircraft Strato-2C, used for flights along streamlines across orographically perturbed regions for direct investigation of PSC effects. This paper presents some preparatory work for the upcoming project and, hence, concentrates on modelling studies including the planning strategies for the future aircraft missions.

Sensitivity of the southern West African mean atmospheric state to variations in low-level cloud cover as simulated by ICON

NASA Astrophysics Data System (ADS)

Kniffka, Anke; Knippertz, Peter; Fink, Andreas

2017-04-01

This contribution presents first results of numerical sensitivity experiments that are carried out in the framework of the project DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa). DACCIWA aims to investigate the impact of the drastic increase in anthropogenic emissions in West Africa on the local weather and climate, for example through cloud-aerosol interactions or impacts on radiation and stability. DACCIWA organised a major international field campaign in West Africa in June-July 2016 and involves a wide range of modelling activities. Several studies have shown - and first results of the DACCIWA campaign confirm - that extensive ultra-low stratus clouds form in the southern parts of West Africa (8°W-8°E, 5-10°N) at night in connection with strong nocturnal low-level jets. The clouds persist long after sunrise and have therefore a substantial impact on the surface radiation budget and consequently on the diurnal evolution of the daytime, convectively mixed boundary layer. The objective of this study is to investigate the sensitivity of the West African monsoon system and its diurnal cycle to the radiative effects of these low clouds. The study is based on a series of daily 5-day sensitivity simulations using ICON, the operational numerical weather prediction model of the German Weather Service during the months July - September 2006. In these simulations, low clouds are made transparent, by artificially lowering the optical thickness information passed on to the model's radiation scheme. Results reveal a noticeable influence of the low-level cloud cover on the atmospheric mean state of our region of interest and beyond. Also the diurnal development of the convective boundary layer is influenced by the cloud modification. In the transparent-cloud experiments, the cloud deck tends to break up later in the day and is shifted to a higher altitude, thereby causing a short-lived intensification around 11 LT. The average rainfall patterns are modified as well, though no conclusion on the long-term impact on rainfall can be made due to the forced initial conditions in the presented experiment. In the future, the impact on the development of the West African monsoon system will be assessed.

Impact of two chemistry mechanisms fully coupled with mesoscale model on the atmospheric pollutants distribution

NASA Astrophysics Data System (ADS)

Arteta, J.; Cautenet, S.; Taghavi, M.; Audiffren, N.

Air quality models (AQM) consist of many modules (meteorology, emission, chemistry, deposition), and in some conditions such as: vicinity of clouds or aerosols plumes, complex local circulations (mountains, sea breezes), fully coupled models (online method) are necessary. In order to study the impact of lumped chemical mechanisms in AQM simulations, we examine the ability of both different chemical mechanisms: (i) simplified: Condensed Version of the MOdèle de Chimie Atmosphérique 2.2 (CV-MOCA2.2), and (ii) reference: Regional Atmospheric Chemistry Model (RACM), which are coupled online with the Regional Atmospheric Modeling Systems (RAMS) model, on the distribution of pollutants. During the ESCOMPTE experiment (Expérience sur Site pour COntraindre les Modèles de Pollution et de Transport d'Emissions) conducted over Southern France (including urban and industrial zones), Intensive observation periods (IOP) characterized by various meteorological and mixed chemical conditions are simulated. For both configurations of modeling, numerical results are compared with surface measurements (75 stations) for primary (NO x) and secondary (O 3) species. We point out the impact of the two different chemical mechanisms on the production of species involved in the oxidizing capacity such as ozone and radicals within urban and industrial areas. We highlight that both chemical mechanisms produce very similar results for the main pollutants (NO x and O 3) in three-dimensional (3D) distribution, despite large discrepancies in 0D modeling. For ozone concentration, we found sometimes small differences (5-10 ppb) between the mechanisms under study according to the cases (polluted or not). The relative difference between the two mechanisms over the whole domain is only -7% for ozone from CV-MOCA 2.2 versus RACM. When the order of magnitude is needed rather than an accurate estimate, a reduced mechanism is satisfactory. It has the advantage of running faster (four times less than CPU time on SGI 3800 with 30 processors). Simplified mechanisms are really important to study cases for which an online coupling is necessary between meso-scale and chemistry models (clouds or aerosols plumes impacts, highly variable meteorology).

PHYS: Division of Physical Chemistry 258 - Properties and Origins of Cometary and Asteroidal Organic Matter Delivered to the Early Earth

NASA Technical Reports Server (NTRS)

Messenger, Scott; Nguyen, Ann

2017-01-01

Comets and asteroids may have contributed much of the Earth's water and organic matter. The Earth accretes approximately 4x10(exp 7) Kg of dust and meteorites from these sources every year. The least altered meteorites contain complex assemblages of organic compounds and abundant hydrated minerals. These carbonaceous chondrite meteorites probably derive from asteroids that underwent hydrothermal processing within the first few million years after their accretion. Meteorite organics show isotopic and chemical signatures of low-T ion-molecule and grain-surface chemistry and photolysis of icy grains that occurred in cold molecular clouds and the outer protoplanetary disk. These signatures have been overprinted by aqueously mediated chemistry in asteroid parent bodies, forming amino acids and other prebiotic molecules. Comets are much richer in organic matter but it is less well characterized. Comet dust collected in the stratosphere shows larger H and N isotopic anomalies than most meteorites, suggesting better preservation of primordial organics. Rosetta studies of comet 67P coma dust find complex organic matter that may be related to the macromolecular material that dominates the organic inventory of primitive meteorites. The exogenous organic material accreting on Earth throughout its history is made up of thousands of molecular species formed in diverse processes ranging from circumstellar outflows to chemistry at near absolute zero in dark cloud cores and the formative environment within minor planets. NASA and JAXA are currently flying sample return missions to primitive, potentially organic-rich asteroids. The OSIRIS-REx and Hayabusa2 missions will map their target asteroids, Bennu and Ryugu, in detail and return regolith samples to Earth. Laboratory analyses of these pristine asteroid samples will provide unprecedented views of asteroidal organic matter relatively free of terrestrial contamination within well determined geological context. Studies of extraterrestrial materials and returned samples are essential to understand the origins of Solar System organic material and the roles of comets and asteroids to providing the starting materials for the emergence of life.

On the imprint of surfactant-driven stabilization of laboratory breaking wave foam with comparison to oceanic whitecaps

NASA Astrophysics Data System (ADS)

Callaghan, A. H.; Deane, G. B.; Stokes, M. D.

2017-08-01

Surfactants are ubiquitous in the global oceans: they help form the materially-distinct sea surface microlayer (SML) across which global ocean-atmosphere exchanges take place, and they reside on the surfaces of bubbles and whitecap foam cells prolonging their lifetime thus altering ocean albedo. Despite their importance, the occurrence, spatial distribution, and composition of surfactants within the upper ocean and the SML remains under-characterized during conditions of vigorous wave breaking when in-situ sampling methods are difficult to implement. Additionally, no quantitative framework exists to evaluate the importance of surfactant activity on ocean whitecap foam coverage estimates. Here we use individual laboratory breaking waves generated in filtered seawater and seawater with added soluble surfactant to identify the imprint of surfactant activity in whitecap foam evolution. The data show a distinct surfactant imprint in the decay phase of foam evolution. The area-time-integral of foam evolution is used to develop a time-varying stabilization function, ϕ>(t>) and a stabilization factor, Θ, which can be used to identify and quantify the extent of this surfactant imprint for individual breaking waves. The approach is then applied to wind-driven oceanic whitecaps, and the laboratory and ocean Θ distributions overlap. It is proposed that whitecap foam evolution may be used to determine the occurrence and extent of oceanic surfactant activity to complement traditional in-situ techniques and extend measurement capabilities to more severe sea states occurring at wind speeds in excess of about 10 m/s. The analysis procedure also provides a framework to assess surfactant-driven variability within and between whitecap coverage data sets.