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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

The Effect of Temperature and Solution pH on the Nucleation of Tetragonal Lysozyme Crystals

Part of the challenge of macromolecular crystal growth for structure determination is obtaining crystals with a volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature, and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over 1 week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable, however, was pH; crystal numbers changed by two orders of magnitude over the pH range 4.0-5.2. Crystal size also varied with solution conditions, with the largest crystals obtained at pH 5.2. Having optimized the crystallization conditions, we prepared a batch of crystals under the same initial conditions, and 50 of these crystals were analyzed by x-ray diffraction techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

Judge, Russell A.↗
NASA NTRS2000

Cross-Linking Studies of Lysozyme Nucleation

Tetragonal chicken egg white crystals consist of 4(sub 3) helices running in alternating directions, the helix rows having a two fold symmetry with each other. The unit cell consists of one complete tetrameric turn from each of two adjacent helices (an octamer). PBC analysis indicates that the helix intermolecular bonds are the strongest in the crystal, therefore likely formed first. AFM analysis of the (110) surface shows only complete helices, no half steps or bisected helices being found, while AFM line scans to measure the growth step increments show that they are multiples of the 4(sub 3) helix tetramer dimensions. This supports our thesis that the growth units are in fact multiples of the four molecule 4(sub 3) helix unit, the "average" growth unit size for the (110) face being an octamer (two turns about the helix) and the (101) growth unit averaging about the size of a hexamer. In an effort to better understand the species involved in the crystal nucleation and growth process, we have initiated an experimental program to study the species formed in solution compared to what is found in the crystal through covalent cross-linking studies. These experiments use the heterobifunctional cross-linking agent aminoethyl-4-azidonitroanaline (AEANA). An aliphatic amine at one end is covalently attached to the protein by a carbodiimide-mediated reaction, and a photo reactive group at the other can be used to initiate crosslinking. Modifications to the parent structure can be used to alter the distance between the two reactive groups and thus the cross-linking agents "reach". In practice, the cross-linking agent is first coupled to the asp101 side chain through the amine group. Asp101 lies within the active site cleft, and previous work with fluorescent probes had shown that derivatives at this site still crystallize in the tetragonal space group. This was also found to be the case with the AEANA derivative, which gave red tetragonal crystals. The protein now has a reactive group that can be photoactivated at a specific point in the nucleation or crystal growth process to "capture" protein molecules bound within reach of the crosslinking agent. If those bound protein molecules have a defined geometric relationship with the capturing molecule, such as would be found in a crystal, then the photoreacted cross-linking site should be consistent. Random protein interactions, typical of an amorphous precipitate or interaction, would show a random cross-linking reaction. The results of these and other experiments will be presented.

Forsythe, Elizabeth↗
NASA NTRS2000

Fluorescence Studies of Protein Crystal Nucleation

One of the most powerful and versatile methods for studying molecules in solution is fluorescence. Crystallization typically takes place in a concentrated solution environment, whereas fluorescence typically has an upper concentration limit of approximately 1 x 10(exp -5)M, thus intrinsic fluorescence cannot be employed, but a fluorescent probe must be added to a sub population of the molecules. However the fluorescent species cannot interfere with the self-assembly process. This can be achieved with macromolecules, where fluorescent probes can be covalently attached to a sub population of molecules that are subsequently used to track the system as a whole. We are using fluorescence resonance energy transfer (FRET) to study the initial solution phase self-assembly process of tetragonal lysozyme crystal nucleation, using covalent fluorescent derivatives which crystallize in the characteristic P432121 space group. FRET studies are being carried out between cascade blue (CB-lys, donor, Ex 376 nm, Em 420 nm) and lucifer yellow (LY-lys, acceptor, Ex 425 nm, Em 520 nm) asp101 derivatives. The estimated R0 for this probe pair, the distance where 50% of the donor energy is transferred to the acceptor, is approximately 1.2 nm, compared to 2.2 nm between the side chain carboxyls of adjacent asp101's in the crystalline 43 helix. The short CB-lys lifetime (approximately 5 ns), coupled with the large average distances between the molecules ((sup 3) 50 nm) in solution, ensure that any energy transfer observed is not due to random diffusive interactions. Addition of LY-lys to CB-lys results in the appearance of a second, shorter lifetime (approximately 0.2 ns). Results from these and other ongoing studies will be discussed in conjunction with a model for how tetragonal lysozyme crystals nucleate and grow, and the relevance of that model to microgravity protein crystal growth

Pusey, Marc L.↗
NASA NTRS2000

Quantifying Main Trends in Lysozyme Nucleation: The Effect of Precipitant Concentration and Impurities

Full factorial experiment design incorporating multi-linear regression analysis of the experimental data allows the main trends and effects to be quickly identified while using only a limited number of experiments. These techniques were used to identify the effect of precipitant concentration and the presence of an impurity, the physiological lysozyme dimer, on the nucleation rate and crystal dimensions of the tetragonal form of chicken egg white lysozyme. Increasing precipitant concentration was found to decrease crystal numbers, the magnitude of this effect also depending on the supersaturation. The presence of the dimer generally increased nucleation. The crystal axial ratio decreased with increasing precipitant concentration independent of impurity.

Burke, Michael W.↗
NASA NTRS1999

Measurements of Nucleation-Mode Particle Size Distributions in Aircraft Plumes during SULFUR 6

This report summarizes the participation of the University of Denver in an airborne measurement program, SULFUR 6, which was undertaken in late September and early October of 1998 by the Deutsches Zentrum fur Luft und Raumfahrt (DLR). Scientific findings from two papers that have been published or accepted and from one manuscript that is in preparation are presented. The SULFUR 6 experiment was designed to investigate the emissions from subsonic aircraft to constrain calculations of possible atmospheric chemical and climatic effects. The University of Denver effort contributed toward the following SULFUR 6 goals: (1) To investigate the relationship between fuel sulfur content (FSC--mass of sulfur per mass of fuel) and particle number and mass emission index (El--quantity emitted per kg of fuel burned); (2) To provide upper and lower limits for the mass conversion efficiency (nu) of fuel sulfur to gaseous and particulate sulfuric acid; (3) To constrain models of volatile particle nucleation and growth by measuring the particle size distribution between 3 and 100 nm at aircraft plume ages ranging from 10(exp -1) to 10(exp 3) s; (4) To determine microphysical and optical properties and bulk chemical composition of soot particles in aircraft exhaust; and (5) To investigate the differences in particle properties between aircraft plumes in contrail and non-contrail situations. The experiment focused on emissions from the ATTAS research aircraft (a well characterized, but older technology turbojet) and from an in-service Boeing 737-300 aircraft provided by Lufthansa, with modem, high-bypass turbofan engines. Measurements were made from the DLR Dassault Falcon 900 aircraft, a modified business jet. The Atmospheric Effects of Aviation Program (AEAP) provided funding to operate an instrument, the nucleation-mode aerosol size spectrometer (N-MASS), during the SULFUR 6 campaign and to analyze the data. The N-MASS was developed at the University of Denver with the support of NOAA's Office of Global Programs and NASA's AEAP and measures particle size distributions in the 4-100 nm range.

Brock, Charles A.↗
NASA NTRS2000

A Mechanistic Study of Nucleate Boiling Heat Transfer Under Microgravity Conditions

Experimental studies of growth and detachment processes of a single bubble and multiple bubbles formed on a heated surface have been conducted in the parabola flights of KC-135 aircraft. Distilled water and PF5060 were used as the test liquids. A micro-fabricated test surface was designed and built. Artificial cavities of diameters 10 microns, 7 microns and 4 microns were made on a thin polished Silicon wafer that was electrically heated by a number of small heating elements on the back side in order to control the surface superheat. Bubble growth period, bubble size and shape from nucleation to departure were measured under subcooled and saturation conditions. Significantly larger bubble departure diameters and bubble growth periods than those at earth normal gravity were observed. Bubble departure diameters as large as 20 mm for water and 6 mm for PF5060 were observed as opposed to about 3 mm for water and less than 1 mm for PF5060 at earth normal gravity respectively. It is found that the bubble departure diameter can be approximately related to the gravity level through the relation D(sub d) proportional 1/g(exp 1/2). For water,the effect of wall superheat and liquid subcooling on bubble departure diameter is found to be small.The growth periods are found to be very sensitive to liquid subcooling at a given wall superheat. However,the preliminary results of single bubble dynamics using PF5060 showed that the departure diameter increases when wall superheat is elevated at the same gravity and subcooling. Growth period of single bubbles in water has been found to vary as t(sub g) proportional g(exp -.93). For water, when the magnitude of horizontal gravitational components was comparable to that of gravity normal to the surface, single bubbles slid along the heater surface and departed with smaller diameter at the same gravity level in the direction normal to the surface. For PF5060, even a very small horizontal gravitational component caused the sliding of bubble along the surface. The numerical simulation has been carried out by solving under the condition of axisymmetry, the mass, momentum, and energy equations for the vapor and the liquid phases. In the model the contribution of micro-layer has been included and instantaneous shape of the evolving vapor-liquid interface is determined from the analysis. Consistent with the experimental results, it is found that effect of reduced gravity is to stretch the growth period and bubble diameter It is found that effect of reduced gravity is to stretch the growth period and bubble diameter at departure. The numerical simulations are in good agreement with the experimental data for both the departure diameters and the growth periods. In the study on dynamics of multiple bubbles, horizontal merger of 2,3 4,and 5 bubbles was observed. It is found that after merger of 2 and 3 bubbles the equivalent diameter of the detached bubble is smaller than that of a single bubble departing at the same gravity level. During and after bubble merger, liquid still fills the space between the vapor stems so as to form mushroom type bubbles. The experimental and numerical studies conducted so far have brought us a step closer to prediction of nucleate boiling heat fluxes under low gravity conditions. Preparations for a space flight are continuing.

Dhir, V. K.↗
NASA NTRS2001

Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

Kelton, K. F.↗
NASA NTRS1995

Dynamics of Vapour Bubbles in Nucleate Boiling: Basic Equations of Bubble Evolution - 1

We consider the behaviour of a vapour bubble formed at a nucleation site on a heated horizontal wall. There is no forced convection of an ambient liquid, and the bubble is presumably separated from the wall by a thin liquid microlayer. The energy conservation law results in a variational equation for the mechanical energy of the whole system consisting of the bubble and liquid. It leads to a set of two strongly nonlinear equations which govern bubble expansion and motion of its centre of mass. A supplementary equation to find out the vapour temperature follows from consideration of heat transfer to the bubble, both from the bulk of surrounding liquid and through the microlayer. The average thickness of the microlayer is shown to increase monotonously with time as the bubble meniscus spreads along the wall. Bubble expansion is driven by the pressure head between vapour inside and liquid far away from the bubble, with due allowance for surface tension and gravity effects. It is resisted by inertia of liquid being placed into motion as the bubble grows. The inertia originates also a force that presses the bubble to the wall. This force is counteracted by the buoyancy and an effective surface tension force that tends to transform the bubble into a sphere. The analysis brings about quite a new formulation of the familiar problem of bubble growth and detachment under conditions of nucleate pool boiling.

Buyevich, Yu A.↗
NASA NTRS1995

Dynamics of Vapour Bubbles in Nucleate Boiling: Evolution of Thermally Controlled Bubbles - 2

The previously developed dynamic theory of growth and detachment of vapour bubbles under conditions of nucleate pool boiling is applied to study motion and deformation of a bubble evolving at a single nucleation site. The bubble growth is presumed to be thermally controlled, and two components of heat transfer to the bubble are accounted of: the one from the bulk of surrounding liquid and the one due to heat conduction across a liquid microlayer formed underneath the bubble. Bubble evolution is governed by the buoyancy and an effective surface tension force, both the forces making the bubble centre of mass move away from the wall and, thus, assisting its detachment. Buoyancy-controlled and surface-tension-controlled regimes are considered separately in a meticulous way. The duration of the whole process of bubble evolution till detachment, the rate of growth, and the bubble departure size are found as functions of time and physical and operating parameters. Some repeatedly observed phenomena, such as an influence of gravity on the growth rate, are explained. Inferences of the model agree qualitatively with available experimental evidence, and conclusions pertaining to the dependence on gravity of the bubble radius at detachment and the whole time of the bubble development when being attached to the wall are confirmed quantitatively.

Buyevich, Yu A.↗
NASA NTRS2002

Nucleation and Growth According to Lysozyme

How does one take a molecule, strongly asymmetric in both shape and charge distribution, and assemble it into a crystal? We propose a model for the nucleation and crystal growth process for tetragonal lysozyme that may be very germane to other monomeric proteins. The first species formed is postulated to be a dimer. Through repeating associations involving the same intermolecular interactions this becomes the 4(sub 3) helix, that in turn serves as the basic unit for nucleation and crystal growth. High salt attenuates surface charges while promoting hydrophobic interactions. Symmetry facilitates helix self-association. Assembly stability is enhanced when a four helix structure is obtained, with each bound to two neighbors. Only two unique interactions are required. The first are those for helix formation, where the dominant interaction is the intermolecular bridging anion. The second is the anti-parallel side-by-side helix-helix interaction, guided by alternating pairs of symmetry related salt bridges along each side. At this stage all eight unique positions of the P4(sub 3)2(sub 1)2(sub 1) unit cell are filled. From the above, the process is one of a) attenuating the most strongly interacting groups, such that b) the molecules begin to self-associate in defined patterns, so that c) symmetry is obtained, which d) propagates as a growing crystal. Simple and conceptually obvious in hindsight, this tells much about what we are empirically doing when we crystallize macromolecules. By adjusting the solution parameters we are empirically balancing the intermolecular interactions, preferentially attenuating the dominant strong (for lysozyme the charged groups) while strengthening the lesser strong (hydrophobic) interactions. Lysozyme is atypical in the breadth of its crystallization conditions; many proteins only crystallize under narrowly defined conditions, pointing to the criticality of the empirical balancing process. Lack of a singularly defined association pathway leads to formation of multiple species, i.e., amorphous precipitation. Weak interactions, such as hydrogen bonds, are promiscuous, serving to strengthen rather than define specific interactions. Participation in an interaction sequesters that surface from subsequent interactions, and we expect the strongest bonds to form first. When two molecules self associate the resulting species will have an axis of symmetry. Subsequent interactions between two associated species having equivalent interactions will also have symmetry. Only a few unique sets of interactions are required to give any of the commonly found space groups for monomeric proteins. This model and what it suggests will be discussed.

Pusey, Marc L.↗
NASA NTRS2002

Midlatitude Cirrus Clouds Derived from Hurricane Nora: A Case Study with Implications for Ice Crystal Nucleation and Shape

Hurricane Nora traveled up the Bala Peninsula coast in the unusually warm El Nino waters of September 1997, until rapidly decaying as it approached Southern California on 24 September. The anvil cirrus blowoff from the final surge of tropical convection became embedded in subtropical flow that advected the cirrus across the western US, where it was studied from the Facility for Atmospheric Remote Sensing (FARS) in Salt Lake City, Utah. A day later, the cirrus shield remnants were redirected southward by midlatitude circulations into the Southern Great Plains, providing a case study opportunity for the research aircraft and ground-based remote sensors assembled at the Clouds and Radiation Testbed (CART) site in northern Oklahoma. Using these comprehensive resources and new remote sensing cloud retrieval algorithms, the microphysical and radiative cloud properties of this unusual cirrus event are uniquely characterized. Importantly, at both the FARS and CART sites the cirrus generated spectacular optical displays, which acted as a tracer for the hurricane cirrus, despite the limited lifetimes of individual ice crystals. Lidar polarization data indicate widespread regions of uniform ice plate orientations, and in situ particle masticator data show a preponderance of pristine, solid hexagonal plates and columns. It is suggested that these unusual aspects are the result of the mode of cirrus particle nucleation, presumably involving the lofting of sea-salt nuclei in thunderstorm updrafts into the upper troposphere. This created a reservoir of haze particles that continued to produce halide-saltcontaminated ice crystals during the extended period of cirrus cloud maintenance. The reference that marine microliters are embedded in the replicas of ice crystals collected over the CART site points to the longevity of marine effects. Various nucleation scenarios proposed for cirrus clouds based on this and other studies, and the implications for understanding cirrus radiative properties or a global scale, are discussed.

Sassen, Kenneth↗
NASA NTRS2002

A Proposed Model for Protein Crystal Nucleation and Growth

How does one take a molecule, strongly asymmetric in both shape and charge distribution, and assemble it into a crystal? We propose a model for the nucleation and crystal growth process for tetragonal lysozyme, based upon fluorescence, light, neutron, and X-ray scattering data, size exclusion chromatography experiments, dialysis kinetics, AFM, and modeling of growth rate data, from this and other laboratories. The first species formed is postulated to be a 'head to side' dimer. Through repeating associations involving the same intermolecular interactions this grows to a 4(sub 3) helix structure, that in turn serves as the basic unit for nucleation and subsequent crystal growth. High salt attenuates surface charges while promoting hydrophobic interactions. Symmetry facilitates subsequent helix-helix self-association. Assembly stability is enhanced when a four helix structure is obtained, with each bound to two neighbors. Only two unique interactions are required. The first are those for helix formation, where the dominant interaction is the intermolecular bridging anion. The second is the anti-parallel side-by-side helix-helix interaction, guided by alternating pairs of symmetry related salt bridges along each side. At this stage all eight unique positions of the P4(sub3)2(sub 1),2(sub 1) unit cell are filled. The process is one of a) attenuating the most strongly interacting groups, such that b) the molecules begin to self-associate in defined patterns, so that c) symmetry is obtained, which d) propagates as a growing crystal. Simple and conceptually obvious in hindsight, this tells much about what we are empirically doing when we crystallize macromolecules. By adjusting the growth parameters we are empirically balancing the intermolecular interactions, preferentially attenuating the dominant strong (for lysozyme the charged groups) while strengthening the lesser strong (hydrophobic) interactions. In the general case for proteins the lack of a singularly defined association pathway may lead to formation of multiple species, i.e., amorphous precipitation. Weak interactions, such as hydrogen bonds, are promiscuous, serving to strengthen rather than define specific interactions. Participation in an interaction sequesters that surface from subsequent interactions, and we expect the strongest bonds to form first. This model, its basis, how it fits into the currently understood osmotic second virial coefficient approach to crystallization, and what it suggests will be discussed.

Pusey, Marc↗
NASA NTRS2003

Time and Space Resolved Heat Transfer Measurements Under Nucleate Bubbles with Constant Heat Flux Boundary Conditions

Investigations into single bubble pool boiling phenomena are often complicated by the difficulties in obtaining time and space resolved information in the bubble region. This usually occurs because the heaters and diagnostics used to measure heat transfer data are often on the order of, or larger than, the bubble characteristic length or region of influence. This has contributed to the development of many different and sometimes contradictory models of pool boiling phenomena and dominant heat transfer mechanisms. Recent investigations by Yaddanapyddi and Kim and Demiray and Kim have obtained time and space resolved heat transfer information at the bubble/heater interface under constant temperature conditions using a novel micro-heater array (10x10 array, each heater 100 microns on a side) that is semi-transparent and doubles as a measurement sensor. By using active feedback to maintain a state of constant temperature at the heater surface, they showed that the area of influence of bubbles generated in FC-72 was much smaller than predicted by standard models and that micro-conduction/micro-convection due to re-wetting dominated heat transfer effects. This study seeks to expand on the previous work by making time and space resolved measurements under bubbles nucleating on a micro-heater array operated under constant heat flux conditions. In the planned investigation, wall temperature measurements made under a single bubble nucleation site will be synchronized with high-speed video to allow analysis of the bubble energy removal from the wall.

Myers, Jerry G.↗
NASA NTRS1994

Nucleation of Crystals From Solution in Microgravity (USML-1 Glovebox (GBX) Investigation)

A new method for initiating nucleation from solutions in microgravity which avoids nucleation on container walls and other surfaces is described. This method consists of injecting a small quantity of highly concentrated, heated solution into the interior of a lightly supersaturated, cooler host gowth solution. It was tested successfully on USML-I, producing a large number of LAP crystals whose longest dimension averaged 1 mm.

Kroes, Roger L.↗
NASA NTRS2003

Surface Characterization of 3C-SiC Mesa Heterofilms: Evidence for Growth by Edge/Corner Nucleation Mechanism

This paper presents the first detailed observations of unique surface morphologies of 3C-Sic films grown on 4W6H-SIC mesas by the step-free surface heteroepitaxy technique. The top surfaces of 3C-Sic films were extensively studied by optical microscopy and atomic force microscopy (AFM) as both film thickness (i.e,, growth time) and growth temperature (i.e., terrace nucleation rate) were varied following complete coverage of each 4W6H mesa by an initial 3C-Sic film. Almost all surface steps observed by AFM were 0.25 nm, the height of a single Si-C bilayer. However, strikingly different step patterns were observed, suggesting that radically different processes dominate the nucleation of new 3C-Sic bilayers on top of existing 3C-Sic film surfaces.

Trunek, Andrew J.↗
NASA NTRS2003

Nucleation and Crystallization as Induced by Bending Stress in Lithium Silicate Glass Fibers

Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.

Reis, Signo T.↗
NASA NTRS2005

Time and Space Resolved Heat Flux Measurements During Nucleate Boiling with Constant Heat Flux Boundary Conditions

The lack of temporally and spatially resolved measurements under nucleate bubbles has complicated efforts to fully explain pool-boiling phenomena. The objective of this current work was to acquire time and space resolved temperature distributions under nucleating bubbles on a constant heat flux surface using a microheater array with 100x 100 square microns resolution, then numerically determine the wall to liquid heat flux. This data was then correlated with high speed (greater than l000Hz) visual recordings of The bubble growth and departure from the heater surface acquired from below and from the side of the heater. The data indicate that microlayer evaporation and contact line heat transfer are not major heat transfer mechanisms for bubble growth. The dominant heat transfer mechanism appears to be transient conduction into the liquid as the liquid rewets the wall during the bubble departure process.

Yerramilli, Vamsee K.↗
NASA NTRS2005

Influence of Nucleation Mechanisms on the Radiative Properties of Deep Convective Clouds and Subvisible Cirrus in CRYSTAL/FACE

During the past few years we have conducted work on several different topics, as reflected by our publications. As one of the Co-Project scientists for The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL FACE) we worked to help design the mission and then conduct it in the field. Another major activity during the past two years has been to pull together various groups to formulate plans for follow on missions to CRYSTAL FACE. We organized a workshop at the University of Colorado during the summer of 2003 to assess the best locations for future missions. Working with a group of about 10 scientists from around the country we prepared a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) that outlined the rationale, locations, strategy to accomplish the goals, and possible payloads for a set of three tropical missions. We also prepared background materials for various NRAs being prepared at NASA Headquarters for missions in Costa Rica, Darwin and Guam. In conjunction with the group at NASA Ames we have helped build a new numerical model for deep convection and have applied that model to simulate the CRYSTAL data. Our goal in particular has been to better understand how convection distributes water vapor isotopes. CRYSTAL observations of water isotopes are very different from those suggested by previous workers who assumed the isotopes would obey Rayleigh fractionation. The water isotope study has several implications. First it is a check on the realism of the deep convection model. Second, the isotopes are a measure of the precipitation removal in the atmosphere. Hence they provide a constraint on a parameter that is difficult to otherwise measure. Finally it has been suggested that isotopes may be the key to unraveling the water transport into the stratosphere and upper troposphere. Such transport is critical both for the radiation balance and for stratospheric chemistry. Ours is the first model that is able to treat this transport. Our initial results have just been submitted to Geophys. Res. Lett (Smith et al., 2005). Essentially we are able to explain the vertical profiles of isotopes in the tropical tropopause transition layer. We are also able to account for stratospheric humidity and isotope abundances with this model. We have also been heavily involved in trying to improve our understanding of nitric acid condensation on ice. Gao et al (2004) have shown that water supersaturations above ice occur when the atmosphere is supersaturated with respect to nitric acid trihydrate. As one of the co-authors of that work, we suggested the mechanism that may explain why this is occurring. Essentially, ice does not like to grow near unit supersaturation, but does so because the water molecules can find sites on the ice surface to attach themselves to before they fly off the ice surface. This phenomena was well known in the 1960s when it was a source of debate about whether condensation and evaporation coefficients for ice would be the same. Evaporation does not require any molecular orientation, while condensation does, so it was possible that the coefficients would differ. They don't differ because the water molecules rapidly move across the surface and find places to attach. Nitric acid may be occupying these preferred sites and therefore the water molecules can't find a desirable place to attach. We anticipate that this research will be the subject of laboratory work during the coming few years. Another possibility that has been suggested is that cubic ice is forming in clouds. We have measured the vapor pressure of cubic ice, and plan to publish that result in the next few months. We have also been working on additional aspects of the condensation of nitric acid on ice. With Y. Kondo we studied the condensation of NOy on ice using the SOLVE data. Gamblin et al. have continued this work. The CRYSTAL NOy and HNO, groups have shown th their data can be fit using standard Langmuir isotherms as suggested in some, but not all, laboratory studies. We have found in the SOLVE data set that this is not the case. Moreover some laboratory studies show there are important kinetic effects that may be occurring in the atmosphere limiting the transfer of nitric acid to the ice. The SOLVE data seem consistent with these studies. We are currently re-analyzing the CRYSTAL data to look for these kinetic effects. There are a number of implications of these studies. One of the more interesting is that the nitric acid coating on ice can be used as a cloud clock to determine how long the cloud parcel has been in existence. We have also been involved with several laboratory studies. We have worked to improve the database on ice optical constants, which are critical for remote sensing. We have also studied the ways in which ice nucleates on clays. We suspect now that the standard theories used for depositional ice nucleation are completely incorrect. Further work will be needed to develop a new theory.

Toon, Owen B.↗