Ideas for Term Paper

1. Ideas for Term Paper • Biosphere-Atmosphere interactions: N fixers in Leaf-cutter ants • Oceans unsaturated wrt CaCO3, plankton skeletons may dissolve. • Paleoatmospheres – S isotopes and ore deposits All found in Science 20 Nov. 2009. 1. What are the adverse impacts on the environ or what is the benefit to forecasting weather or climate. 2. What is the chemistry or physics behind the impact. For example sources and sinks of a trace species or parameterization of a weather process such as graupel or convective clouds. Is there a quantitative relationship that is useful for future studies? 3. Is the paper well written? good or bad? right or wrong? consistent or not? Are there mistakes or steps left out? 4. Summary of what you learned from the paper,

2. Some more paper on clouds and ice. • Herman J. R., G. Labow, N. C. Hsu, D. Larko (2009), Changes in cloud and aerosol cover (1980–2006) from reflectivity time series using SeaWiFS, N7-TOMS, EP-TOMS, SBUV-2, and OMI radiance data, J. Geophys. Res., 114, D01201, doi:10.1029/2007JD009508. • Weigelt A., M. Hermann, P. F. J. van Velthoven, C. A. M. Brenninkmeijer, G. Schlaf, A. Zahn, A. Wiedensohler (2009), Influence of clouds on aerosol particle number concentrations in the upper troposphere, J. Geophys. Res., 114, D01204, doi:10.1029/2008JD009805. Waliser D., et al. (2009), • Cloud ice: A climate model challenge with signs and expectations of progress, J. Geophys. Res., 114, D00A21, doi:10.1029/2008JD010015. • 20 July 2009 | Nature | doi:10.1038/news.2009.705, How raindrops fall • Exploding drops produce miniature showers. By Fiona Tomkinson concerning Villermaux, E. & Bossa, B. Nature Phys. doi:10.1038/NPHYS1340 (2009).

3. AOSC 620Formation and Growth of Snow and Ice(Cold Cloud Microphysics)(Rogers and Yau Chapt. 9; Wallace and Hobbs, Chapt. 6)Russell Dickerson, 2009 Millions of km2 http://arctic.atmos.uiuc.edu/cryosphere/

4. AOSC 620 Formation and Growth of Ice Crystals Lecture 23 • Direct observations show that supercooled liquid cloud water is common at temperatures well below 0°C (i.e., -20°C) • Small droplets of pure H2O freeze only below temperatures of -40°C, the spontaneous freezing level. • At higher temperatures, pure water droplets freeze only if injected with tiny foreign particles called ice nuclei. • The equilibrium vapor pressure over ice is lower than that over liquid water. March 2, 2009 Getty Images / Win McNamee

5. Water favors ice.

6. Common Ice Crystal Shapes Hexagonal Plates Hexagonal Prisms Stellar Crystal/ Dendrites Ice needles

7. Goal: To shed light on the origin of the myriad of sizes and shapes of ice and snow.

8. http://www.its.caltech.edu/~atomic/snowcrystals/class/snowtypes4.jpghttp://www.its.caltech.edu/~atomic/snowcrystals/class/snowtypes4.jpg

9. H O O H H O O H H O H O Molecular Structure of Ice X-Ray and neutron diffraction experiments have shown the basic crystal structure of ice at atmospheric temperatures to consist of six oxygen atoms arranged in a hexagon. Each oxygen atom is bonded to two hydrogen atoms and (if you count H-bonding) each hydrogen is bonded to two oxygen atoms.

10. Ice in the hexagonal crystalline structure.

11. Ice Formation Generally considered to be of two types 1. Deposition - transformation from vapor to solid (the reverse is sublimation) Note that homogeneous deposition does not occur in the atmosphere. 2. Freezing - transformation from liquid to solid. Includes riming, the freezing of supercooled water droplets.

12. Qualitative Description of Freezing(homogeneous) • Consider a volume of air with T < 0°C in which water droplets are suspended. • The H2O molecules in a drop at a given instant may come into temporary alignment similar to that of an ice crystal. This lower entropy increases the free energy of the transition. • Such molecular aggregates may grow but they may also be destroyed by random molecular motions. • If an aggregate happens to grow to such a size that it is no longer affected by these thermal agitations, the entire droplet quickly freezes. The probability of growth of an aggregate to this critical size increases as T decreases. (Fleagle and Bussinger)

13. H2Ol ↔ H2Os DG = DH –T Df = 0 at 273 K DH = – 6008 J/mole (334 J/g) Df = DH/T = 334/273 = – 1.22 J/gK (22.0 J/moleK) As the temperature drops, the free energy becomes more negative. Liquid cloud water at temperatures below –40°C is rare, but supercooled water is common, and a hazard to aviation. Bottom line: Homogeneous nucleation doesn’t happen in real clouds.

14. Qualitative Description of Freezing(heterogeneous) • Add a foreign particle to droplet • The particle makes the initial growth more probable by attracting a surface layer of H2O molecules on which the ice crystal lattice can form more readily than in the interior of the liquid. • Freezing of a droplet requires that only one aggregate reach critical size.

15. Ice Nucleation Mechanisms • Heterogeneous Deposition - vapor is transformed to ice on a nucleus. • Condensation Followed by Freezing - droplet forms on a nuclei which then freezes. • Contact - nuclei makes contact with a droplet which then freezes (airplane wing). • Immersion- nuclei becomes immersed in a droplet which then freezes about the nuclei. The relative importance of the different modes has not been established. It is difficult to distinguish between deposition and freezing mechanisms. Usually refer to the process as ice nucleation and the nuclei as ice nuclei.

16. Ice Forming Nuclei

17. Important Features of Ice Nuclei • Temperature • Lattice structure - many of the most active natural nuclei have crystal structures similar to ice. • Molecular binding - • Low interfacial energy Theory not yet able to explain which is most important but, the most common natural nuclei appear to be surface clays such as kaolinite. However, it has been discovered that bacteria in decaying plant leaf material can be effective nuclei, but its importance has not yet been established. (Russ Schnell & Gabor Vali)

18. Silver iodide (AgI) in the hexagonal crystalline structure. Solubility is low ~3 × 10−7 g/100mL, at 20 °C. [Bernard Vonnegut, the older brother of the late novelist Kurt, uncovered silver iodide's weather-modifying properties as a researcher for General Electric in 1946. He later taught atmospheric science at the State University of New York at Albany before passing away in 1997. See Cat’s Cradle by K. Vonnegut] Ice in the hexagonal crystalline structure.

19. Kaolinite (Al2Si2O5(OH)4) Clay Particles Ca2+ Mg2+ K+ Acids can replace nutrient cations with H+ for efficient nucleation, but in soils, acids reduce fertility. Electron micrograph.

20. Ice Nuclei Concentration Typical concentration is one nucleus per liter of air at a temperature of -20°C, increasing by a factor of ten for each additional 4°C of cooling. However, the count on any given day may be greater or less than the typical values by an order of magnitude! Taking 104 cm-3 as the typical concentration of atmospheric aerosols, one nucleus per liter is only one aerosol particle in 107! That is, ice forming nuclei are a very rare component of atmospheric aerosols. The concentration of active ice nuclei is a strong function of temperature. ln(N) = a(T1 – T) Where N is then umber of ice nuclei, 0.3 < a <0.8, and T1 is the temp for one active ice nucleus per liter.

21. Number of active ice nuclei as a function of supersaturation. N (m-3) S (or –DT)

22. Thin film of transparent ice on outside Drop + nucleus If Nuclei Are So Rare, Why Are There So Many Crystals? Once freezing of supercooled droplets starts, it progresses rapidly through a cloud. The entire shell may explode to produce hundreds of splinters, each of which can act as a freezing nucleus As interior freezes and expands the outer shell may rupture through which a jet of water emerges and freezes to form a spike Also, collisions between crystals

23. Diffusional Growth of Ice Crystals Basic Assumptions • The surface of the crystal has uniform temperature; therefore, it has uniform vapor pressure. • The vapor pressure at an infinite distance is assumed uniform as is the temperature. • The vapor pressure and vapor density in the neighborhood of the crystal may be represented by surfaces that follow the contour of the crystal. • Beyond a certain neighborhood of the crystal these surfaces approach a spherical shape.

24. Vapor Diffusion The flux of water vapor to the crystal by diffusion occurs in the direction normal to the surfaces of constant vapor density. Therefore, near a sharp point vapor diffuses toward the point from all directions. Ice may accumulate more rapidly there than on flat surfaces. Contours of vapor density

25. Ice Crystal Growth Equations(similar to eq’s for liquid water) where Tc and T¥ are the temperatures of the crystal and environment (¥), respectively, K is the thermal conductivity of air, and C is the crystal shape factor.

26. Sphere C = r Circular disk Prolate spheroid of majorand minor semi-axes a and b Shape FactorSkip for 2009 instead read: Tao, W.-K., et al., 2009: Multi-scale modeling system: Development, applications and critical issues, Bull. Amer. Meteor. Soc. 90, 515-534. The shape factor is nothing but the capacitance of a subject. It depends upon the geometrical shape of the crystal. It has units of length. Examples: This one might be good too: Zeng, X., et al., 2009: The indirect effect of ice nuclei on atmospheric radiation. J. Atmos. Sci., 66, 41-61.

27. Note that Crystal Growth Rate Estimate Let Following the procedure used for a water droplet (S is the saturation w.r.t. liquid water) we obtain: Supersaturation wrt ice (Si) grows linearly as cloud temps drop below 273 K.

28. At T = -15°C andfor S = 1.001 Comparison of Droplet and Crystal Growth For a liquid water droplet of radius r For an ice crystal R&Y Figure 9.4

29. Saturation Vapor Pressure Relativeto Ice and Liquid Water Absolute value of es – ei peaks ~ – 12oC, but relative difference grows at lowest temps.

30. From Eq. 9.4 we see that the ice growth rate due to diffusion varies inversely with pressure and reaches a max near – 15oC at tropospheric pressures.

31. Growth of different shapes is temperature dependent Why so many forms and shapes of ice? A molecular kinetic approach is required to explain different habits/shapes.

32. Growth by Accretion Definitions (following Rogers and Yau, 1989; Glossary of Meteorology, 2000) Accretion is the capture of supercooled droplets by an ice-phase precipitation particle. If the droplets freeze immediately on contact, this forms a rimed crystal or graupel. Slow freezing creates a denser structure; e.g., hail (dia. hail > 5 mm). Coalescence is the capture of small cloud droplets by larger cloud drops. Agglomeration is the collection of smaller ice particles. Aggregation is the clumping together of ice crystals to form snowflakes

33. Accretional growth Aggregational growth Growth by Accretion - cont.,or how do we get rain and snow? The derivation of an equation for the continuous growth of ice crystals by capture of other crystals or cloud droplets would follow the same procedures as for liquid drops. Complications arise due to difficulties in prescribing the dependence of crystal fall speeds and their collection efficiencies. Snowflake sizes indicate that significant aggregation occurs only for T > -10°C. E – collection Efficiency; M condensed water mass (R&Y use m); R – radius; V – fall speed.

34. Crystal Fall Speeds Fig. 9.7 from Rogers and Yau, 1989

35. Snowflake Growth - Qualitative • Must have an appropriate number of ice nuclei to initiate freezing - 0.1 to 1 per liter at -20°C. • Crystals form around nuclei and grow by diffusion. • A few crystals grow faster and larger than their neighbors by either enhanced diffusion or by chance collisions with other crystals or droplets. • These crystals fall faster than their neighbors and grow by diffusion and by collisions with other crystals or cloud droplets until they reach a size where they can fall against an updraft and reach the ground. A snowflake of 1 cm diameter requires a cloud depth of about 1500 m.

36. Both coalescence and aggregation can happen in a Cb.Times Required for Growth is different. Droplet collision - coalescence crystal - diffusional growth

37. Precipitation Growth - Summary • Condensation-diffusion is more effective for ice clouds than for water clouds. • In warm clouds, coalescence is the major scheme for precipitation to occur. • In cold clouds, both diffusion and aggregation are important. • Ice nuclei remain mysterious. • Loss is glaciers and sea ice is a major environmental threat.

38. Stopping By Woods On A Snowy Evening Robert Frost Whose woods these are I think I know. His house is in the village though; He will not see me stopping here To watch his woods fill up with snow. My little horse must think it queer To stop without a farmhouse near Between the woods and frozen lake The darkest evening of the year. He gives his harness bells a shake To ask if there is some mistake. The only other sound's the sweep Of easy wind and downy flake. The woods are lovely, dark and deep. But I have promises to keep, And miles to go before I sleep, And miles to go before I sleep.