1. Balloelectric genesis of intermediate ions (a synopsis) Hannes Tammet, Urmas Hõrrak, Kaupo Komsaare, Markku Kulmala

2. CHRONOLOGY 1744: Richmann – air conductivity 1785: Coulomb – rediscovery of air conductivity 1834: Faraday – term ion 1840: Faraday – explanation of Seghill incident 1892: Lenard – studies of balloelectric effect 1896: Thomson & Rutherford – mobility 1899: Elster & Geitel – atmospheric small ions 1905: Langevin – large ions 1913: Christiansen – term balloelectric effect 1915: Pollock – intermediate ions 1937: Chapman – mobility of balloelectric ions 1973: Siksna – water clathrates 1999: Chaplin – water superclusters

3. Annalen der Physik 1892 Lenard, P. (1915) Über Wasserfallelektrizität und über die Oberflächenbeschaffenheit der Flüssigkeiten. Annalen der Physik 47, 463–524. Philipp Eduard Anton von Lénárd, a Magyar from Bratislava, Nobel Prize 1905

4. Previous work by the authors of the presentation

5. Experimental study of the “rain effect” on the mobility distribution of air ions. Experiments with water jet. U. Hõrrak, H. Tammet, E.Tamm, A. Mirme. Institute of Environmental Physics, University of Tartu, 18 Ülikooli St., 50090 Tartu, Estonia. E-mail: Urmas.Horrak@ut.ee Pikajärve, June 27–29. 2005

6. Hõrrak, U., Tammet, H., Aalto, P.P., Vana, M., Hirsikko, A., Laakso, L., Kulmala, M. (2006) Formation of Charged Nanometer Aerosol Particles Associated with Rainfall: Atmospheric Measurements and Lab Experiment. In Report Series in Aerosol Science, Helsinki, 81, 180-185. ?

8. Size of the balloelectric ions H. Tammet, U. Hõrrak, M. Kulmala Pühajärve 2008

9. 2009

10. Raintime bursts of intermediate ions

11. Tartu, Tähe 4 attic storey and roof

12. Precipitation A rainy day in Tartu, April 2004

15. A rainy day in Hyytiälä, 6 December 2006. Air temperature +5.0…+8.5 ºC and RH 83…96% during the day.

16. Average mobility distribution of negative atmospheric ions during the rain of different intensity in Hyytiälä.

17. Diameter = f (charge, mobility) THE PROBLEM: singly or multiply charged particles? We can measure the mobility. How to estimate the size?

18. Rayleigh limit charge Half of the Rayleigh limit Single charge Mobility of a typical balloelectric ion

19. Singly charged particles: The concentration decreases, but the mobility does not change. Multiply charged particles: The number concentration does not change, the mobility and the charge concentration decrease proportionally to each other. Idea of the neutralization experiment:

20. REPEATED MEASUREMENTS AT FOUR LEVELS OF NEUTRALIZATION

21. Old particles are neutralized and do not affect this curve Large mobility → small size Old particles are waned due to the evaporation Small ions dn /d (log Z) cm -3 Results of experiments: mobility decreases a little, far from the proportionality Concentration of neutralizing small ions, cm -3

22. Conclusion: The balloelectric ions are mostly the singly charged nanometer particles and diameter = f (1 e, mobility)

23. Composition: water or dry residue of a droplet?

24. The rainwater contains about 10 mg/l of TDS (total dissolved solids). The waterworks water used in the experiments contains 550 mg/l of TDS. Conclusion: the dry residues of the waterworks water droplets should have 3-4 times bigger diameters when compared with the dry residues of the rainwater droplets. Let’s compare…

25. Comparison of measurements at Hyytiälä SMEAR station (left) and results of the experiment with water jet (right) Size distributions of negative ions Rain event. Hyytiälä Laboratory water-jet. Tartu

26. Blue – natural rain at Hyytiälä, green – natural rain at Tartu, red – laboratory experiment splashing the waterworks water

27. Conclusion: The size of balloelectric ions does not depend on the TDS and they cannot be considered as dry residues of droplets.

28. How the balloelectric ions are created ?

29. Critical point: the surface tension requires a lot of energy to be saved in the surface of nanodroplets, where is the source? The speed of large raindrops is 6-7 m/s. If 100% of the kinetic energy is to be transformed into the surface energy then the required speed is: Dispersion of a raindrop fully into nanodrops seems to be impossible. However, the law of energy balance cannot exlude creating of a limited number of nanodrops. The nanometer scale processes during the splashing are hard to study and the mechanism of creating the nanodrops is almost unknown. d : nm 10100100010000 v : m/s 29090299

30. Nobel prize winner 2002 John B. Fenn studied generating of ions of dissolved substances. (ESI = electrospray ionization) Wide field of ESI applications motivated research of Coulomb dispersion of droplets. Indeed, the fragments can be very small. However, they are MULTIPLY CHARGED

31. Why they are not instantly evaporated ?

32. The characteristic evaporation time of 2.5 nm liquid water droplets at 10ºC and 100% relative humidity does not exceed 1 μs according to the kinetic theory. This time is about 7 magnitudes less than the estimated time of passage of the air to the instrument and 5 magnitudes less than the time of passage of the air through the analyzer. If these estimates were true then the observation of 2.5 nm droplets in the described measurements would be recognized as impossible.

33. WATER JET OPENWATER JET CLOSED fine + coarse + coarse – fine –

34. Conclusion: The balloelectric ions are not composed of the liquid water. ICE CRYSTALS ? CLUSTERS ?

35. Lenard 1915 n = 21 d = 1.06 Z = 0.96 SIZE OF A BALLOELECTRIC ION CORRESPONDS TO 200…300 MOLECULES OF WATER

36. Chaplin’s superclusters?

37. Number of water molecules n = (πρd 3 / 6) / (18 u) n  17.5 (d / 1 nm) 3 n = 280 follows d = 2.52 nm. The water clusters known in mass spectrometry have maximum n = 21. Chaplin did not use mass spectrometry and does not refer experts like Beyer, Kebarle, Keesee and Castleman. He studied clusters not in the gas but in the water environment. Chaplin’s magic icosahedron has n = 20×14 = 280

38. LINKS http://www.lsbu.ac.uk/water http://www.waterjournal.org http://www.mdpi.com/journal/water http://water.sigmaxi.org/?page_id=39 the last site contains a list of more than 60 journals related to water and hydrology

39. Pictures from Chaplin’s web: Stable supercluster A superlcuster can break down during long time

40. Distribution of balloelectric ions according to the number of water molecules A, B, C ja D are levels of neutralizing ionization in the laboratory experiment

41. Final conclusions: Nature of rain-induced intermediate ions seems to be the same as nature of balloelectric ions in laboratory and near waterfalls. We proved that the balloelectric ions are probably 1) singly charged nanoparticles, 2) not dry residues of droplets, 3) not composed of classic liquid water, 4) of size the Chaplin's 280-superclusters. We still don't know 1) their actual composition, 2) how they are created, 3) why they are not instantly evaporated.

42. Thank you for attention ! ? ? ? ? ? ? ? CONCLUSION