1. Estimating of neutral nanoparticles according to measurements of intermediate ions Hyytiälä 20130611 Hannes.Tammet@ut.ee Kaupo Komsaare & Urmas Hõrrak University of Tartu Estimating of neutral nanoparticles according to measurements of intermediate ions

2. The presentation is based on a published paper:

3. Aim of the presentation is to explain the concept of RCGP and one special figure SymbolQuantityUnit n(d) Size distribution of particle concentration dN / dd cm –3 nm –1 n 1 (d) Size distribution of + or – particle concentration dN 1 / dd cm –3 nm –1 NB: n(d) = n 0 (d) + 2 n 1 (d) GR(d)Growth ratenm s –1 GF(d)Growth flux (or apparent nucleation rate J ) GR(d) × n(d) cm –3 s –1 GP(d)Growth product GF(d) dt cm –3 N 1(3–7) Concentration of charged particles of one polarity in diameter range of 3–7 nm cm –3 N 1(3–7) Upper limit of N 1(3–7) cm –3 w(t, N 1(3–7) )Condition function if (N 1(3–7) (t) < N 1(3–7) ) then 1 else 0 GP w (d, N 1(3–7) ) Conditional growth product w(t, N 1(3–7) ) GF(d) dt cm –3 RCGP(d, N 1(3–7) ) Relative Contribution to Growth Product GP w (d, N 1(3–7) ) / GP(d) 0 = neutral1 = charged (one polarity)

4. The figure will suggest that the burst events in Tartu generate about 1/3 of new particles in diameter range of 3…7 nm and about 2/3 of new particles are generated during quiet periods of NPF. WARNING: the special figure is based on very rough approximations and the conclusion above is rather a hypothesis. Why 3…7 nm?

5. PREVIEW Relative Contribution to the Growth Product

6. REPLACEMENT FOR INTRODUCTION: fragments of the published paper

7. STATEMENTS: High concentrations of intermediate ions appear during burst events of NPF, which typically last a few hours. The quiet periods between the events can last for weeks. During quiet periods the old burst-generated nanoparticles are grown to larger sizes, coagulated with large particles or deposited. However, intermediate ions are still found in the air during the long pauses between the NPF events which indicates that atmospheric aerosol nucleation is continuous.

8. Theoretical model is based on general equations copied from: Iida, K., Stolzenburg, M. R., McMurry, P. H., and Smith, J. N.: Estimating nanoparticle growth rates from size-dependent charged fractions: Analysis of new particle formation events in Mexico City, J. Geophys. Res., 113, D05207, 2008. NB: we assume steady state, no time dependence Concentration of small ions Attachment coefficient Sink on background aerosol particles Index 0 marks neutrals and 1 marks the charged particles of one polarity + or – Growth flux Attachment coefficients

9. Empiric data is acquired from the paper: Tammet, H., Komsaare, K., and Hõrrak, U.: Intermediate Ions in the Atmosphere, Atmos. Res., In Press, http://dx.doi.org/10.1016/j.atmosres.2012.09.009, 2012. n 1 ( d ) (cm –3 nm –1 )

10. Empiric equations are acquired from the paper: Tammet, H. and Kulmala, M.: Empiric equations of coagulation sink of fine nanoparticles on background aerosol optimized for boreal zone, Boreal Environ. Res., should appear in Press 2013. Concentration of particles in range of 50…500 nm (typical values 1000 cm –3 at Hyytiälä and 2000 cm –3 in Tartu)

11. The second general equation was: Let’s assume that  GR 1 is a constant,  N 50–500 is known,  n 1 (d) is known. In this case Unfortunately, the value of GR 1 is still unknown.

12. Size distributions of neutral nanoparticles n 0 (d) in case of the near-median distribution of intermediate ions in Tartu and N 50–500 = 2000 cm –3 as calculated for the trial values of charged nanoparticle growth rate GR 1 :

13. We assumed that GR 0 (d) may differ from GR 1. Now the first general equation is transformed into a linear differential equation for GR 0 (d): This equation can be integrated when an initial value GR 0 (d 0 ) at an arbitrary diameter d 0 is known. It is assumed that a possible dependence of the growth rate on the particle charge fades with an increase in particle size. Thus a hypothesis GR 0 (7 nm) = GR 1 seems to be an acceptable initial condition.

14. Growth rate of neutral nanoparticles GR 0 (d) in case of the near-median distribution of intermediate ions in Tartu and N 50–500 = 2000 cm –3 calculated at the assumption GR 0 (7 nm) = GR 1 for trial values of charged nanoparticle growth rate GR 1 INTUITIVE UNREALISTIC

15. The growth flux GF or apparent nucleation rate J estimated for the near-median distribution of intermediate air ions in Tartu assuming GR 0 (3 nm) = GR 0 (7 nm) = GR 1 and N 50–500 = 2000 cm –3 GF or J (cm –3 s –1 ) GR  2 nm h –1 GF(d) = GR 0 (d)n 0 (d) + 2GR 1 (d)n 1 (d) ≈ GR (n 0 (d) + 2n 1 (d))

16.  consider all 7647 individual hourly size distributions available in the reference dataset of intermediate air ion measurements in Tartu,  estimate for every hour (?) the growth flux,  calculate the growth product for hours when the concentration of intermediate ions does not exceed certain limit,  calculate Relative Contribution to Growth Product as function of the limit of intermediate ion concentration,  draw a diagram of cumulative distribution function of intermediate ion concentration (CDF) together with a diagram of Relative Contribution to Growth Product (RCGP),  analyze the diagram. PLAN of extra calculations:

17. Remark about technique: The long term average size distribution of intermediate ions was approximated with a sophisticated 4-parameter curve in the ACPD paper. This is not reasonable when considering the one-hour measurements and limiting the size range with 3–7 nm. A convenient parameterization is Here we have only 2 parameters and easy way to estimate the concentration in the limited size range of 3–7 nm:

19. Relative Contribution to Growth Product

20. CONCLUSION The figure suggests that the burst events in Tartu generate less than half of new particles in diameter range of 3…7 nm and most of new particles are generated during quiet periods of NPF. WARNING: the figure is based on very rough approximations and the statement above is still problematic. TO DO: ► Improve the theoretical model, ► acquire data of simultaneous ion and aerosol measurements, ► consider alternative criteria for discrimination of NPF event situations.

21. Thank you !