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
The presentation is based on a published paper:
Aim of the presentation is to explain
the concept of RCGP and one special figure
Symbol Quantity Unit
n(d) Size distribution of particle concentration dN / dd cm–3nm–1 n1(d) Size distribution of + or – particle concentration dN1 / dd cm–3nm–1
NB: n(d) = n0(d) + 2 n1(d)
GR(d) Growth rate nm s–1
GF(d) Growth flux (or apparent nucleation rate J ) GR(d) × n(d) cm–3s–1
GP(d) Growth product GF(d) dt cm–3
N1(3–7) Concentration of charged particles of one polarity
in diameter range of 3–7 nm cm–3
N1(3–7) Upper limit of N1(3–7) cm–3
w(t, N1(3–7)) Condition function if (N1(3–7)(t) < N1(3–7) ) then 1 else 0 GPw(d, N1(3–7)) Conditional growth product w(t, N1(3–7)) GF(d) dt cm–3 RCGP(d, N1(3–7)) Relative Contribution to Growth Product GPw(d, N1(3–7)) / GP(d)
0 = neutral 1 = charged (one polarity)
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?
PR EV IEW
Relative Contribution to the Growth Product
REPLACEMENT FOR INTRODUCTION:
fragments of the published paper
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 .
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
) ( ) ( )
( ) ( 2
) ( ) ( ) 2
( ) ( GR
0 0
0 0
1 0 1
0
c d n d c d n d S d n d
dd
d n d d
bkg
GR ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
1 1
1 1
0 1 0
1
c d n d c d n d S d n d
dd
d n d d
bkg
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
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.
2 3 4 5 6
1 2 3 4 5 6 7
d (nm) positive ions
approximation negative ions
n
1( d ) ( cm
–3n m
–1)
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.
1 - 3 6
6 . 1 500
0 50
10 cm s
) nm 1
/ (
45 . ) 1
(
d d N
S
bkg) ) (
2 nm
1 / (
4 nm
1 /
5 . 1 1
)
(
2 01
S d
d d d
S
bkg
bkg
Concentration of particles in range of 50…500 nm (typical values 1000 cm–3
at Hyytiälä and 2000 cm–3 in Tartu)
dd d dn d
d c d n
c
d S
d d c
n
bkg( )
) ( ) GR
) ( (
) ( )
) (
(
10 1 1
0
1
0 1
) ( ) ( )
( ) ( )
( ) ) (
( ) ( GR
1 1
1 1
0 1 0
1
c d n d c d n d S d n d
dd
d n d d
bkg
The second general equation was:
Let’s assume that
GR
1is a constant,
N
50–500is known,
n
1(d) is known.
In this case
Unfortunately, the value of GR
1is still unknown.
Size distributions of neutral nanoparticles n0(d) in case of the near-median distribution of intermediate ions in Tartu and
N50–500 = 2000 cm–3 as calculated for the trial values of charged nanoparticle growth rate GR1:
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
0is 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
1seems to be an acceptable initial condition.
) ( )
( ) 2
( ) ) (
( 2
) ( ) GR (
) ( 1 )
( GR
0 0
0 1 1
0 0 0
0
c d S d
d n
d d n
c dd d
d dn d
n dd
d d
bkg
Growth rate of neutral nanoparticles GR0(d) in case of the near-median distribution of intermediate ions in Tartu and N50–500 = 2000 cm–3 calculated at the assumption
GR0(7 nm) = GR1
for trial values of charged nanoparticle growth rate GR1
INTUITIVE UNREALISTIC UNREALISTIC
The growth flux GF or apparent nucleation rate J estimated for the near-median distribution of intermediate air ions in Tartu assuming GR0(3 nm) = GR0(7 nm) = GR1 and N50–500 = 2000 cm–3
GF or J (cm–3 s–1)
GR 2 nm h
–1GF(d) = GR
0(d)n
0(d) + 2GR
1(d)n
1(d) ≈ GR (n
0(d) + 2n
1(d))
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),
PLAN of extra calculations:
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:
) exp(
)
1
( d a bd
n
7 7 3
3