J, Aerosol Sci., 1976, Vol. 7. pp. 479 to 483. Pergamon Press. Printed in Great Britain.

LARGE AEROSOL PARTICLES AS FREEZING

NUCLEI
J. ROSINSKI and C. T. NAGAMOTO
National Hail Research Experiment, National Center for Atmospheric Research*, Boulder, CO, U.S.A.
(First received 19 January 1976; and in revised form 28 May 1976)

Abstract--Aerosol particles ingested by cloud supply nuclei which initiate formation of ice.
These particles may either condense water or collide with cloud droplets thus becoming hydrosol
particles. Ice nucleation through freezing was found to be time-dependent; nucleation sites are
being formed or exposed continuously on the surfaces of hydrosol particles. In severe storms
large soil particles (dia. > 40 #m) accrete cloud droplets; they freeze the accreted supercooled
water at temperatures warmer than the ice nucleation temperature of their submicron- and
micron-sized shed particles. Solid phase (ice) formation in clouds cannot be reconstructed by
determining freezing temperature spectra of hydrosol present in precipitatation samples where
surfaces of hydrosolized aerosol particles have already undergone physical and chemical changes.

1. I N T R O D U C T I O N
Particles larger than ~ 40/~m dia., which are an intrinsic part of the aerosol population
ingested by severe storms in semi-arid areas, will accrete cloud droplets from the time
of their entry into a cloud, and consequently are always in contact with water. Average
cloud base temperatures in northeastern Colorado are 4.2, 8.4 and 8.6C in May-June,
June-July and July-August, respectively, and therefore these particles are first wetted
at temperatures above 0C. These particles always nucleate ice through freezing as hydrosol particles. Large aerosol particles, when transferred into water, shed submicronsized particles from their surfaces (Rosinski et al., 1973; Rosinski and Langer, 1974),
which can also nucleate ice.
Hoffer (1961) has shown that soluble salts commonly present in water droplets in
the atmosphere caused the freezing temperatures of the droplets to become lower than
would be anticipated by bulk-freezing-point-lowering calculations. Droplets containing
insoluble hydrosol particles can freeze at warmer temperatures than "particle-free" droplets.
L a b o r a t o r y experiments were designed and performed to elucidate the role of large
aerosol particles as freezing nuclei.
2. E X P E R I M E N T A L P R O C E D U R E
The experiments were performed using techniques described previously by Rosinski
and N a g a m o t o (1976).
2.1 In the first series of experiments designed to provide a contribution to in-cloud
ice nucleation the ice nucleation temperature spectra of large soil particles and of the
shed particles were determined. The temperature spectra of large soil particles were
determined using single drop-single particle technique. Particles were transferred singly
into a distilled particle-free water drop approx. 3 m m dia. placed on a slide coated
with a water repellant residue left from evaporating a thin layer of silicone oil. Slides
containing 15 such drops were then cooled in a cold chamber at a constant rate of
0.5C/min and freezing events were recorded. The freezing temperature spectra of the
parent (large) particles and their shed particles were determined by placing drops on
a treated slide placed on a cold stage under a microscope. To simulate to some extent
* This research was performed as part of the National Hail Research Experiment, managed by the National
Center for Atmospheric Research and sponsored by the Weather Modification Program, Research Applications
Directorate, National Science Foundation.
479

480

J. ROSINSKIand C. T. NAGAMOTO

the temperature history of a large particle in a storm, a test particle was placed inside
the drop at +4~C and allowed to stay in it for three minutes, during which the drop
was cooled to ~ - 2 C . Then the supercooled drop was transferred by a plastic-tipped
syringe to another area on the slide; care was taken to avoid drawing the test particle
into the syringe. Inevitably a small amount of water was left behind with the test particle.
This was evaporated in the light beam of the microscope lamp. Meanwhile, another
particle-free drop was placed on the same slide and allowed to cool to ~ - 2 C . The
just-dried test particle was then picked up with a camel's hair fibre and placed inside
this second drop. The slide with the pair of drops, one containing the parent test particle
and the other containing the shed particles, was then transferred into a cold chamber
at ~ - 2 C and allowed to cool at a constant rate of 0.5~C/min. The freezing temperatures of the drops were recorded. Approximately one hundred drops were used for
each experiment.
The number of particles shed from a single soil particle was determined by means
of the Roy.co light-scattering, liquid-borne particle counter (Royco Instruments, Inc.,
Menlo Park, CA). The background counts of the particle-free water used were 0.2
counts/cm 3 for 2-4 #m diameter particles and zero for larger particles. The entire experiment was performed on a particle-free bench. Particles from two soils from NE Colorado were used in the experiments; minerological composition is given in Rosinski and
Nagamoto (1976). Soil No. 1 is the predominant one in the National Hail Research
Experiment (NHRE) test area.
2.2 A second series of experiments was performed at constant temperatures to study
ice nucleation by freezing. Approximately 5 particle-free 3 mm dia. drops placed on
a silicone oil treated slide were super cooled to a predetermined temperature. Dry soil
particles or soil particles previously submerged in water were then placed singly inside
each drop at that temperature. Drops were kept at a constant temperature and the
times of freezing were recorded. When an aerosol particle is placed inside a drop, it
could nucleate ice immediately upon contact. Nucleation of ice at the time of contact
occurred with a small percentage ( ~ 2 / ) of particles of both soils at temperatures of
- 1 0 and --12:C. It was noted that contact nucleation increased to 16,,~, at - 1 0 C
for particles which were first immersed in water; experiments with "first immersed"
particles were not performed at - 1 2 C . In presenting the results on ice nucleation
through freezing, these drops frozen by contact nucleation were not taken into account.

3. RESULTS AND D I S C U S S I O N
3.1 In-cloud ice nucleation through.fkeezing
The temperatures of ice nucleation through freezing of 40 and 60F~m dia. hydrosol
particles were determined for the two soils used in the experiments (Table 1). The results
indicate that modelling of ice formation in a storm cloud is not possible unless the
contribution of different soils to the overall aerosol population ingested by each storm
is known. Aerosol particles must be collected in updrafts of storms and their temperature
of ice nucleation should be determined for each case.
Temperatures of ice nucleation through freezing of single 40450 pm diameter particles
of soil No. 2, and of their shed particles, are given in Table 2. Numbers of particles
larger than 2 #m dia. that were shed from large particles are given in Table 3; submicron
particles shed from surfaces of those particles were present (Rosinski et al., 1973) but
their concentrations were not determined. The ratio of the temperature of ice nucleation
by the large (parent) hydrosol particle to that by the shed particles is plotted in Fig.
1. All ratios except three cases (0.99, 0.99 and 0.98) are larger than one. In general,
the large soil particles nucleated ice through freezing at temperatures warmer than the
temperature of ice nucleation by the shed particles; they will nucleate ice in droplets
or drops formed around them in an updraft at temperatures corresponding to their

L a r g e a e r o s o l p a r t i c l e s as f r e e z i n g n u c l e i

481

T a b l e 1. T e m p e r a t u r e o f ice n u c l e a t i o n t h r o u g h f r e e z i n g o f ~ / a m
dia. hydrosol particles from two different soils from NE Colorado

Temperature
ATC

F r a c t i o n (%) o f p a r t i c l e s
n u c l e a t i n g ice i n A T
Soil No. 1
Soil N o . 2

range,

-8--9
-9--10
-10--11

0.1
0.3
0.6

10.6

-11--12

1.1

10.6

-12--13

1.2

15.1

12.1
15.1

13--

14

1.3

16.7

14--

15

1.5

6.1

15--

16

2.0

7.6

16--

17

3.0

4.6

17--

18

5.0

1.5

-18--19
-

19--

below-

5.5
20

6.0

20

72.4

freezing temperature spectra. The solid line (Fig. 1) corresponds to the average temperature of ice nucleation by the shed particles; if all data points were gathered around
this curve, it would indicate that all shed particles are similar and do not depend
on the minerological composition of large particles.
3.2 Rates of ice nucleation through freezing
Delayed ice nucleation by freezing was investigated in the series of experiments in
which drops containing test particles were kept at a constant temperature. The rate
T a b l e 2. T e m p e r a t u r e
o f ice n u c l e a t i o n ( T ) t h r o u g h
freezing of 40-60/am diameter particles of soil No. 2
a n d o f t h e s h e d p a r t i c l e s (Tsp)
TC

T~pC

T C

TspC

-8.1
-8.2
-8.3
-8.4
-8.6
-8.8
- 8.9
-9.3
-9.4
-9.5
-9.7
-9.7
-9.8
-9.8
-9.8

- 16.1
- 15.6
- 12.4
- 15.0
- 12.5
- 14.2
- 20.0
- 16.5
- 12.5
- 19.8
- 12.8
-15.8
- 11.0
-13.6
- 14.3

- 12.0
- 12.0
- 12.3
- 12.3
- 12.4
- 12.5
- 12.5
- 12.6
- 12.6
- 13.0
- 13.2
-13.3
- 13.4
-13.5
- 13.5

- 16.2
-20.0
- 17.3
- 18.0
- 16.7
- 15.9
- 16.6
- 15.0
- 17.3
- 17.0
- 15.1
-14.5
- 19.3
-15.3
- 19.0

10.0

16.6

13.6

13.5

10.2

12.4

13.6

18.8

10.3

12.8

13.7

13.6

10.3

15.0

13.8

16.0

10.5

16.5

13.8

19.5

10.5

18.5

14.0

17.4

10.6

13.5

14.3

17.0

10.6

15.1

14.4

15.6

-10.7

-13.6

-14.5

-15.1

10.8

12.4

15.0

15.0

11.1

14.4

15.1

16.0

11.1

16.0

15.2

19.6

11.2

12.0

15.5

16.0

11.3

14.4

15.6

16.4

11.5

13.5

16.0

16.2

11.5

16.0

16.1

16.6

- 11.5

-20.0

- 16.5

12.0

12.7

17.2

- 16.7
-

16.9

a v - 15.7

482

J. ROSINSKIand C. T. NAGAMOTO
I

20

x
I--

"~ 1.5

x
x

xx
x x

x
x

x
xx
x
x

x
XxXx x Xx ~
x x
x x

I.O

I
I

-5

-I0

-15

-20

TEMPERATURE, T C

Fig. 1. Ratios of temperatures of ice nucleation through freezing by shed particles (T~p) to
those of 40450/zm dia. large (parent) particles (soil No. 2).
of drop freezing, which must be equal to the rate of formation of ice nucleating sites
on the surface of hydrosol particles, is given in Fig. 2. At the time of immersion of
a wettable soil particle the surface of a particle is exposed to an immensely turbulent
water layer. The release of heat by immersion, the dissolution of chemical compounds,
and the shedding of submicron- and micron-sized particles take place from the m o m e n t
a particle is wetted. Turbulent diffusion on a microscale transports shed particles and
dissolved solids away from the surface of a large particle. This process slows dowr~
after a few minutes and the particle returns to a thermal equilibrium.
F r o m results of experiments it is seen that the rate of ice embryo formation increases
with lower temperatures and generally decreases with time. Peaks in ice nucleation
rates for particles of soil No. 2 at temperatures of - 8 and - 10C are the manifestation
of formation of ice embryos on the surface of particles during particle shedding and
dissolution of solids. Soil No. 2 is approximately ten times more soluble than soil
i,,,,l,,Vll

-8C

"r" .o..

"~

I0

F.-"'

C,
I.,,~

,' ' . . . . . . . . . . . . .

"" i ";','i ........

,.
,

........, ...... ; ........ ,........ ,o:--

I0
,~

-12C

-,ooc

I0

20

30
TiME

40

I0

20

(Minutes)

Fig. 2. Ice nucleation rates from drop freezing experiments (single drop-single particle) with
40-60/~m dia. soil particles at three different temperatures. (Closed symbols--soil No. 1; open
symbols, x and xx--soil No. 2; x--particles immersed in water prior to freezing; x x shed
particles, indeterminate number.)

Fig. 3. The early stage of ice growth on a single, approx. 60 tzm dia. soil particle at
temperature of --8.5C.

[A.S. f..p. 482]

Large aerosol particles as freezing nuclei

483

Table 3. Average number of shed hydrosol particles from different-sized parent particles of soil No. 2
Parent
particle
d (#m)
20
30
40
50
60

No. of shed particles per Ad (#m*)

Ad (/~m)
2-20
2-4
4-7
7-11
11-20
1.0
1.3
1.3
2.2
6.5

1.0
2.3
1.2
2.3
5.0

1.0
0.2
2.2
1.0
4.2

0.1
0.1
0.2
0.8
1.2

3.1
3.9
4.9
6.3
16.9

* 8~o of parent particles shed, at random, 10-22 particles in

the 2-4/~m size range; those are not included in the table.
No. 1; the latter did not produce this effect. Similar particles first suspended in water
and subsequently used in freezing experiments did not exhibit enhanced ice nucleation
rates; 6.1~o of particles nucleated ice in the first minute, and 3~o in the second minute;
66.5~o of those particles did not nucleate ice even when kept for more than 50rain
at a constant temperature. A small difference ( ~ 2~) in ice nucleation rates at time
"zero" of particles first immersed in water and fresh aerosol particles may be due to
the presence of more numerous ice nucleating sites exposed on particles which were
immersed in water prior to freezing.
An example of a single, approx. 60 pm dia. soil particle nucleating ice at temperature
of - 8 . 5 C after dissolution and shedding was completed is shown in Fig. 3. A thermocouple placed just under the surface of the drop was used to trigger the flash for the
photograph. After the drop was frozen it was melted and then refrozen; the same particle
nucleated ice upon refreezing (lower frame) at exactly the same temperature in this particular case.
4. C O N C L U S I O N S
Two observations were made and one conclusion was drawn from this study:
4.1 O b s e r v a t i o n s
1. Ice nucleation through freezing on hydrosolized aerosol particles is time-dependent;
ice nucleation sites are being formed (or exposed) continuously at different rates on
the surfaces of hydrosolized aerosol particles.
2. Larger (dia. > 40/~m) soil particles nucleate ice through freezing at warmer temperatures than the ice nucleation temperature of the shed (submicron- and micron-sized)
particles.
4.2 C o n c l u s i o n
Ice nucleation temperature spectra and the rates of ice nucleation of hydrosolized
aerosol particles in clouds must be determined in experiments with aerosol particles
collected below clouds (before ingestion into a storm) and cannot be reconstructed
by determining the freezing temperatures of precipitation samples through refreezing
where the surfaces of particles have already undergone physical and chemical changes
during the aerosol-to-hydrosol transition.
The conclusions drawn in this article are based on results of experiments with aerosol
particles collected in the Colorado-Nebraska region, and do not purport to apply generally to all hail-producing storms.
Acknowledoement--Stimulating discussions with Drs. M. L. Corrin and C. S. Kiang are acknowledged.

REFERENCES
Hoffer, T. E. (1961) J. Met. 18, 766.
Rosinski, J. and Langer, G. (1974) J. Aerosol Sci. $, 373.
Rosinski, J., Nagamoto, C. T., Kerrigan, T. C. and Langer, G. (1973) J. Atmos. Sci. 30, 644.
Rosinski, J. and Nagamoto, C. T. (1976) J. Aerosol Sci., 7, 1.