JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 108, NO. D14, 4434, doi:10.

1029/2003JD003420, 2003

Solubility and freezing effects of Fe2+ and Mg2+ in H2SO4

solutions representative of upper tropospheric and lower
stratospheric sulfate particles
Matthew E. Wise,1,2 Sarah D. Brooks,1,2 Rebecca M. Garland,1,2 Daniel J. Cziczo,2,3
Scot T. Martin,4 and Margaret A. Tolbert1,2
Received 15 January 2003; revised 1 April 2003; accepted 14 April 2003; published 31 July 2003.

[1] Chemical elements characteristic of earth minerals and meteorites are present within
background tropospheric and stratospheric sulfate aerosol particles. However, it is
unknown if these elements are present predominantly as solids, including possible
sulfates, carbonates, and oxides, or rather as soluble aqueous metal ions or complexes.
Further, it is unclear how these impurities could affect particle freezing. To address
these questions, we have determined the total equilibrium metal solubility ([Fe2+]T and
[Mg2+]T) in 20–90 wt % sulfuric acid solutions over the temperature range 200–300 K.
We have measured solubilities using samples of MgSO4, FeSO4 7H2O, and a mixture of

metal sulfates representative of some meteorite samples. Because Fe2+ oxidation by O2
was found to be negligible over a 28 day period when air was bubbled through the
solutions, we conclude that aqueous Fe2+ may be present at high concentrations in
atmospheric sulfuric acid particles. We estimate that soluble Fe2+ and Mg2+ compose
0.01–0.28 wt % of the H2SO4/H2O/{Fe2+, Mg2+} solutions at temperatures and acid
compositions representative of the atmosphere. Compared to composition measurements
done by mass spectrometry of atmospheric particles showing 0.75 wt % Fe and 0.20 wt
% Mg, we conclude it is plausible that solid Fe2+ and Mg2+ minerals often occur inside
atmospheric sulfuric acid particles. Bulk freezing experiments were also carried out on
H2SO4 solutions containing amounts of dissolved metal determined by the low-
temperature solubility studies. It was found that 57.6 wt % H2SO4 containing soluble
meteoritic metal and 60 wt % H2SO4 containing either soluble Fe or soluble meteoritic
metal froze 12–20 K higher than solutions containing no soluble metal. Soluble metal
ions in sulfuric acid solution may therefore provide a mechanism for sulfuric acid
tetrahydrate formation in the lower stratosphere. INDEX TERMS: 0305 Atmospheric
Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and
Structure: Cloud physics and chemistry; 0340 Atmospheric Composition and Structure: Middle atmosphere—
composition and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and
chemistry; KEYWORDS: polar stratospheric cloud formation, phase transformations, stratospheric aerosol,
metal solubility, sulfuric acid, meteoritic metals
Citation: Wise, M. E., S. D. Brooks, R. M. Garland, D. J. Cziczo, S. T. Martin, and M. A. Tolbert, Solubility and freezing effects of
Fe2+ and Mg2+ in H2SO4 solutions representative of upper tropospheric and lower stratospheric sulfate particles, J. Geophys. Res.,
108(D14), 4434, doi:10.1029/2003JD003420, 2003.

1. Introduction impact the Earth’s atmosphere in several ways. These

particles can affect the Earth’s radiation balance directly
[2] Sulfate aerosol particles are ubiquitous in the upper
by scattering solar radiation or indirectly by serving as
troposphere and the lower stratosphere and are known to
cloud condensation nuclei [DeMott and Rogers, 1990].
1
Sulfate aerosol particles are also important for chemistry
Department of Chemistry and Biochemistry, University of Colorado, in the Earth’s atmosphere. In the lower stratosphere, polar
Boulder, Colorado, USA.
2
Cooperative Institute for Research in the Environmental Sciences,
stratospheric clouds (PSCs) form on background sulfate
University of Colorado, Boulder, Colorado, USA. aerosols and convert inert chlorine species into active chlo-
3
Aeronomy Laboratory, National Oceanic and Atmospheric Adminis- rine species that destroy ozone in the Antarctic [Solomon,
tration, Boulder, Colorado, USA. 1988]. Direct reactions of chlorine on sulfate aerosols have
4
Division of Engineering and Applied Sciences, Harvard University,
Cambridge, Massachusetts, USA.
also been implicated in global ozone loss [Solomon et al.,
1997].
Copyright 2003 by the American Geophysical Union. [3] While most studies of the chemistry and climate
0148-0227/03/2003JD003420 impact of sulfate aerosol particles have assumed pure

AAC 15 - 1
AAC 15 - 2 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS

H2SO4/H2O compositions, new data reveal that there is account only H2SO4 and H2O present in the system, with
many trace species present in the particles, including no corrections due to metal sulfate dissolved. The waters of
meteoritic material [Cziczo et al., 2001]. The main trace
metal constituents found in meteoritic particles are Fe, Mg,


hydration present in the FeSO4 7H2O were included in the
determination of the H2SO4 concentration. Temperature was
Al, Ca, Na, Ni, Mn, and K. These trace species may measured using a Type T copper/constantan thermocouple.
influence important properties of the sulfate aerosol. For The uncertainty in the temperature measurement was always
instance, if these trace substances are present as solids, they 1
C (specified by Omega Engineering, Inc.). This uncer-
may serve as heterogeneous nuclei for cloud formation. If tainty was used to produce temperature error bars in the
present in dissolved form, metal ions may catalyze liquid- solubility experiments.
phase reactions in the sulfate particles. The exact physical [7] The maximum solubility of Fe2+ and Mg2+ in 20– 90
form (solid or aqueous) of the metals in the sulfate particles wt % H2SO4 was first determined at room temperature by
is not currently known.
[4] The question of metal solubility is complex, depend-


separately mixing FeSO4 7H2O and MgSO4 into the
H2SO4 until solid dissolution ceased. The solutions were
ing on equilibrium thermodynamics, dissolution rates, and mixed for 72 hours to ensure that the metals in solution
chemical form. For instance, Fe2+ salts such as FeSO4 are were in equilibrium with the undissolved solid. After
highly soluble in water and in dilute sulfuric acid and mixing, the solutions were centrifuged for 20 min at 4000
rapidly achieve dissolution equilibrium. In contrast, the rpm to remove all solids from the saturated solutions. The
equilibrium solubility of Fe3+ such as Fe2O3 is orders of supernatant was then analyzed for Fe and Mg content using
magnitude lower, dissolution kinetics is slow, and equili- ICP/AES. Total iron analyzed here ([Fe]T) is the sum of
bration times are long [Stumm and Morgan, 1996]. There- Fe2+(aq), Fe3+(aq), and any aqueous complexes (e.g., sul-
fore a kinetic/mechanistic approach is necessary which fates) of each. The same holds for [Mg]T. As discussed
initializes the system with the mass of each mineral present further below, we measure negligible amounts of Fe3+ in our
in an atmospheric particle at the temperature and composi- systems. Thus we abbreviate hereafter [Fe2+] for [Fe]T and
tion of the surrounding aqueous sulfuric acid. Identified similarly for [Mg2+].
meteoritic materials including Ca2+, Mg2+, Na+, Ni2+, and [8] To ensure that the 3 day period was adequate to obtain
K+ have a single common oxidation state. In contrast, Fe solubility equilibrium, H2SO4 solutions were left to mix
and Mn minerals can be found in much more soluble Fe2+ with an abundance of FeSO4 and MgSO4 for a period of 28
and Mn2+ states or much less soluble Fe3+ and Mn3+/4+ days. Each week a sample of each solution was analyzed for
states [Cotton and Wilkinson, 1972]. Finally, meteoritic metal content. Because the metal content was the same
material may also contain any number of other minerals within error in the solutions mixed for 3 days and over the
including insoluble oxides of silicon and aluminum. The period of a month, we concluded that the 3 day mixing
current paper concentrates specifically on the subsystem period was adequate for the determination of equilibrium
Fe2+ and Mg2+. An important simplification found in the solubility.
current work is that the Fe 2+ and Fe 3+ systems are [9] The setup used in our low-temperature solubility
decoupled (i.e., slow Fe2+ auto-oxidation kinetics), at least experiments was an insulated methanol bath that was chilled
for the typical timescales and temperatures of atmospheric using a recirculating flow of methanol from a Neslab
sulfate particles. refrigerator through a copper coil. Using this method, the
[5] We have determined the solubility of the parent methanol bath in the cooler was chilled from 0
C to 70
C
metals of MgSO4, FeSO4, and a mixture of metal sulfates and solubility experiments were carried out at a desired
representative of meteorite samples in sulfuric acid solu- temperature in this range. To determine Fe2+ and Mg2+
tions from 20– 90 wt % over the temperature range 200 – solubility in 20– 50 wt % H2SO4 at low temperatures, a
300 K. We have also investigated the kinetics of Fe2+ metal sulfate saturated H2SO4 solution at room temperature
oxidation by O2 under these conditions. Finally, we have was placed in a test tube in the cold bath. Because the
performed bulk freezing experiments to determine the solution was supersaturated with respect to the metal sulfate
influence of soluble metal ions on the freezing temperatures at colder temperatures, solid metal sulfate precipitated out of
of sulfuric acid solutions. solution to reach equilibrium. After precipitation, the super-
natant was sampled and analyzed for metal content using
ICP/AES. If the metal sulfate solution froze, a lower metal
2. Experiments sulfate concentration was used that did not freeze but still
2.1. Solubility Experiments resulted in solid precipitation upon cooling.
[6] In all experiments, reagent grade 96.4 wt % H2SO4 [10] Because no solid precipitated in 60– 70 wt % H2SO4
was diluted to 20– 90 wt % using distilled water. Analysis of at low temperatures, a different method was employed to
the distilled water using an ARL-3410+ inductively coupled determine Fe2+ and Mg2+ solubility. Initially, H2SO4 with
atomic emission spectrometer (ICP/AES) showed negligible no metal in it was placed in the bath at the desired
amounts of dissolved metals. Therefore no further purifica- temperature. Once the H2SO4 reached the bath temperature,
tion process was employed. The H2SO4 concentration was crystalline metal sulfate was added stepwise into the H2SO4
determined prior to each experiment by titration with a until solid dissolution ceased. This solid was removed by
standardized NaOH solution. Each standardization and titra- passing the solution through 0.1 mm syringe filter that was
tion was performed multiple times, and the standard devia- chilled to the bath temperature. The filtrate was analyzed for
tion of these trials was used to produce H2SO4 concentration metal content using ICP/AES.
error bars in each experiment. In all experiments the H2SO4 [11] To measure how the metal ion solubility was affected
weight percent concentrations are calculated taking into by other metal ions, we also measured mixed metal sulfates
 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS AAC 15 - 3

Figure 1. Weight percent soluble metal, [MZ+] (where M is metal studied and z is 1 or 2), using the
‘‘centrifuge method’’ versus using the ‘‘filter method’’ of removing solid particles from solution. Each
symbol represents a different metal studied in 89.1 wt % H2SO4 at 22.9
C.

1
of composition dictated by that likely found in meteoritic 1,10-phenanthroline and sodium bicarbonate in a Hach
samples. Previous work has shown that stratospheric par- AccuVac Ampul. After a three-minute reaction period, the
ticles contain 0.75 wt % extraterrestrial Fe [Cziczo et al., solution was placed in the spectrophotometer and analyzed
2001]. Using this percentage, the weight percent of other for ferrous ion content using 510 nm light. Because this
major meteoritic constituents such as Ca, K, Mn, Na, Ni, method requires ferrous iron concentrations to be between
and Mg were estimated by Cziczo et al. [2001]. These 0.02 and 3 mg/L and pH values to be between 3 and 9, each
metals in ratios consistent with actual stratospheric particles solution was diluted by a factor of 1000 to 50,000 with
were simultaneously added as sulfate salts to 40– 70 wt % distilled water. It was determined that once diluted, the
H2SO4 that was previously cooled to a specific temperature experimental limits of this method were not violated. To
in the cold bath. These solutions were mixed and then investigate the kinetics of Fe2+ auto-oxidation, compressed
forced through a 0.1 mm syringe filter chilled to the bath air was bubbled through only the 20 and 70 wt % H2SO4
temperature. The filtered solution was then analyzed for samples. Ferrous ion content was determined each week for
metal content using ICP/AES. a period of 28 days using the method outlined above.
[12] To determine if the syringe filter affected metal
solubility, 89.1 wt % H2SO4 was mixed separately with 2.2. Freezing Experiments
each metal sulfate tested as described in the room temper- [14] To probe the influence of metal ions on the sulfuric
ature solubility experimental section. Half of each solution acid freezing temperature, 10 mL of 20– 70 wt % H2SO4
was centrifuged to remove solid particles and the superna- was mixed with a small amount of solid FeSO4, MgSO4, or
tant analyzed for metal content. The other half was filtered meteoritic components present as sulfate salts. The amount
to remove solid particles with the 0.1 mm syringe filter. of metal sulfate added to the H2SO4 corresponded to the
Parent metal solubility using the ‘‘centrifuge’’ preparation least amount of metal soluble determined by the low-
method is plotted versus parent metal solubility using the temperature solubility experiments. This precluded solid
‘‘filter’’ preparation method in Figure 1. Each metal exhibits precipitation during the experiment. The sample was
different solubility in 89.1 wt % H2SO4 with K+ exhibiting contained in a plastic tube and was sealed with a screw
the greatest solubility at 10 wt % and Mg2+ exhibiting the cap. The screw cap had a thermistor mounted in it so that
lowest solubility at less than 0.01 wt %. There is good when the cap was screwed tight, the thermistor was sub-
agreement with the two preparation methods. It is thus merged in the sample. The thermistor head was covered
unlikely that any undissolved metal sulfate is contributing with plastic insulation and the headspace of the tube was
to our solubility values. capped with nitrogen to minimize any heterogeneous nu-
[13] To determine the oxidation state of soluble Fe in our cleation that the thermistor or tube might facilitate.
experiments, we sampled Fe saturated H2SO4 solutions [15] Two types of freezing experiments were performed.
once a week for a period of 28 days. One sample from In the first, the plastic tubes were submerged in a liquid
each H2SO4 concentration was analyzed for total Fe content methanol bath that was cooled from 273 to 183 K at a rate
using ICP/AES. A second1 sample was analyzed for ferrous of 0.5 K/min. Freezing was indicated by a rise in
ion content using a Hach DR/2000 direct reading spectro- temperature, which was caused by the heat of fusion and
photometer. Specifically, each solution was reacted with was sensed by the submerged thermistors. Because the
AAC 15 - 4 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS

Figure 2. FeSO4 and MgSO4 solubility as a function of wt % H2SO4 at 22.9
C (solid symbols)
compared to previous studies at 25
C for FeSO4 and 12.6
C for MgSO4 (open symbols). Conversion is as
follows: wt % H2SO4 is mH2SO4/(mH2SO4 + mH2O) and wt % FeSO4 is mFeSO4/(mFeSO4 + mH2SO4 + mH2O).
At ‘‘18.7 wt % H2SO4’’ and ‘‘14.6 wt % FeSO4’’ actual solution composition by mass (in g) is then {17.2,
18.7, and 81.3} for {FeSO4, H2SO4, and H2O}.

thermistors were not accurate at low temperatures, a ther- studies while solubility in more concentrated H2SO4 differ
mometer submerged in the methanol bath (calibrated to
±0.2 K) was used to determine the actual temperature of the


slightly. Cameron [1930] found that FeSO4 7H2O (present
as deep green monoclinic crystals) is the stable solid phase
samples at the time of freezing. For samples with the same in contact with solutions of up to 45.6 wt % H2SO4 at room
wt % H2SO4 and metal content, three to six freezing temperature. At H2SO4 concentrations greater than 45.6 wt
experiments were performed. % H2SO4, the stable solid phase in contact with the solution
[16] In the second type of freezing experiment, the
samples were cooled from 273 K down to 227 K at a rate


is FeSO4 H2O, which is present as a white, crystalline fine
powder. We are in qualitative agreement with this study: we
of 0.5 K/min. Once the sample temperature reached observed a change in color from green to white of any solids
227 K, the temperature was held constant for 30 min. After in H2SO4 solutions of 50 wt % and above. While the phases
this time period, the temperature was reduced by 4 K and are known at room temperature [Cameron, 1930], the phase
held for another 30 min. This stepwise decrease of the sample diagram has not been determined at low temperature where
temperature by 4 K every 30 min was performed until all of the region of stability may shift.
the samples froze or the temperature reached 190 K. [18] MgSO4 shows the same solubility trends as FeSO4,
though more soluble than FeSO4, over the acid concen-
trations studied. MgSO4 solubility is slightly higher in our
3. Results and Discussion measurements than in the previous solubility studies, but
3.1. Solubility Experiments our measurements were obtained at 22.9
C, whereas the
[17] Fe2+ and Mg2+ solubility measurements were carried literature values were determined at 12.6
C. Because the
out in 20– 90 wt % H2SO4 at 22.9 ± 1.0
C. From the mass solubility of MgSO4 in H2SO4 is higher at warmer temper-
of soluble metal, we calculated the mass of soluble metal atures, our solubility values at 22.9
C are in good agree-
sulfate by assuming a 2+ oxidation state for each metal and ment with the literature values at 12.6
C. As with the FeSO4
adding the corresponding mass of sulfate. These results are solubility study, MgSO4 solubility differs slightly from the
summarized in Figure 2 along with previous results for literature values at the highest H 2SO4 concentration.
these systems at near room temperature [Belopol’skii et al., Montemartini and Losana [1929] report several stable solid
1948; Bullough et al., 1952; Cameron, 1930; Montemartini phases of MgSO4 in contact with the solutions depending
and Losana, 1929]. The room temperature results show on acid content. Below 28 wt % H2SO4, the predominant
FeSO4 solubility of greater than 14 wt % in 18.7 wt %
H2SO4 (e.g., 17.2 g FeSO4, 81.3 g H2O, and 18.7 g H2SO4).


stable solid phases are MgSO4 7H2O and MgSO4 H2O.
Between 28 and 60 wt % H2SO4, the predominant solid


However, as the H2SO4 concentration increases, we find
that the amount of soluble FeSO4 decreases to a value of



phases are MgSO4 H2SO4 3H2O and MgSO4 3H2SO4.

Above 60 wt % H2SO4, the predominant solid phase is
less than 0.10 wt %. Solubility of FeSO4 in 20– 50 wt %
H2SO4 is in good agreement with the previous solubility


MgSO4 3H2SO4. Because all of these phases appear as
white solids, it could not be determined if we were in
 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS AAC 15 - 5

agreement with the previous study. Again the phases have temperatures representative of the atmosphere. Because our
only been studied at room temperature. solubility data are extrapolated to at most 30 K colder than
[19] The temperature dependence of the Fe2+ and Mg2+ our experimental temperatures, we feel that the equation (5)
solubilities in H2SO4 was also examined. General equilib- will give a reasonable approximation of metal solubility at
rium reactions for the metal sulfates in solution are formally actual atmospheric temperatures.
written in equations (1) and (2) [Krauskopf and Bird, 1995]: [22] The temperature dependence of Fe solubility in
sulfuric acid is shown in Figure 3. Figure 3a shows the
 2þ  2
FeSO4 $ Fe2þ þ SO2
4 ; K ¼ Fe SO4 ð1Þ Fe2+ conditional equilibrium constant as a function of
inverse temperature in 20– 50 wt % H2SO4, and Figure 3b
 2þ  2 shows data for 60– 70 wt % H2SO4. A straight line fit can
MgSO4 $ Mg2þ þ SO2
4 ; K ¼ Mg SO4 ð2Þ be placed through the 20– 40 wt % Fe solubility points;
however, at lower temperatures the 50 wt % points deviate
where K is the solubility equilibrium constant and {MZ+} is slightly from a straight line. For H2SO4 concentrations
the chemical activity of species MZ+. The thermodynamic between 60 and 70 wt %, as temperature decreases the
formulation of the temperature dependence of mineral mole fraction of soluble Fe remains the same within error
solubility is given by equation (3) [Krauskopf and Bird, for both concentrations of acid. A completely different
1995]. behavior of metal solubility in high acid concentrations is
not surprising because as the concentration of H2SO4
log KT ¼  ½ð
H
=2:303RÞð1=TÞ increases, the amount of water in solution decreases. Thus
þ ½log KT ref þ ð
H
=2:303RÞð1=Tref Þ ð3Þ the solution ceases to behave like an aqueous H2SO4
solution with an abundance of free water participating in
where
H
is the enthalpy change under standard state
conditions, R is the universal gas law constant, and KT ref is

the equilibrium. Also note that FeSO4 H2O becomes the
stable solid at room temperature at the highest H2SO4
a known solubility equilibrium constant at some Tref concentrations and that this may be the cause of the
(usually 25
C). Equation (3) assumes that the standard different behavior. Table 1 shows the calculated constants
enthalpy change is invariant with temperature and that the based on straight line fits to equation (5) when FeSO4 is
difference between standard entropy change at the reference dissolved in 20 –70 wt % H2SO4.
temperature and the standard entropy change at the [23] The temperature dependence of the Mg solubility in
temperature of interest can be neglected. H2SO4 is shown in Figure 4. Figure 4a shows the data for
[20] Total metal solubility in concentrated H2SO4 is 20– 50 wt % H2SO4 and Figure 4b shows data for 60–
complicated by the presence of aqueous HSO 2
4 , SO4 , 70 wt % H2SO4. As was the case for Fe, the Mg solubility
and aqueous metal complexes in solution. At equilibrium decreases as temperature decreases for 20– 50 wt % H2SO4.
the solubility and speciation equations must all be simulta- For the Mg data, a straight line fit can be placed through the
neously satisfied. A complete description of temperature entire 20 –50 wt % data set, and only at the lowest temper-
dependence of solubility must quantify the temperature atures do the points deviate slightly from a straight line. For
dependence of all equilibrium constants, including not only H2SO4 concentrations between 60 and 70 wt % the solu-
the solubility product but also the speciation constants. The bility was temperature independent. Again, this may be due
constants are also strictly for ion activities, rather than to a limited amount of water and a change in the stable
concentrations, and the activity coefficients and their tem- solid. Table 1 shows the calculated constants based on
perature dependencies are unknown in the concentrated straight line fits to equation (5) when MgSO4 is dissolved
acids we are studying. In short, a complete detailed analysis in 20–70 wt % H2SO4.
requires more information than available. An alternative in [24] In addition to the solubility studies of FeSO4 and
these cases is the use of a conditional equilibrium constant, MgSO4 separately in H2SO4, we also probed the solubilities
Kcond MZ+ [Stumm and Morgan, 1996], which we calculate of combinations of these and other metals, as occurs for
using equation (4): meteoritic material. To test how the presence of the other
    meteoritic metals influences Fe and Mg solubility, mixtures
Kcond MZþ ¼ MZþ T SO42 T ð4Þ of various metal sulfates in various concentrations of H2SO4
with mass loadings representative of actual meteoritic
where [MZ+]T denotes the molarity of metal in solution and material were made [Cziczo et al., 2001]. Some of the
[SO42]T denotes the molarity of sulfate in solution due to metals dissolved substantially while others slightly dis-
mineral dissolution. The conditional equilibrium constant solved. The solubility results for these ‘‘artificial’’ meteor-
holds only for a specific and defined range of chemical and itic mixtures and extrapolated Fe and Mg solubility values
physical conditions, which are limited to a single sulfuric from the binary metal sulfate/H2SO4 study (at the meteoritic
acid composition in the current study. experimental conditions) are shown in Table 2. While the
[21] As an empirical approximation, we write an analogue results show quite complex behavior, the overall solubility
to equation (3): of Fe and Mg is roughly comparable (within a factor of 2) to
the solubility when the metals were added separately.
log Kcond MZþ ¼ að1=TÞ þ b ð5Þ
with the thermodynamic values replaced as empirical fitting 3.2. Ionic State and Phase of Fe and Mg in
parameters ‘‘a’’ and ‘‘b.’’ This empirical equation satisfac- Atmospheric Particles Based on Solubility Study
torily fits all of the collected data. Further, we use it in [25] It could be possible that Fe2+(aq) (ferrous iron) in the
section 3.2 to extrapolate the amount of soluble metal to presence of atmospheric O2 oxidizes to Fe3+(aq) during the
AAC 15 - 6 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS

Figure 3. Fe2+ conditional equilibrium constant as a function of inverse temperature in (a) 20 –50 wt %
H2SO4 and (b) 60– 70 wt % H2SO4. Each symbol represents a different wt % H2SO4 studied, and the
lines represent a linear fit through each data set.

residence time of atmospheric aerosol. In our experiments, determined to what extent the iron remained in the ferrous
there is insufficient O2 in the sealed tubes to significantly form because, in some cases, the amount of ferrous iron in
perturb the Fe2+: Fe3+ ratio. To test this we measured the solution determined by the Hach 1 method slightly
ferrous and total Fe content in each of our 20– 70 wt % exceeded that of total iron determined by ICP/AES.
H2SO4 solutions (contained in sealed tubes) each week for
a period of 28 days. We found that over this time period
the amount of ferrous iron in all solutions was the same Table 1. Calculated Constants Based on Straight Line Fits to
(within error) as the total iron content. To overcome this Equation (5)a
experimental limitation, which would not be encountered wt % H2SO4b a (Fe) b (Fe) a (Mg) b (Mg)
by atmospheric particles (i.e., open systems), we bubbled 20 2.24 7.75 2.79 10.11
air through one 20 wt % and one 70 wt % H2SO4 solution 30 2.74 9.21 2.79 10.11
at room temperature and sampled them once a week for a 40 2.38 7.65 2.79 10.11
50 0.94 1.42 2.79 10.11
period of 28 days. In the 20 wt % H2SO4 solution, the 60 0 3.77 0 1.55
ferrous iron content was reduced to 70% [Fe]T over the 70 0 4.71 0 1.89
duration of the experiment. We verified that the majority of a
Log KcondMZ+ = a(1/T) +b.
the iron remained in the ferrous form, at least for <70 wt %. b
Actual percentages are 18.7, 28.9, 39.0, 49.6, 59.6, and 68.7 for Fe and
In the 70 wt % H2SO4 solution, it cannot be exactly 20.4, 30.3, 40.0, 49.9, 59.6, and 68.7 for Mg.
 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS AAC 15 - 7

Figure 4. Mg2+ conditional equilibrium constant as a function of inverse temperature in (a) 20– 50 wt
% H2SO4 and (b) 60– 70 wt % H2SO4. Each symbol represents a different wt % H2SO4 studied, and the
lines represent a linear fit through each data set.

Because there is so little iron in the 70 wt % solutions, atmospheric oxidants such as O3 were not included in
small experimental errors most likely account for this these studies.
discrepancy. Assuming a typical stratospheric climatology [26] Extrapolations of the linear fits in Figures 3a and 3b
of 210 – 225 K and 40– 70 wt % H2SO4, we infer that most and 4a and 4b can be made to estimate the amount of
of the iron initially present as ferrous ion inside atmo- soluble Fe and Mg in solution for H2SO4 particles under
spheric H2SO4 droplets will remain in the ferrous form, upper tropospheric and lower stratospheric conditions. The
rather than oxidize, in the presence of oxygen. Other estimation of Fe and Mg solubility under these conditions is

Table 2. Solubility of Artificial Meteorite Metal in Sulfuric Acid Solutions

H2SO4, Component Soluble, wt %

wt % T (K) Ca K Mn Na Ni Fea Mga
40.5 215.4 0.0030 0.0027 0.0017 0.0284 0.0169 0.0517 (0.0853) 0.0470 (0.0709)
49.0 223.8 0.0005 0.0017 0.0011 0.0194 0.0081 0.1289 (0.1700) 0.0684 (0.1161)
60.0 219.1 0.0006 0.0045 0.0001 0.0425 0.0253 0.0643 (0.0488) 0.1227 (0.2752)
69.1 219.1 0.0004 0.0016 0.0001 0.0046 0.0410 0.0193 (0.0155) 0.0923 (0.1744)
a
Parentheses indicate metal solubility extrapolated from binary solubility experiments.
AAC 15 - 8 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS

Table 3. Estimated Amount of Soluble Fe2+ and Mg2+ in Atmospheric Sulfuric Acid Particles
Fe2+ Mg2+
Atmospheric H2SO4,a Kcond Fe2+, Soluble,c Kcond Mg2+, Soluble,d
Region wt % T,b K mol2 L2 wt % mol2 L2 wt %
UT 20 219 3.16 103 0.278 2.38 103 0.104
UT 30 222 6.88 104 0.121 3.72 103 0.122
LS 40 193 2.00 105 0.019 4.37 105 0.012
LS 50 197 4.84 104 0.088 8.88 105 0.017
LS 60 204 1.70 104 0.049 2.84 102 0.275
LS 70 214 1.95 105 0.015 1.30 102 0.174
a
Actual percentages are 18.7, 28.9, 39.0, 49.6, 59.6, and 68.7 for Fe and 20.4, 30.3, 40.0, 49.9, 59.6, and 68.7 for Mg.
b
Calculated assuming UT water of 3 102 mbar and LS water of 4 104 mbar.
c
Calculation: wt % soluble Fe2+ = [(Kcond Fe2+)1/2(55.85)]/[(10)(rH2SO4)].
d
Calculation: wt % soluble Mg2+ = [(Kcond Mg2+)1/2(24.31)]/[(10)(rH2SO4)].

shown in Table 3. To determine extrapolated temperatures, Mg2+, or a mixture of meteoritic metals in concentrations
it was assumed that the 20– 30 wt % H2SO4 solutions were below those determined from the low-temperature solubil-
in equilibrium with a relevant upper tropospheric water ity experiments. With this approach, solid inclusions, which
partial pressure of 3.0 102 mbar. Likewise, it was could lead to heterogeneous nucleation, are absent. An
assumed that the 40– 70 wt % H2SO4 solutions were in example of the temperature change produced in a 60 wt %
equilibrium with a relevant lower stratospheric water partial ‘‘fast freezing’’ experiment is shown in Figure 5. Temper-
pressure of 4 104 mbar. As seen in Table 3, we estimate ature is plotted as a function of time with the bath
that Fe and Mg have solubilities of 0.01 – 0.28 wt % of the temperature shown as a thick solid line and sample temper-
H2SO4/H2O solutions at temperatures and acid composi- atures (measured using thermistors mounted in the samples)
tions representative of the atmosphere. Compared to com- as thin solid lines. Each experiment was performed multiple
position measurements done by mass spectrometry of times on an identical sample and is labeled according to
atmospheric particles showing 0.75 wt % Fe and 0.20 metal content and sample number in Figure 5 (i.e., Fe 2 is
wt % Mg, we conclude it is plausible that solid Fe2+ and sample number 2 containing iron). In 60 wt % H2SO4, a
Mg2+ minerals often occur inside atmospheric sulfuric acid solid nucleated from one of the samples containing iron at
particles. 217.9 K causing a steep rise in temperature due to the
release of the latent heat of fusion. Each of the other
3.3. Freezing Experiments samples containing iron subsequently froze, until the last
[27] Bulk freezing experiments were performed to deter- sample froze at 211.1 K. In contrast, no nucleation occurred
mine if the dissolved metal ions could impact the freezing for samples containing magnesium until 196.6 K where one
of sulfuric acid solutions. Each solution contained Fe2+, sample froze, while the remaining samples froze by 193.4 K.

Figure 5. Temperature as a function of time in a 60 wt % H2SO4 ‘‘fast freezing’’ experiment with the
cooling bath temperature designated as a thick line and solution temperatures designated as a thin lines.
The temperature spikes denoted as ‘‘Fe’’ were the point at which the bulk solutions containing soluble Fe
froze, and the temperature spikes denoted as ‘‘Mg’’ were the points at which the solutions containing
soluble Mg froze.
 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS AAC 15 - 9

Figure 6. Lowest freezing temperatures of various solutions as a function of wt % H2SO4. The line with
circles designates the equilibrium H2SO4/H2O phase diagram from Gable et al. [1950]; the dashed line
designates temperatures of ice nucleation from sulfuric acid/water aerosols from Prenni et al. [2001]; the
triangles, circles, and squares represent the lowest temperature at which a 10 mL H2SO4 solution
containing ‘‘artificial meteorite’’, Fe2+, and Mg2+, respectively, froze. The diamonds represent the lowest
temperature at which ‘‘blank’’ 10 mL H2SO4 solutions froze. Each freezing experiment was performed at
least 3 times on the same solution. Some freezing experiments were performed 6 times and are noted by
shaded symbols in Figure 6. All of the samples froze by the indicated temperatures, or none of the
samples froze (as indicated by a downward arrow).

The spread of freezing points in solutions containing the solution temperature affected the freezing point. In every
same amount of mineral appears somewhat scattered. This case, the ‘‘slow freezing’’ experiments yielded approximately
is not surprising because of the stochastic nature of the same freezing temperature as the ‘‘fast freezing’’
freezing; however, it appears that the presence of iron in experiments.
60 wt % H2SO4 increases the freezing point of the solution [29] The only solutions that exhibit an increase in freez-
substantially. ing temperature over the ‘‘blank’’ solutions are the 57.6 wt
[28] The lowest observed freezing temperatures for 10 mL % (SAT composition) solution containing meteoritic metal
samples of binary H2SO4/H2O solutions and for H2SO4/ and the 60 wt % solutions containing meteoritic metal and
H2O solutions containing metals is plotted as function of Fe separately. These solutions froze 12– 20 K higher than
wt % H2SO4 in Figure 6. Also shown in Figure 6 is the solutions containing no soluble metal. The remaining sol-
equilibrium binary H2SO4/H2O phase diagram [Gable et al., utions containing metal sulfates froze at the same temper-
1950] and parameterized ice nucleation data [Prenni et al., ature as the ‘‘blank’’ solution.
2001]. Each solution containing different metal sulfates are [30] Bulk freezing experiments have several limitations
plotted as a different symbol on the graph along with that are not present in aerosol freezing experiments. For
‘‘blank’’ H2SO4 solutions that contain no metal sulfates. example, particles present in the sample or imperfections in
Each freezing experiment was performed at least 3 times on the tube walls can trigger the heterogeneous nucleation of
the same solution and in every case, all of the samples froze SAT, which may explain the deviation in our ice freezing
by the noted temperatures or none of the samples froze (as points from Prenni et al. [2001]. Quantitative results may
indicated by a downward arrow). If there was a solution that not be attainable in these bulk experiments but the qualita-
was of particular interest to us, we performed three addi- tive results are intriguing. Luo et al. [1994] used theoretical
tional freezing experiments on a separate solution that calculations to report a maximum SAT homogeneous nu-
contained approximately the same amount of metal. The cleation rate of 5 108 cm3 s1 between 50 and
solutions on which we performed additional freezing 60 wt % H2SO4 at about 205 K. Koop et al. [1997] refined
experiments are indicated by shaded symbols in Figure 6. these calculations by introducing updated values of H2SO4/
In every case, these solutions froze at approximately the H2O parameters such as diffusion activation energies and
same temperature as the first solution we tested. We also solid/liquid interface energy. They calculated a maximum
performed ‘‘slow freezing’’ experiments with certain solu- SAT homogeneous nucleation rate of 1 103 cm3 s1
tions to determine if the speed at which we lowered the at about 52 wt % H2SO4 and 187 K. It is consistent with
AAC 15 - 10 WISE ET AL.: EFFECTS OF METALS IN SULFURIC ACID SOLUTIONS

these theoretical studies that our bulk solutions exhibited an [34] Cziczo et al. [2001] determined that stratospheric
increase in freezing temperature in the same H2SO4 con- sulfate particles contain 0.75 wt % Fe and 0.20 wt % Mg
centration range. Therefore it is not surprising that solutions by mass, respectively. Because the analytical technique
in the SAT equilibrium regime did not freeze unless the employed by Cziczo et al. [2001] destroys the aerosol
H2SO4 concentration was between 50– 60 wt %. sampled, it is not directly known whether the aerosol
[31] The most interesting results are the solutions that contains any solid metal. Our solubility data suggest that
exhibited an increase in freezing temperatures in the pres- the majority of solid, if introduced as the sulfate salt, will
ence of dissolved metal ions. Even if heterogeneous effects, remain in the solid form in the atmosphere. However, a
such as adsorption of metals on inner walls and alterations small percentage of the solid would dissolve in solution.
of heterogeneous nucleation efficiency, play a role in the Therefore heterogeneous nucleation of a solid (e.g., SAT)
freezing of these solutions, they still freeze 12 –20 K inside a particle containing metal sulfates is possible.
higher than solutions containing no metals or solutions Mineral inclusions have previously been shown to increase
containing solely Mg. We hypothesize that soluble Fe the ease of the crystallization of ammonium sulfate and
played a role in the increased freezing temperature for these nitrate from solutions at room temperature [Han and Martin,
solutions. However, the 57.6 wt % solution showed an 1999; Han et al., 2002; Martin et al., 2001].
increase in freezing temperature with the meteoritic metal [35] To determine if soluble metal in solution had an
solution and not with the solution containing only Fe. This effect on solid formation from H2SO4 solutions, we per-
result was surprising because both solutions contained formed bulk freezing experiments on solutions that
approximately the same amount of Fe. We then performed contained soluble metals. For the majority of acid concen-
freezing experiments on 57.6 wt % solutions containing trations and metal sulfates studied, there was no effect on
each meteoritic metal separately and all of them froze at the the freezing temperatures of the solutions. However, for
same temperature as the ‘‘blank’’ solution within error. 57.6 wt % H2SO4 containing dissolved ‘‘artificial’’ meteor-
Therefore a combination of soluble metals increases the ites and 60 wt % H2SO4 containing dissolved Fe or
freezing temperature of the 57.6 wt % solution. dissolved ‘‘artificial’’ meteorites, there was an increase in
[32] Using the formalism of Koop et al. [1995], the upper freezing temperature of 12– 20 K. From the bulk experi-
bound of the freezing rate w (s1) can be calculated from a ments we estimate an upper limit to homogeneous nucle-
single freezing experiment with w = t1 ln [1/(1  x)], ation of Jhom < 0.0046 cm3 s1 at 220 K. While this
where t is the freezing time period and x is the confidence nucleation rate is too slow to suggest minerals cause SAT
level. Using a typical freezing period of 100 s and a formation at 220 K, they may induce SAT formation at
confidence level of 99 %, we can calculate the upper bound lower atmospheric temperatures.
of the freezing rate to be w  0.046 s1. Using this freezing
rate we can also calculate an upper bound for the homoge- [36] Acknowledgments. The National Science Foundation under
neous nucleation rate coefficient, Jhom, using the relation grant ATM-0137261 supported this work. M.E.W. would like to thank
the NASA-ESS Fellowship Program for funding. The authors would also
Jhom = w/V, where V is the volume of the solution (10 mL). like to thank Daniel Murphy, Carl Koval, and Margaret Asirvatham for
For our bulk freezing experiments, Jhom  0.0046 cm3 s1 helpful discussions and the University of Colorado Geology Department for
and 220 K. Obviously, a stratospheric aerosol droplet with a metal analysis using the ICP/AES.
very small volume would not freeze homogeneously under
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