JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 107, NO. D23, 4682, doi:10.

1029/2002JD002120, 2002

Primary sulfate aerosol and associated emissions from Masaya

Volcano, Nicaragua
A. G. Allen,1 C. Oppenheimer,2 M. Ferm,3 P. J. Baxter,4 L. A. Horrocks,5 B. Galle,2,3
A. J. S. McGonigle,2 and H. J. Duffell6
Received 22 January 2002; revised 23 May 2002; accepted 21 August 2002; published 4 December 2002.

[1] Existing studies of the composition of volcanic plumes generally interpret the presence
of sulfate aerosol as the result of comparatively slow oxidation of gaseous SO2. We report
here new observations from Masaya Volcano, Nicaragua, which demonstrate that sulfate
aerosol may also be emitted directly from volcanic vents. Simultaneous aerosol and
gaseous S, Cl, and F compounds were collected at the rim of the passively degassing crater
in May 2001. Mean concentrations of SO42
, Cl
, and F
within the plume were 83, 1.2,
and 0.37 mg m
3, respectively (fine aerosol fraction <2.5 mm) and 16, 2.5, and 0.56 mg
m
3, respectively (coarse aerosol fraction >2.5 mm). The aerosols were highly acidic, with
estimated pH of <1.0 in the fine aerosols. Sulfate was present mainly in smaller particles,
with the fine fraction accounting for 80% of the mass. The bulk of the sulfate was
emitted directly from the magmatic vent. Acidity in the aerosols derived from the presence
of sulfuric acid and, to a lesser extent, hydrofluoric acid, with [H+]/[SO42
] equivalent
values of 0.5–0.8 and 0.3–3 for fine and coarse aerosols, respectively. Gas phase/aerosol
phase mass ratios were, on average, 458 (S), 330 (F), and 186 (Cl), with ranges of
95–1178, 37–659, and 43–259, respectively. These observations of highly acidic aerosol
emitted directly from crater vents have implications for plume chemistry and
environmental and health impacts of volcanic degassing. INDEX TERMS: 0305 Atmospheric
Composition and Structure: Aerosols and particles (0345, 4801); 0322 Atmospheric Composition and
Structure: Constituent sources and sinks; 0370 Atmospheric Composition and Structure: Volcanic effects
(8409); 8409 Volcanology: Atmospheric effects (0370); 8419 Volcanology: Eruption monitoring (7280);
KEYWORDS: volcanic aerosols, sulfuric acid, sulfur dioxide, hydrogen fluoride, hydrogen chloride, Masaya
Citation: Allen, A. G., C. Oppenheimer, M. Ferm, P. J. Baxter, L. A. Horrocks, B. Galle, A. J. S. McGonigle, and H. J. Duffell,
Primary sulfate aerosol and associated emissions from Masaya Volcano, Nicaragua, J. Geophys. Res., 107(D23), 4682,
doi:10.1029/2002JD002120, 2002.

1. Introduction sphere [e.g., Coffey, 1996], relatively little is known about

the chemistry of, and deposition from, tropospheric volcanic
[2] Volcanic emissions are an important source of atmos-
plumes [e.g., Cadle et al., 1979; Lazrus et al., 1979; Rose et
pheric gases and aerosols, including various sulfur and
al., 1986; Delmelle et al., 2001].
halogen compounds. They play important roles in the
[3] Reactive sulfur, chlorine and fluorine compounds are
Earth’s radiation budget [e.g., Robock, 2000; Graf and
present in either aerosol or vapor phase forms, and emitted
Timmreck, 2001], in tropospheric and stratospheric chem-
in association with other components including water vapor
istry and dynamics [e.g., Tabazadeh and Turco, 1993; Chin
and silicate ash particles. Once in the atmosphere, physical
and Jacob, 1996; Graf et al., 1998; Thornton et al., 1999],
and chemical processes act to convert gaseous SO2 to
and can impact terrestrial ecosystems and human health
sulfate, with gaseous HF and HCl establishing equilibria
over local to regional scales [e.g., Sutton and Elias, 1993;
with aqueous phase H+, F
, and Cl
. SO2 reacts with the
Mannino et al., 1996; Thordarson et al., 1996; Raga et al.,
hydroxyl radical (OH) during daylight [Stockwell and
1999; Johnston et al., 2000]. Despite a rather good under-
Calvert, 1983], with an atmospheric lifetime of around 1
standing of the chemistry of volcanic volatiles in the strato-
week, considering this reaction and excluding other mech-
1 anisms of removal [Seinfeld and Pandis, 1998]. However,
School of Geography, University of Birmingham, Birmingham, UK.
2
Department of Geography, University of Cambridge, Cambridge, UK. in most cases, the lifetime of SO2 is shorter due to efficient
3
IVL Swedish Environmental Research Institute, Gothenburg, Sweden. dry deposition and aqueous phase reactions forming sulfate.
4
Institute of Public Health, University of Cambridge, Cambridge, UK. In a volcanic plume, the rate of aqueous phase oxidation by
5
Met Office, Bracknell, Berkshire, UK. hydrogen peroxide [Penkett et al., 1979; McArdle and
6
Department of Earth Sciences, University of Cambridge, Cambridge,
UK.
Hoffmann, 1983] will be limited by H2O2 availability due
to the high sulfur loading; other oxidants include ozone
Copyright 2002 by the American Geophysical Union. [Penkett et al., 1979; Harrison et al., 1982] and metal-
0148-0227/02/2002JD002120 catalyzed molecular oxygen [Martin and Good, 1991]. The

ACH 5-1
ACH 5-2 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO
rate constant for oxidation of S(IV) to S(VI) by ozone
decreases rapidly as pH reduces from 6 to 1. For an ozone
concentration of 30 ppb, the reaction rate at pH 6 is around
3000 mM h
1 (ppb SO2)
1, but at pH 2 it is less than 0.001
mM h
1 (ppb SO2)
1 [Seinfeld and Pandis, 1998]. The
adsorption of F onto ash particles has been well documented
[e.g., Oskarsson, 1980], and metal-catalyzed oxidation of
SO2 could be enhanced on the surface of fine ash aerosols
coemitted with SO2 [Oppenheimer et al., 1998a].
[4] The relative magnitudes of the different processes
eventually determine the atmospheric lifetimes of volcanic
sulfur, chlorine and fluorine, since (1) dry deposition
velocities differ for gases and aerosols, and according to
aerosol size (which is influenced by relative humidity), (2)
activation of aerosols as cloud condensation nuclei accel-
erates removal in precipitation, and (3) scavenging effi-
ciency of gases by cloud or rainwater droplets depends on
droplet size and composition. The fine aerosols released or
formed have long residence times (days to weeks) within
the troposphere [Savoie and Prospero, 1989; Wilson and
Suh, 1997], and may therefore be transported over consid-
erable distances (thousands of kilometers) before deposi-
tion, which can result in enrichment of trace species,
including S, Cl, F, and Br, as well as acidity, in precipitation
[Aiuppa et al., 2001]. It has been suggested that the sulfate
present in wet deposition influenced by volcanic plumes
may arise from the incorporation of sulfuric acid particles,
rather than from dissolution of SO2 [Kawaratani and Fujita,
1990]. Given restricted rates of SO2 oxidation in the near-
source plume, rainfall scavenging of directly emitted pri-
mary sulfuric acid aerosols could therefore be a major
source of acidity in surface deposits. The predominance of
sulfate in rainfall collected in the vicinity of Kilauea
[Harding and Miller, 1982], which shows similar degassing
characteristics to Masaya, seems to support this hypothesis.
[5] We report here new measurements of acidic aerosol
emissions from Masaya Volcano, Nicaragua, and of asso-
ciated emissions, and the relationships between gas phase
and aerosol sulfur, chlorine and fluorine compounds. Our
main objective is to establish whether sulfuric acid aerosols
can be released directly from volcanic vents, and therefore if
plumes may contain both ‘‘primary’’ sulfate aerosol in
addition to ‘‘secondary’’ sulfate aerosol generated by SO2
oxidation in the plume during downwind transport. Primary
sulfate emissions could exert a strong control on plume
chemical evolution, and play an important role in the
observed impacts of volcanic emissions on ecosystems
and human health, and would have implications for calcu-
lations of in-plume SO2 oxidation rates based on assump-
tions of zero sulfate content at source. Physical and
chemical characterization of both gas and aerosol phases
in volcanic emissions is also essential for the future devel-
opment of linked models describing the transport and
chemical evolution of plumes, and will contribute to a better
understanding of volcanogenic pollution.
1.1. Masaya Volcano and Impacts of Degassing on
Environment and Human Health
[6 ] Our measurements were carried out at Masaya
(115902.400N, 8609039.600W and 600 m asl), an active
basaltic volcano in western Nicaragua, situated about 25 km
southeast of Managua. Prehistoric plinian and ignimbrite
eruptions (most recently 6500 years B.P.) formed the large
(11  6 km) Masaya caldera, within which is located a
complex of historically active craters. The Santiago summit
crater contains a persistent lava pond, or lava-filled conduit,
which has shown strong episodic degassing in recent years.
Measurements of SO2 emissions rates in the late 1990s
typically fell in the range 9 –21 kg s
1 [Williams-Jones,
2001], but had fallen to about 4 kg s
1 (350 Mg d
1) in 2001
[Galle et al., 2002]. The plume has been shown to reach ground
level downwind and as a consequence of this, as well as of wet
deposition of pollutants, the degassing has destroyed large
tracts of vegetation, and affected local populations southwest
of the crater [Baxter et al., 1982; Delmelle et al., 2001].
Chemical burning of leaves and flowers of vegetation down-
wind of the crater is a common observation during degassing
crises of Masaya, historically with substantial economic
impact from the loss of coffee crops. Respiratory symptoms
have been reported in these areas, but no formal health surveys
have been possible. Forest cover has been eliminated in the
region within 15 km of the crater, and cultivation of food crops
is difficult throughout the downwind sector.
[7] The role of concentrated sulfate aerosols in contribu-
ting to the above effects warrants further investigation. In
1993 during the degassing crisis at Poás volcano, Costa Rica,
evaporation of the acid crater lake during the dry season was
associated with widespread vegetation damage and health
complaints in the area impacted by the plume [Nicholson et
al., 1993]; at these times acid aerosols with the same
composition of the highly acid waters of the lake (pH < 1)
were being entrained in the gas plume (their size distribution
was not studied). Reports of human health effects from
exposure to fine, concentrated sulfuric acid aerosols are rare
and confined to industrial incidents. In a community in Japan,
between 1960 and 1969, asthmatic symptoms were reported
in about 600 persons living within 5 km of a titanium dioxide
plant producing such emissions [Kitagawa, 1984].
[8] Our measurements at Masaya were obtained during
7– 9 May 2001. At this time, degassing appeared focused
from two vents on the floor of the Santiago crater, one of
which had been recently formed by a minor explosive
eruption on 23 April 2001. Weak incandescence from one
of the vents can be taken as an indication of active lava at
shallow depth in the conduit (probably 50 m) but the
apparently phreatic nature of the April eruption, and
changes in gas ratios observed by Fourier transform infrared
spectroscopy (H. J. Duffell et al., unpublished data) suggest
some degree of magmatic – hydrothermal interaction. The
sustained strong gas emissions from the summit crater have
been explained as the result of degassing-driven convection,
which cycles volatile-charged magma from a deeper reser-
voir through the shallow plumbing system [e.g., Horrocks et
al., 1999]. This manner of degassing characterizes other
persistently active basaltic volcanoes such as Stromboli and
Etna (Italy), Kilauea (Hawaii), and Erta ’Ale (Ethiopia),
though with variations in eruptive style [Francis et al.,
1993; Kazahaya et al., 1994; Stevenson and Blake, 1998].
2. Methods
2.1. Sample Collection
[9] Figure 1 illustrates the Santiago crater, sampling
location, and degassing vents. Samples were collected at
 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO ACH 5-3

Figure 1. (a) Aerial photograph of Masaya showing Santiago crater (in center) and sampling site
(marked with a star). Image from the Instituto Nicaragüense de Estudios Territoriales (INETER). (b)
Photograph of Santiago crater seen from above the east rim (with the sampling site indicated as in (a) and
plume rising passively in center). (c) View into Santiago crater from sampling site showing the two
degassing vents. Vent 2 formed in a phreatic explosion on 23 April 2001. (d) Close-up view of the 23
April 2001 vent, estimated to have a diameter of approximately 10 m.

varying times between 7 and 9 May 2001, for individual
sampling intervals of 12– 110 min. Aerosols (i.e., solid or
liquid particles present within the plume) were sampled
using the actively pumped sequential filtration technique
described by Allen et al. [2000]. Filters were housed in all-
Teflon multiple-stage cartridges, with the airflow passing
through (1) a 47 mm diameter, 12 mm pore size, polycar-
bonate membrane filter (Nuclepore) and subsequently
through (2) a 47 mm PTFE filter (Whatman type
WTP7590004), which collected all aerosols passing through
the prefilter. Airflow of 30 L min
1 was provided using 12
V pumps powered by standard automobile batteries, giving
a 50% cutoff diameter at the Nuclepore filter of 2.5 mm.
Thus coarse aerosols (>2.5 mm) were collected on the
prefilter, and fine aerosols (<2.5 mm) on the PTFE filter.
A total of eight samples were collected within the visible
plume, with an additional sample collected outside of the
plume to provide an estimate of background concentrations
of the aerosol species measured.
[10] SO2, HCl, and HF were collected using polypro-
pylene tube diffusive samplers [Ferm and Svanberg,
1998; Ferm, 2001]. A Teflon membrane over the inlet
was used to avoid turbulent diffusion, and the gases col-
lected on a carbonate-impregnated cellulose filter sorbent
located at the closed end of the tube at the end of the
diffusion path.
2.2. Analytical Procedures
[11] After sample collection the exposed filters were
placed in several layers of small sealable plastic bags,
and packed in plastic boxes containing an ammonia
absorbent (ascorbic acid) to avoid any possibility of neu-
tralization of acidity during transit and storage, and
returned to the UK for analysis. All filters were extracted
into 10 mL of distilled, deionized water, in sealed poly-
propylene vials, for 30 min using a mechanical shaker. A
small aliquot was then decanted into a 1 mL polycarbonate
cup for immediate measurement of pH using an Orion
M701A meter, calibrated using fresh buffer solutions at pH
7 and pH 4. Anions (F
, Cl
, NO
2

3 , and SO4 ) in the
remaining extract solutions were then determined by ion
chromatography, using an automated Dionex DX500 sys-
tem with AG11A/AS11A columns and hydroxide gradient
elution. Details of the analytical procedures have been
published previously [Allen et al., 2000]. SO2, HCl and
HF were similarly determined as SO42
, Cl
, and F
using
ion chromatography following aqueous extraction of the
diffusion tubes.
2.3. Sampling and Analytical Errors
[12] Inaccuracies arising from random background fluc-
tuations in the ion chromatograph conductivity detector
signal and/or analyte column retention characteristics were
estimated by measuring the responses obtained from anal-
ysis of a standard solution containing 1 ppm of each anion
species, repeated at three equally spaced intervals during
the analytical run. Maximum differences obtained were
±2.9% (F
), ±1.4% (Cl
), ±3.1% (NO
3 ), and ±2.8%
(SO42
). The maximum drift in the pH meter signal was
determined to be ±0.03 pH units from repeated analysis of
individual samples. A further allowance is made for a 5%
error in rotameter sample collection flow rate measure-
ACH 5-4 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO

Figure 3. Relationship between total aerosol nitrate and

total aerosol acidity. Error bars indicate estimated total error
on the measurement.

fine aerosols and 0.3– 3.0 for the coarse fraction (for the
coarse fraction, ratios for all samples, except one, were
within 0.3– 0.5).
[14] Concentrations of gaseous SO2, HCl and HF within
the plume (no background data are available for the gases)
were in the ranges 360 –3140, 130– 900, and 30 –570 ppb,
respectively (Table 1, gas phase).
3.1. Sources of Aerosol Acidity
[15] Strong correlations between H+(c), H+(f ), SO2
4(c) , and
2

SO4(f ) (subscripts c and f are used to indicate the coarse and
fine aerosol fractions, respectively) show that most of the
acidity was due to the presence of sulfuric acid (H2SO4), and
that H2SO4 in both fine and coarse fractions derived from the
same source (Table 2 and Figure 2). Correlation between H+
and fluoride, although weaker than that with sulfate, sug-
gests that additional acidity derived from the presence of
dissociated HF. Concentrations of fluoride and chloride were

Figure 2. Correlations obtained for in-plume samples

between (a) fine fraction H+ and coarse fraction H+, (b) fine Table 1. Concentrations of Fluoride, Chloride, Nitrate, Sulfate,
fraction H+ and fine fraction SO42
, (c) coarse fraction H+ and Hydrogen Ions in (a) Fine Aerosol Fraction, (b) Coarse Aerosol
and coarse fraction SO42
, and (d) fine fraction SO42
and Fraction, and (c) Gaseous HF, HCl, and SO2 Concentrations
coarse fraction SO42
. Error bars indicate estimated total (a) Fine aerosol fraction (<2.5 mm, concentrations as mg m
3)
error on the measurement. F
Cl
NO
3 SO42
H+
Background sample concentrations:
0.06 1.33 1.89 3.72 0.08
ments. The resultant cumulative errors are illustrated in
In-plume concentrations:
Figures 2 and 3. Minimum 0.16 0.22 0.00 11.56 0.13
Maximum 0.90 4.87 0.03 165.4 2.81
Mean 0.37 1.23 0.00 82.77 1.27
3. Results and Discussion SD 0.29 1.50 0.01 43.38 0.75
[13] Mean total (combined fine and coarse fractions) in- (b) Coarse aerosol fraction (>2.5 mm, concentrations as mg m
3)
plume aerosol concentrations were 99 mg m
3 (SO42
), 3.7 F
Cl
NO
3 SO42
H+
mg m
3 (Cl
), 1.4 mg m
3 (H+), 0.93 mg m
3 (F
), and Background sample concentrations:
0.28 mg m
3 (NO
3 ). The aerosols collected were highly 0.03 1.12 0.92 0.77 0.01
acidic, with levels of H+ and sulfate in fine (<2.5 mm) and
coarse (>2.5 mm) aerosol fractions of up to 2.8 and 0.3 mg In-plume concentrations:
Minimum 0.22 0.62 0.00 2.26 0.07
m
3 (H+) and 165 and 32 mg m
3 (SO42
), respectively, Maximum 1.21 11.50 1.45 32.29 0.33
considerably exceeding background concentrations (Table Mean 0.56 2.47 0.28 16.26 0.15
1). On average, the fine aerosol fraction (<2.5 mm) SD 0.34 3.72 0.48 8.62 0.08
accounted for 89% (H+), 84% (SO42
), 40% (F
), and (c) Gas phase
33% (Cl
) of the total masses of these species; thus while HF HCl SO2
H+ and SO42
were present mainly in fine particles, F
and ppb mg m
3
ppb mg m
3
ppb mg m
3
Cl
were more evenly distributed between the two size Minimum 32 25 127 183 362 916
fractions, and the contribution of fine aerosols (<2.5 mm) to Maximum 567 448 902 1300 3138 7950
total acidity exceeded that of coarse aerosols by a factor of Mean 257 203 644 929 1877 4756
about 8. [H+]/[SO42
] equivalent ratios were 0.5– 0.8 for SD 216 171 300 432 1308 3314
 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO ACH 5-5

Table 2. Correlation Matrix (Correlation Coefficient, r) for In- (derived from CRC [1985]), from which pH < 1.0 is
Plume Fine and Coarse Fraction Aerosol Species (Subscripts (c) achieved when the H2SO4 concentration exceeds 0.8 wt%.
and (f ) Refer to Coarse and Fine Aerosol Fractions, Respectively) For atmospheric aerosols, an equilibrium solution concen-
n=8

F(c)

Cl(c) NO
2

3(c) SO4(c)
+
H(c) F(f
) Cl
(f ) NO
2

3(f ) SO4(f )
tration of 5 wt% H2SO4 is obtained at a relative humidity
(RH) of 98% [Seinfeld and Pandis, 1998], at which the
Cl
(c) 0.7
NO

0.2 0.1 corresponding solution pH is 0.3. Although coemission of
3(c)
SO2
4 (c) 0.3
0.3
0.7 water vapor will have resulted in elevated relative humidity
+
H (c) 0.4
0.2
0.2 0.8 close to emission vents, transport of the plume into lower
F

(f ) 0.4
0.3
0.1 0.7 0.8 humidity regimes will have acted to increase further the
Cl
0.7 1.0 0.0
0.3
0.1
0.2
NO

(f )

0.2 0.1 1.0
0.7
0.1
0.1 0.0
H2SO4 mass fraction. At RH = 90% the equilibrium H2SO4
3(f )
SO2
4 (f ) 0.2
0.4
0.7 0.9 0.7 0.7
0.3
0.7 mass fraction is 15%, and at RH = 80% and 50% it is
+
H (f ) 0.3
0.3
0.6 0.9 0.7 0.7
0.2
0.6 1.0 25% and 45%, respectively [Seinfeld and Pandis, 1998],
so that aerosol acidity will have increased further during
downwind transport (prior to any significant neutralization
by ammonia). Acidity in the smallest aerosols, <0.1 mm
covariant in coarse aerosols only, presumably due to the diameter, will be even higher due to the Kelvin effect.
greater stability of HF and HCl in larger aqueous droplets of
lower acidity than the fine sulfuric acid containing aerosols, 3.2. Volatilization Losses
as shown in the fine/coarse mass ratios and in a higher ratio
[18] Weak inverse correlation of chloride with acid species
for [F
]/[SO42
] in the coarse fraction.
(H+ and SO42
) in both fine and coarse aerosols (Table 2) is
[16] No sulfite species (SO32
or HSO3
) were present, as
indicative of loss by volatilization; although association
expected since S(IV) exists almost exclusively in the form
between chloride and fluoride in the less acidic coarse
SO2H2O at low pH. Under these conditions most aqueous
aerosols indicates that both HCl and HF were coemitted,
phase oxidation reactions are slow [Seinfeld and Pandis,
fluoride was apparently volatilized from both fractions at a
1998]. Although oxidation by H2O2 has been found to be
slower rate than HCl.
relatively pH insensitive [Eatough et al., 1994], the low
[19] The nitrate present in background aerosol advected
availability of this oxidant could not generate any significant
into the study area was also displaced following aerosol
aerosol sulfate during the short (tens of seconds) transit
acidification, resulting in losses from all aerosols and
between vent and sampler. However, the possibility that
increasing depletion with increasing H+ concentration (Fig-
dissolved SO2 could be oxidized forming sulfate during
ure 3). Assuming normal background nitrate levels to be
sample storage was examined by consideration of the
consistently similar to our ‘‘background’’ sample, loss of
quantity of S(IV) present at equilibrium in the aerosols
nitrate was complete in almost all of the fine fraction
collected. The concentration of total dissolved SO2, which
samples. This finding is further supported by the inverse
diminishes rapidly as acidity increases to pH  2, and more
correlations obtained between nitrate and other aerosol
slowly below pH  2, is described by:
species (with the exception of chloride).

½SðIVÞ
¼ HS*ðIVÞ  pSO2 ; ð1Þ 3.3. Gas/Aerosol Mass Ratios
[20] In-plume gas phase/aerosol phase ratios (by mass)
were, on average, 458 (S), 330 (F), and 186 (Cl), with
where H*S(IV) is the pH dependent Henry’s law constant for ranges of 95– 1178 (S), 37– 659 (F), and 43– 259 (Cl).
SO2, and pSO2 is the SO2 mixing ratio. From this we can Hobbs et al. [1991] measured sulfur gas/aerosol ratios of
derive a solution S(IV) concentration of 3  10
6 M for
H*S(IV)  1.5 M atm
1, at a gas phase mixing ratio of 2000
ppb (our mean measured value was 1877 ppb), at a
temperature of 25C (during sampling temperatures ranged
between 20C and 34C). This is equivalent to 96  10
6
mg mL
1 of S(IV), or 288  10
6 mg mL
1 of potential
SO42
, so that the oxidized S(IV) contribution to total
sulfate is very small; an aerosol mass of 1 mg would
contain only 288  10
6 mg of S(IV) sulfate, assuming
complete oxidation, which is approximately eight orders of
magnitude smaller than the measured mass of (primary)
sulfate. This is an important finding as it confirms our
initial hypothesis that near-source sulfate within the plume
almost entirely arises from primary vent emissions. The
visual appearance of fine particle scattering in the plume
directly exiting the vents on the floor of Santiago crater is
also consistent with this conclusion (Figures 1b –1d).
[17] The pH of sulfuric acid solutions may be described
by:
½H2 SO4
ð% wtÞ ¼ 10:56e
2:5584pH ; ð2Þ ing the same observation period (H. J. Duffell et al.,
700 in the plume of Mount Redoubt (Alaska), while at
Soufrière Hills Volcano (Montserrat) near-source gas/aero-
sol ratios (by mass) were 1.4– 25, 8 – 245, and 183 – 269 for
S, F, and Cl, respectively [Allen et al., 2000]. The latter
ratios are of similar magnitude to those at Masaya for F and
Cl but not S. Observed gas phase ratios (Table 3) show
divergence between the two volcanoes, attributed to unusu-
ally high HCl at Soufrière Hills Volcano, perhaps combined
with rapid depletion of SO2 [Oppenheimer et al., 1998b].
While the magnitude of HF/SO2 ratios was similar at the
two locations, ratios HCl/SO2 and HF/HCl were very
different, supporting the notion that this was due to anom-
alous HCl emissions. Published data (Table 3) suggest that
HCl/SO2 ratios exceeding 1 in volcanic emissions are rare,
although the work of Symonds et al. [1990] at Augustine
Volcano suggests that ratios may increase with progressive
degassing of magma, while HF/HCl ratios are also typically
1. Our measured HCl/SO2 ratios are in reasonable agree-
ment with a mean mass ratio of 0.13 obtained at Masaya
using Fourier transform infrared (FTIR) spectrometry dur-
ACH 5-6 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO

Table 3. Reported Gas Phase Mass Ratios for HCl, HF, and SO2 Close to Volcanic Sources
Parameter HCl/SO2 HF/SO2 HF/HCl Technique Location, year Reference
a
Min 0.137 0.018 0.089 Direct (filters and Masaya, 2001
Max 1.00 0.089 0.363 diffusion tubes)
Mean ± SD 0.310 ± 0.341 0.045 ± 0.026 0.195 ± 0.108
b
Mean 0.34 0.04 0.12 OP-FTIR Masaya, 1998/9
c
Mean ± SD (day) 0.36 ± 0.005 – – FTIR Masaya, 1998
Mean ± SD (night) 0.26 ± 0.033 – –
d
Mean 0.27 0.024 0.087 FTIR Masaya, 2000
e
Mean 0.13 0.01 0.087 FTIR Masaya, May 2001
f
Min 1.782 0.041 0.003 Direct (filters) Soufrière Hills, 1996
Max 25.140 0.114 0.023
Mean ± SD 12.63 ± 9.170 0.077 ± 0.025 0.010 ± 0.007
g
Mean 5.7 – – FTIR Soufrière Hills, 1996
h
Mean 0.142 0.031 0.219 FTIR Etna, 1997
i
Min 0.114 – – FTIR Etna, 1994
Max 0.189 – –
i
Min 0.406 – – FTIR Vulcano, 1994
Max 0.812 – –
j
Estimated 0.057 0.123 2.14 Petrologic Laki, 1783 – 1784
a
Present work.
b
Horrocks et al. [1999].
c
Burton et al. [2001].
d
Duffell et al. [2001].
e
Oppenheimer et al. (unpublished data).
f
Allen et al. [2000].
g
Oppenheimer et al. [1998b].
h
Francis et al. [1998].
i
Francis et al. [1995].
j
Thordarson et al. [1996].

unpublished data). While differences are likely to occur due
to variable rates of dissolution of HCl into water droplets,
particularly at night [Burton et al., 2001], Duffell et al.
[2001] showed that HCl/SO2 ratios did not change signifi-
cantly during daytime transit for distances of up to 15 km
from the summit crater.
[21] Given an estimated total SO2 flux of 350 Mg d
1
(from the UV spectroscopic data obtained during May
2001) [Galle et al., 2002], our measured gas phase/aerosol
phase ratios infer a mean flux of primary SO2
4 of 1 Mg
d
1 (range of 0.23 – 2.9 Mg d
1). To place this into
perspective, total aerosol (i.e., sulfate, ash, and other spe-
cies) flux rates of 1.3 Mg d
1 have previously been
estimated at White Island [Rose et al., 1986], 21 Mg d
1
at Erebus [Chuan et al., 1986], and 20 and 24 Mg d
1 at
Poás and Colima volcanoes, respectively [Casadevall et al.,
1984]. Hobbs et al. [1991] estimated a SO42
flux of 9 –
170 Mg d
1 during the 1990 eruptions of Mount Redoubt.
3.4. Origin of Primary Sulfate Aerosol
[22] We are unsure of the precise mechanisms of forma-
tion of sulfate aerosol at, or very close to, the magma – air
interface but consider three potential origins: (1) a primary
magmatic vapor phase, (2) the product of magmatic – hydro-
thermal interactions, and (3) very high temperature oxida-
tion of gaseous SO2 immediately above the magma surface.
Any subsurface processes which generate sulfuric acid and
associated acidic chlorine and fluorine compounds will be
governed by the volatile contents and physicochemical
conditions within the magma, as well as by hydrothermal
interactions [Oppenheimer, 1996; Symonds et al., 2001],
either directly between hydrothermal and magmatic fluids,
or via incorporation of sulfate precipitates present in rocks
modified by hydrothermal action. In terms of condensation
of volatile species, the conditions in the upper conduit
region of Masaya may be analogous to those associated
with late stages of degassing of cooling lava flows [Oskars-
son, 1981]. Such processes may act to form vapor phase
sulfuric acid, which rapidly condenses at the lower temper-
atures encountered near emission vents, forming fine aero-
sol droplets that are emitted directly from the crater. The
droplets may contain a mineral component, where conden-
sation occurs on to preexisting ash particles. We also
consider the possibility that the sulfate aerosol forms as a
combustion product of SO2 instantaneously as it passes
from magma into the atmosphere, in an analogous fashion
to the formation of ultrafine sulfate particles in the exhaust
of jet aircraft.
[23] Further work will be necessary to identify how
widespread is the phenomenon of primary sulfate aerosol
emission from volcanic vents but we suspect that it may be
common for open-vent degassing (i.e., across a magma – air
interface). [H+]/[SO42
] equivalent ratios at Masaya were
similar to those measured at Soufrière Hills volcano in 1996
[Allen et al., 2000], which were 0.5 – 0.8 (fine fraction
aerosols) and 0.1– 0.9 (coarse fraction aerosols), at locations
within or close to the crater. In addition, measurements of
the size distribution of emitted sulfate at the Soufrière Hills
showed that around 70% of the total mass of sulfate was
present in the fine fraction, again similar to Masaya. Such
similarities in physicochemical composition lend support to
the notion that primary acid sulfate aerosol emissions may
characterize many volcanic emissions.
4. Conclusions
[24] We have shown that highly acidic sulfate particles
are released directly as primary emissions during the type of
volcanic activity characterized by relatively frequent small-
scale eruptions and persistent degassing, and that for short
 ALLEN ET AL.: PRIMARY SULFATE AEROSOL FROM MASAYA VOLCANO
transport distances this source of aerosol sulfate greatly
exceeds that formed by in-plume oxidation of SO2. This is
an important finding as it may help to explain both the
mechanics of plume chemical evolution as well as the
observed impacts of volcanic plumes on ecosystems and
human health. It also has implications for field measure-
ments of SO2 to sulfate conversion rates in volcanic plumes,
if they assume that all sulfate present is the product of SO2
oxidation; this would result in overestimation of the rates of
aerosol sulfate formation (J. N. Porter et al., Sun photometer
and lidar measurements of the plume from the Hawaii
Kilauea volcano Pu‘u ‘O‘o vent: Estimates of aerosol flux
rates and SO2 lifetime submitted to Geophysical Research
Letters, 2002.) The most acidic aerosols were found to be
present within fine particles, which may be readily inhaled
causing pulmonary damage. Further work will be needed to
(1) study in greater detail the processes of plume physical
and chemical evolution, including changes in the size
distribution of acidic particles, (2) develop chemical trans-
port and health impact models having predictive capabil-
ities, and (3) identify the source of the sulfate; if this can be
shown to be a magmatic phase it could provide insight into
processes of magma degassing, chemistry and dynamics,
with implications for volcano surveillance.
[25] Acknowledgments. Fieldwork at Masaya was funded by the GNV
and NERC and carried out in collaboration with the INETER (Managua) and
with the kind support of the staff of the Masaya National Park. We also
gratefully acknowledge the assistance of the British Embassy, Managua. BG
and AM were funded by the EC 5th Framework project ‘‘MULTIMO’’ and
HJD was funded by a NERC studentship (GT4/99/ES/43). Financial support
for the diffusion tube measurements was gratefully received from the King
Carl XVIth Gustaf’s 50th Anniversary Foundation. We are especially grateful
to the three anonymous referees for their highly insightful and constructive
comments and criticisms of the original manuscript.
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A. G. Allen, School of Geography, University of Birmingham,
Edgbaston, Birmingham B15 2TT, UK. (a.g.allen@bham.ac.uk)
P. J. Baxter, Institute of Public Health, University of Cambridge,
Robinson Way, Cambridge CB2 2SR, UK.
H. J. Duffell, Department of Earth Sciences, University of Cambridge,
Downing Street, Cambridge CB2 3EQ, UK.
M. Ferm, IVL Swedish Environmental Research Institute, P.O. Box
47086, SE-40258, Gothenburg, Sweden.
B. Galle, A. J. S. McGonigle, and C. Oppenheimer, Department of
Geography, University of Cambridge, Downing Place, Cambridge CB2
3EN, UK.
L. A. Horrocks, Met Office, London Road, Bracknell, Berkshire RG12
2SZ, UK.