PERSPECTIVE

PUBLISHED ONLINE: 8 AUGUST 2016 | DOI: 10.1038/NGEO2771

Role of atmospheric chemistry in the climate

impacts of stratospheric volcanic injections
Allegra N. LeGrande1*, Kostas Tsigaridis1,2* and Susanne E. Bauer1,2
The climate impact of a volcanic eruption is known to be dependent on the size, location and timing of the eruption. However, the
chemistry and composition of the volcanic plume also control its impact on climate. It is not just sulfur dioxide gas, but also the
coincident emissions of water, halogens and ash that influence the radiative and climate forcing of an eruption. Improvements
in the capability of models to capture aerosol microphysics, and the inclusion of chemistry and aerosol microphysics modules
in Earth system models, allow us to evaluate the interaction of composition and chemistry within volcanic plumes in a new
way. These modelling efforts also illustrate the role of water vapour in controlling the chemical evolution — and hence climate
impacts — of the plume. A growing realization of the importance of the chemical composition of volcanic plumes is leading to
a more sophisticated and realistic representation of volcanic forcing in climate simulations, which in turn aids in reconciling
simulations and proxy reconstructions of the climate impacts of past volcanic eruptions. More sophisticated simulations are
expected to help, eventually, with predictions of the impact on the Earth system of any future large volcanic eruptions.

V
olcanic eruptions fascinate people, not only because of the
tremors, glowing cascades of ash and rivers of lava, but also
because of the regional disruptions they cause, including ash
deposition and ‘dry fogs’ — airborne masses of sulfate aerosols that
do not feel wet like normal fogs. Sulfuric acid aerosol particles have
long been suspected of creating climate disturbances. As far back
as the eighteenth century, Benjamin Franklin conjectured that the
1783–1784 eruption of the Icelandic Laki volcano had been the cause
of several cold and harsh winters1.
Mount Agung in Indonesia erupted in 1963, reinvigorating inter-
est in the principal mechanism through which volcanic eruptions
affect climate. Initially, the most explosive volcanoes with the great-
est amount of ash emission were suspected of having the greatest
influence on climate2,3. Later analysis using radiative transfer calcu-
lations revealed that the volume of sulfur dioxide (SO2) injected into
the atmosphere, and its subsequent conversion into sulfate aerosols
in the stratosphere, is the principal cause of global-scale cooling fol-
lowing an eruption4,5. This insight has been confirmed by numerous
studies using measurements from the TOMS and SAGE II satellite
instruments and their descendants6–9, and was further borne out by
the eruption of Mount Pinatubo in 1991, which released huge quan-
tities of SO2. Consequently, global surface temperatures dropped by
half a degree Celsius10, and tropical and monsoonal rainfall decreased
markedly 11. This event’s forcing at its peak exceeded 6 W m–2 (simi-
lar in magnitude but opposite in sign to anthropogenic greenhouse
gas forcing)6.
Volcanic eruptions also influence the variability of climate modes,
for instance in causing the onset of positive North Atlantic Oscillation
conditions12. For the twentieth century, eruptions were coincident
with establishment of positive phases of the El Niño/Southern
Oscillation (El Niño events)13; in the past, they were instead, para-
doxically, associated with negative phases14. Thus the link between
the occurrence of El Niño events and volcanic eruptions remains
uncertain. Eruptions have been found to be probable disruptors
of deep water circulation in the Atlantic15. The exact mechanisms
through which these changes occur are not yet fully understood.
Volcanic aerosols and atmospheric chemistry
Studies on the climate impacts of sulfate aerosols2–4 occurred in
parallel with research into associated changes in atmospheric
chemistry 16,17. Atmospheric water has long been known to be vital
in contributing to the formation rate of sulfate aerosols from SO2
emissions18, and it has been hypothesized to be a limiting factor
in volcanic aerosol formation19, specifically through the creation
of OH radicals from water. Modelling experiments based on the
1991 Mount Pinatubo eruption and on the Toba eruption about
74,000 years ago20, which was several orders of magnitude larger,
indicate a potential for the creation of OH radicals to accelerate
the conversion of SO2 gas into sulfate aerosols19. Sulfur dioxide is
a greenhouse gas that may temper the negative forcing of sulfate
aerosols21, which makes the balance between SO2 and sulfate a
significant controller of the climate response following an erup-
tion. But it is not certain that a state in which water was depleted
through the production of OH radicals could exist — not only
because the stratospheric warming from such an aerosol layer 22
would warm the tropopause (the extremely cold boundary which
removes moisture) and allow in more moisture, but also because
volcanoes do not exclusively inject SO2 (ref. 16).
Water, in addition to converting SO2 into sulfate, affects the
oxidizing capacity of the stratosphere and influences ozone (O3)
concentration23. Modulating ozone concentrations can cause either
positive or negative forcing, depending on the chemical state of the
stratosphere, including reactive nitrogen and halogen levels. The
stratosphere is practically dry when compared with the troposphere,
and this demands a closer look at the composition of the volcanic
injection itself, since an eruption can co-inject water 24 and halogens
directly into the stratosphere16. The role of injected water from an
eruption whose plume stays in the troposphere is not expected to be
significant, owing to the abundance of water vapour below the trop-
opause, but it could be important for eruptions reaching the strato-
sphere. Note that here we use the term ‘plume’ to cover the various
phases of the volcanic ejecta, and the evolution and interaction of
these emissions in the climate system.

NASA Goddard Institute for Space Studies, 2880 Broadway New York, New York, USA. 2Center for Climate Systems Research, Columbia University, 2880
1

Broadway New York, New York, USA. *e-mail: allegra.n.legrande@nasa.gov; kostas.tsigaridis@columbia.edu

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PERSPECTIVE NATURE GEOSCIENCE DOI: 10.1038/NGEO2771

SW

Halogens

Sulfate

Sulfate

SO SO2
2 +
Ash

H2
O
Tropopause LW
H2O (g)

Time

Figure 1 | Volcanic water in the stratosphere alters aerosol evolution. The injection of stratospheric water along with volcanic SO2 (blue band) yields a
much enhanced rate of sulfate formation relative to SO2 injection alone (red band). Water increases the availability of OH radicals, converting SO2 more
quickly into sulfate aerosols (green spheres) and increasing the rate of aerosol growth. While these aerosols reflect shortwave radiation (SW) from
space, leading to cooling, sulfate aerosols may also scatter longwave radiation (LW) from the Earth, promoting warming. The nature, formation rate and
abundance of the aerosols formed will control the regional and global climate response following a volcanic eruption. The different altitudes of the two
bands is for illustration purposes only.

The water-limited stratospheric chemistry complicates the sim-
ple climate-impact story of a thermal warming in the stratosphere
and a shortwave cooling in the troposphere as a direct response
to sulfate aerosol formation. For instance, stratospheric warming
increases the temperature of the tropopause, allowing more mois-
ture to reach the stratosphere from below 22, which has the potential
to dampen the negative solar forcing from sulfate aerosols25. This
dynamical water source in the lower stratosphere can also reduce
the water limitation of the SO2 oxidation and enhance aerosol for-
mation rates.
These intricacies within the basic mechanics of volcanoes’
capacity to influence climate were reasonably well understood by
the mid-1990s. The potential roles of ash, water and even halo-
gens as confounding factors to SO2 were also recognized decades
ago4. However, three-dimensional general circulation models were
not yet capable of handling the chemistry, aerosols and radiative
impacts of volcanic injections simultaneously. For this, parameter-
izations were developed to provide external forcing to the models
for the historical period22, and the chemistry impacts and feedbacks
were not implemented. Probably owing to the inability to model the
chemistry, the interest and development in improving the way that
we represent volcanoes in climate models scaled back significantly
for the next decade.
Pushing models to the brink
As part of the Coupled Model Intercomparison Project Phase 5
(CMIP5), the palaeoclimate community coordinated a suite of
experiments to emulate the past millennium26. Throughout this
period, the largest abrupt climate perturbations were related to vol-
canic eruptions, and large numbers of volcanic eruptions over an
extended period were linked to intervals of centennial-scale cool-
ing 27. This study of the past millennium brought about renewed
interest in volcanic modelling 28,29, but it lacked any improvements
to the way in which the effects of volcanoes were implemented. The
model representation of volcanoes ranged from externally specified
top-of-the-atmosphere negative forcing to more sophisticated (but
again externally specified) aerosol layers with prescribed optical
thickness of the aerosol layer. The earlier efforts to understand the
potential emissions from volcanic events (and their significance to
atmospheric chemistry and radiative forcing) were, unfortunately,
left out of these parameterizations.
As a consequence, it is not surprising that notable mismatches
existed between model simulations of climate and either direct or
proxy measures of climate30,31. The most obvious was the models’
response to the prescribed aerosol forcing, which was too large
relative to the cooling implied by data compilations31. These mis-
matches have reinvigorated the interest in past climate records of
responses to volcanic events, and encouraged the modelling com-
munity to take a closer look at the evolution of the chemistry and
physics of a volcanic plume32. From the data side, more rigorous
investigation of the model forcing 33 and climate response34 has been
initiated as well. These studies have served to reduce the uncertainty
in the forcing and climate response, and hence enhance our ability
to test the skill of chemistry and aerosol modules when including
the effects of volcanoes in models.
For atmospheric chemistry and climate modellers, it is an
exciting time to be involved in the research on volcanic impacts
on climate. Collaborative, comparative initiatives such as SSiRC
(Stratospheric Sulfur and its Role in Climate) and VolMIP (Volcano
Model Intercomparison Project, CMIP6) are seeking out smarter,
more physically based ways to implement volcanic eruptions.
Similar to the advances in climate modelling resulting from the
coupling of dynamic ocean modules with sophisticated atmospheric
schemes, the evolution of climate models to include a prognostic
calculation of volcanic aerosols yields the potential to predict the
impact of future volcanic eruptions on climate, once the magnitude
and location of the gaseous injection are constrained. Determining
the impact of each constituent of volcanic eruptions will aid this
capacity for predicting the climate impact of future volcanic events.
We have capitalized on improvements to the aerosol microphysics35
of the NASA Goddard Institute for Space Studies GISS ModelE36
to make a preliminary assessment of how the joint injection of

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NATURE GEOSCIENCE DOI: 10.1038/NGEO2771 PERSPECTIVE
volcanic SO2 and water vapour modulate stratospheric chemistry,
particularly the oxidizing capacity of the stratosphere and the con- 0.10

Global stratospheric mean

aerosol optical depth
version rate of SO2 to sulfate aerosol. 0.08

It’s all in the chemistry 0.06

Chemistry plays an important role in a volcanic plume: both directly,
by converting SO2 into sulfate aerosols; and indirectly, by influenc-
ing the OH abundance (oxidizing capacity) in the plume. Following
a volcanic injection of material into the stratosphere, the oxida-
tion of SO2 by OH radicals begins, briefly forming HOSO2 before
reacting with O2 to form SO3 and HO2 radicals37. In the presence
of water vapour, SO3 then forms sulfuric acid (H2SO4). Owing to
its extremely low vapour pressure, the H2SO4 formed either nucle-
ates to form new particles, or condenses on pre-existing aerosols,
increasing the sulfate aerosol mass.
The concentration of water vapour controls nucleation, since
the main mechanism of new particle formation is believed to begin
with binary H2SO4–H2O nucleation38, which is especially true under
stratospheric conditions. For simplicity, models form sulfuric acid in
a single step, directly from the SO2 oxidation by OH, which is inde-
pendent of water concentration. Models with aerosol microphysi-
cal parameterizations then form sulfate aerosols either through new
particle formation (which is dependent on sulfuric acid concentra-
tion and relative humidity) or through condensation39. In contrast,
bulk aerosol models simply assume that the sulfuric acid formed is
in the aerosol phase40. Nucleation rates decrease exponentially with
increasing temperature and decreasing relative humidity 38, and are
extremely low at typical stratospheric conditions, where relative
humidity is below 1%.
Water also has an indirect impact on sulfate aerosol formation
in the stratosphere through OH radicals. The main OH formation
pathway in the atmosphere starts with ozone photolysis that pro-
duces excited atomic oxygen, O(1D) (ref. 41) which in the presence
of water vapour can react with H2O and form two OH radicals. The
production of OH radicals through this mechanism has two impor-
tant implications: first, it decreases the O3 formation potential of
the system by taking O(1D) out of the Chapman cycle42; second, it
increases the SO2 oxidation by OH, accelerating the sulfate aerosol
formation rate. Thus, a stratospheric volcanic injection that included
both SO2 and H2O would result in a much faster production of sul-
fate aerosol in the otherwise extremely dry stratospheric air because
of significantly higher OH levels, resulting in both a faster decay rate
of SO2 and a faster formation of a sulfate aerosol layer, with impor-
tant climate implications (Fig. 1).
The chemistry of the stratosphere will be affected as a whole
by the OH formation following a large water injection, with the
reduced methane lifetime due to the increased OH being one of
the most climate-relevant changes. The concentration of O3 will
also be affected, and can either decrease or increase43–45, depend-
ing on the halogen levels in the stratosphere and changes in
stratospheric dynamics46.
The changes in gas-phase chemistry following a ‘wet’ erup-
tion have global-scale implications. We tested this using the GISS
ModelE36 coupled with gas-phase chemistry and the aerosol
microphysical module MATRIX35. We simulated a Pinatubo-sized
wet eruption with injections of ~18  Tg SO2 (Tg, 1012 grams; refs
7,47) and ~150  Tg H2O (refs 25,48). We determined that during
the month of the eruption, the stratospheric global-mean aerosol
optical depth (AOD) produced by the wet eruption is more than
double the mean for a ‘dry’ eruption that only injects SO2 (Fig. 2).
A month later, the global-mean AOD is still ~40% higher in the wet
eruption case. Two months later and beyond, the slower chemis-
try in the dry eruption catches up, and the simulated global-mean
AODs between the two cases are very similar. A single wet erup-
tion injects an amount of water into the stratosphere comparable to
that formed by methane oxidation over the course of a full year 24,
0.04
0.02 SO2-only injection
SO2 + H2O injection
0.00
Jul Aug Sep Oct
Figure 2 | Evolution of stratospheric global-mean aerosol optical depth
following a volcanic eruption. Sulfate aerosols form faster in the presence
of water vapour as a result of the higher abundance of OH radicals, which
accelerates SO2 oxidation. The initial new particle formation rapidly creates
a large abundance of very small sulfate aerosols which later coagulate.
The resulting reduced number of larger, but still small, particles explains
the brief drop in aerosol optical depth. Further coagulation, together with
condensation, ultimately forms the accumulation-mode volcanic aerosol
layer. By comparison, the SO2-only injection has much slower chemistry,
which reduces the initial rate (first 3 months) of aerosol formation.
and increases the OH concentration in the plume by a factor of ten
(ref. 47) as a direct consequence of the O(1D) reaction with water
vapour. The faster stratospheric AOD formation during the first
few months in the wet eruption agrees better with stratospheric
AOD reconstructions8,49.
Moving forward
Volcanic eruptions could inject massive amounts of water into the
stratosphere. For the Toba eruption, a water release of as much
as 27 Pg (Pg, 1015 grams) has been estimated, although the mag-
nitude is uncertain50. Such water injections have the potential to
severely influence the rates of chemical reactions and of aerosol
formation. To quantify the effect of such injections in the water-
limited stratosphere, it is essential to couple gas-phase chemistry
with aerosol microphysics in climate models, so that the climate
impact of such massive events, and their evolution in space and
time, can be quantified.
If such an eruption were to occur today, we have much improved
models for estimating its climate impact, and a better apprecia-
tion of the importance of determining the volume not only of sul-
fur injection, but also of water and other ingredients including ash
and halogens. A growing awareness of the importance of including
atmospheric chemistry when assessing the climate impacts of vol-
canic eruptions will help with better estimates in future events.
Received 29 March 2016; accepted 21 June 2016;
published online 8 August 2016
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Acknowledgements
We thank NASA GISS for institutional support. We also thank the NASA MAP
programme for continued support. Resources supporting this work were provided by
the NASA High-End Computing (HEC) Program through the NASA Center for Climate
Simulation (NCCS) at Goddard Space Flight Center.
Author contributions
A.N.L. was inspired to seek out better aerosol microphysics modules by the mismatches
of simulated and inferred climate impacts for volcanoes in the CMIP5/PMIP3 last
millennium experiment. A.N.L. and K.T. conceived the work, performed the model
simulations and analysed the results. All authors contributed to the text and the design of
figures. K.T. and S.E.B. contributed expertise with the MATRIX model.
Competing financial interests
The authors declare no competing financial interests.

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