Atmospheric Aerosol Sulfate: Present Earth's Atmosphere

Chapter-5
Atmospheric Aerosol Sulfate: Present Earth's Atmosphere
The importance of sulfur in the Earth's atmosphere and environment is well
established. Aerosol sulfate is known to alter atmospheric radiative processes due to
its role in increasing the Earth's albedo and as a cloud condensation nucleus and is a
component of the sulfur cycle and environmental acidification. While these
important roles are recognized, there remain significant gaps in understanding the
role of aerosols in these processes. An important role of isotopic analysis is for source
identification, transport, and mechanistic definition of in situ chemical
transformational processes. Sulfate and nitrate aerosols are known agents in
increasing the incidence of cardiovascular disease and definition of surface
characteristics may be of relevance to such studies but are notoriously difficult to
measure. Nitrate is an agent in alteration of terrestrial biodiversity when sufficient
quantities are added to soils and streams. Apportionment of nitrate sources is
difficult because of the multitude of vectors; consequently, new techniques to aid in
source recognition are welcome. Single isotope ratio measurements have been of
limited utility in addressing these issues in the past due to limited specificity of single
isotope ratio measurements such as δ15N, δ34S, or δ18O.
It is known that 70–80% of atmospheric sulfur species in the northern hemisphere
are anthropogenic (Rasch et al., 2000). A gap in strict quantification of the
atmospheric sulfur cycle partially arises from the inability to adequately define the
oxidation processes that govern sulfur dioxide oxidation and chemical
transformational chemistry (Kasibhatla et al., 1997; Lelieveld et al., 1997). Model
calculations underestimate the observed sulfate concentrations in northern latitudes,
and it is plausible that heterogeneous chemical reactions are of importance, but
inadequately recognized. Measurements of oxygen and sulfur mass-
independent isotopic compositions of sulfate aerosols have been developed to
provide independent means to study issues of atmospheric sulfur. Mass-independent
isotopic compositions are observed in atmospheric aerosol sulfate (Lee and
Thiemens, 2001; Lee et al., 2001, 2002; Savarino et al., 2003). The measurements of
the δ17O, δ18O isotopic composition of aerosol sulfate provide a new means to identify
homogeneous versus heterogeneous oxidative pathways, especially coupled with
isotopic measurements of atmospheric H2O2 and ozone (Alexander et al., 2002,
2003, 2004; Savarino and Thiemens, 1999a,b). Characterization of reaction rate
constants, pH reaction rate dependence, and reaction isotopic fractionation factors
(Savarino et al., 2000) allows the homogeneous and heterogeneous reaction
pathways to be quantified (purely gas-phase vs. liquid-phase oxidation). The
foundation for the kinetic model (Alexander et al., 2003, 2005) is the recognition
that the exclusive gas-phase oxygenation pathway for SO2 oxidation is by reaction
with OH radical, known to be strictly mass dependent. Liquid-phase oxidation
proceeds via reaction with ozone and hydrogen peroxide, both mass independent. If
the isotopic composition of oxidizing molecules, as well as associated atmospheric
variables such as pH, temperature, and ambient concentration of the oxidants are
known, the relative oxidation pathways may be accurately quantified from isotopic
measurements and models (Lee et al., 2001; Savarino et al., 2000). The precise
attribution of these oxidative pathways is important for understanding particle
formation processes and transportation.
Advanced modeling efforts (Alexander et al., 2005; Kunasek et al., 2010) using
GEOS-CHEM global models have permitted more specific reaction features to be
identified, such as the role of aerosol particle surfaces above the Indian Ocean. This
work identified a new aerosol generation process previously not considered in
aerosol models. Using multi-oxygen isotopic measurements of sulfate collected
at Trinidad Head, California, specific reaction characteristics, such as ozone-driven
oxidation of SO2 on sea spray, were noted in addition to the identification of
individual source of pollution (Patris et al., 2007).
Measurements of Δ17O, δ18O, and δ34S of atmospheric sulfates in Baton Rouge, Los
Angeles, for a near two year period have shown the ability to resolve secondary
aerosol sulfate formation processes (Davis et al., 2001). In contrast to coastal
California, the Baton Rouge region is dominated by H2O2 oxidation rather than OH.
The work confirmed model predictions for atmospheric chemical reactions among
liquid water, gas, and the role of temperature, pH, and aerosols in a region such as
Baton Rouge.
The use of multi-oxygen isotopes has been applied toward reaction resolution in
chemically anomalous regions. Measurements of sulfate collected in Alert, Canada in
the Arctic have shown that, unlike other geographic regions studied, Arctic oxidation
processes are dominated by SO2(S(IV)) reaction with O2 via transition metal
catalysis on aerosol surfaces, rather than OH and H2O2 (Alexander et al., 2009). A
global chemical transport model was used to interpret the data and quantify the role
of Fe (III)- and Mn (II)-catalyzed oxidation of S(IV) by O2. The inclusion of these
reactions and isotope measurements revealed that the solubility and oxidation state
of the metals are set by cloud water content, chemical source, and sunlight. Inclusion
of the metals' characteristic of the Arctic in the sampling time period was able to
account for the isotope measurements and define the unusual role of O2-catalyzed
reactions in the Arctic.
Besides model considerations of oxidative mechanisms, single source
characterization has been achievable. Both sulfur and oxygen isotopic measurements
of sulfates produced in controlled combustion processes provided new means to
characterize individual source and oxidation mechanism of sulfates in the
atmosphere (Lee et al., 2002). These experimental observations were conducted at
the Centre de Recherches Atmospheriques in Lannemezan, France, in a
dark combustion chamber to isotopically characterize aerosol and gas emissions
from fuel combustion and emission. The chamber has a volume of ~ 160 m3, which
effectively minimizes wall effects and maximizes mixing. The collections were done
in the dark to reduce potential photochemical effects. Fossil fuel and vegetation
burns were performed, including savanna grasses, Lamto grass, rice grass, hay, diesel
fuel, and charcoal. All of these processes produce sulfur and oxygen
isotopic compositions that are strictly mass dependent. Recent atmospheric oxygen
isotopic sulfate measurements at La Jolla, California, a coastal location, were able to
define contributions from maritime shipping – the largest poorly regulated global
sulfur source (Dominguez et al., 2008). In this work, the point sources of primary
ship sulfate contributions were measured and revealed to be mass dependent and
equal to tropospheric O2 (δ18O of ~ 23‰). Based upon the precise three-isotope
source characterization and back trajectory calculations it was demonstrated that
ships contribute between 10 and 44% of the non-sea-salt sulfate found in the fine
diameter (< 1.5 μm) particulate material in the southern coastal California region. As
concluded, these findings are relevant for public health issues, especially with the
predicted increase in ship traffic.
In summary, multi-oxygen isotope ratio analyses of present-day aerosol sulfate
samples have revealed source and chemical mechanistic details in many cases, such
as oxidative pathway quantification, that are new and quantitative and supplement
existing concentration and modeling efforts. Similarly, source
apportionment methodologies are also further amplified with the new multi-isotopic
measurements.