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@PHDTHESIS{Milousis:1042327,
author = {Milousis, Alexandros},
title = {{A}dvances in {U}nderstanding {N}itrate {A}erosol
{F}ormation and the {I}mplications for {A}tmospheric
{R}adiative {B}alance},
volume = {663},
school = {Köln},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2025-02530},
isbn = {978-3-95806-823-0},
series = {Schriften des Forschungszentrums Jülich Reihe Energie $\&$
Umwelt / Energy $\&$ Environment},
pages = {195},
year = {2025},
note = {Dissertation, Köln, 2025},
abstract = {Recent decades have highlighted the profound consequences
of air pollution on air quality and human health, resulting
in millions of deaths worldwide and contributing to the
intensification of the Earth’s climate due to ongoing
anthropogenic emissions. These emissions, originating from
densely populated and industrialized regions, lead to the
release of gaseous pollutants that undergo chemical
transformations in the atmosphere, producing secondary
particulate pollutants. Atmospheric modeling is a valuable
tool that facilitates a more profound comprehension of
physicochemical processes, thereby providing guidelines for
mitigating air pollution and enhancing our understanding of
climatic feedback mechanisms. Recent policies aimed at
reducing emissions from anthropogenic activities have
predominantly focused on specific species, including carbon
dioxide (CO2), methane (CH4), sulfur dioxide (SO2), and
nitrogen oxides (NOx). This is expected to cause a change in
the landscape of secondary aerosol population
characteristics as the abundancy of their precursors will
also change. For example, the observed historical increase
in ammonia (NH3) emissions is expected to enhance the
importance of certain inorganic aerosol species at the
expense of others. A substantial body of research conducted
in the most heavily polluted regions of the Northern
Hemisphere has already demonstrated that the average
concentration of aerosol nitrate is comparable to, if not
greater than, the respective concentration of aerosol
sulfate. Sulfate is currently recognized as the most
substantial contributor to the total inorganic aerosol mass
on a global scale. Consequently, the estimation of aerosol
nitrate by atmospheric models has become increasingly
crucial, and the number of models that include this species
in their calculations is steadily rising, despite not being
the norm in the past. This thesis aims to address a key
assumption that can influence the estimation of nitrate
aerosols (NO3 -) by models. This assumption is their
physical state (i.e., solid or liquid). Aerosols typically
crystallize and form solids when exposed to decreasing
ambient relative humidity, though this process is often
complex due to various aerosol compositions and the
hysteresis effect .In thermodynamics, particles that form
solids are considered to be in a stable state; however,
aerosol water can exist even in very low humidity values,
leaving particles in a supersaturated aqueous state called
metastable. Utilizing a state-of-the-art chemistry and
climate model (EMAC) and a recently developed version of a
thermodynamic equilibrium model (ISORROPIA-lite), the study
explores the hypothesis that the state assumption
significantly impacts inorganic aerosol estimations.
Additionally, it examines the impact of the aerosol physical
state on the estimated particle acidity, as this is another
quantity that influences the aerosol partitioning process.
Furthermore, the thesis investigates a number of factors
that are known to influence the model’s ability to
accurately estimate NO3 - concentrations in regions of high
anthropogenic activity, with a particular focus on the
polluted North Hemisphere (East Asia, India, Europe, and
North America). The objective is to ascertain the most
significant factors that contribute to the best replication
of observations of NO3 - in sizes less than 1 μm and 2.5
μm in diameter (PM1 and PM2.5, respectively). The analysis
is further expanded to encompass the recognition of any
seasonal patterns as well as measurement location patterns.
Finally, the study examines the interactions between nitrate
aerosol and mineral dust, thereby investigating the climatic
impact of NO3 - with respect to its radiative effect from
both aerosol-radiation interactions (direct effect) and
aerosol-cloud interactions (indirect effect).The importance
of considering dustnitrate interactions when examining such
metrics is also quantified. The study found that the
physical state assumption has a minimal impact on the global
budget of key inorganic aerosol species, including NO3 -,
SO4 2-, and NH4 +, as well as non-volatile cations, with
overall differences being less than $10\%.$ Consequently,
for the purposes of climatic or air quality simulations that
cover a long time period and consider a global scale, that
choice is not expected to have a significant impact.
However, the metastable assumption has been shown to yield
faster simulation times, with an average increase of
approximately $4-5\%.In$ regions characterized by
consistently low relative humidity values and/or mid-range
temperatures, the assumption of considering only liquid
particles has been found to result in lower concentration
estimates, with NO3 - concentrations being reduced by up to
$40\%,$ and slightly more acidic particles by up to 1 unit.
Consequently, for analyses that consider specific regions,
the aerosol physical state assumption assumes greater
importance. Concerning the factors influencing the accuracy
of NO3 - estimations, it was ascertained that, on average, a
high model grid resolution and a low dinitrogen pentoxide
(N2O5) hydrolysis coefficient tend to yield better agreement
with observations in both sizes. The employment of disparate
anthropogenic emissions databases emerged as a significant
factor influencing model estimations, particularly in
replicating PM1 NO3 - concentrations across diverse regions.
In general, there is no ’perfect’ model setup capable of
best capturing both PM1 and PM2.5 NO3 - concentrations
across all regions simultaneously. Depending on the area of
interest, different parameterizations yield superior rates
of agreement. Furthermore, it was determined that nitrate
aerosols induce a net cooling direct radiative effect of
-0.11 W/m2, primarily attributable to the scattering of SW
radiation by smaller size modes, accounting for $85\%$ of
this estimate. Conversely, nitrate aerosols have been
observed to induce a net warming indirect radiative effect
of +0.17 W/m2, which is attributed to the depletion of
smallersized particles (i.e., anthropogenic pollution)
through coagulation with larger particles (i.e., dust). This
depletion results in the formation of less low-level warm
clouds, which decreases the amount of SW radiation that is
reflected back to space. The efficacy of this mechanism is
further augmented by nitrate-dust interactions, which
augment the size of dust particles through adsorption and
coating processes. The incorporation of dust chemistry is of
paramount importance when compared to assumptions for dust
composition or dust loading, as its omission engenders an
underestimation of the aforementioned estimates by up to
$45\%.$},
cin = {ICE-3},
cid = {I:(DE-Juel1)ICE-3-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
urn = {urn:nbn:de:0001-2507140935090.986494451029},
doi = {10.34734/FZJ-2025-02530},
url = {https://juser.fz-juelich.de/record/1042327},
}