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% makeindex style file created by the glossaries package
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preamble "\\glossarysection[\\glossarytoctitle]{\\glossarytitle}\\glossarypreamble\n\\begin{theglossary}\\glossaryheader\n"
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% !TeX program = lualatex
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\documentclass[../main/main.tex]{subfiles}
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%% DOCUMENT
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\begin{document}
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\pagestyle{mainbody}
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\chapter{Acknowledgements}
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\thispagestyle{mainbody}
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Dr. David Bell, Laso Blabla, Dominik Blabla, Wei Huang, Thorsten Bartels-Rausch, Marco Paolini, Yiwei Gong, Sacha Fallah, Francesca Salteri,
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\end{document}
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% !TeX program = lualatex
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\documentclass[../main/main.tex]{subfiles}
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%% ------------------------------------------------------------------%
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%% DOCUMENT
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\begin{document}
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\pagestyle{mainbody}
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\chapter{Introduction}
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\thispagestyle{mainbody}
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Iodine is the heaviest stable halogen element with atomic number \qty{53}{}. It has an average atomic weight of \qty{126.904}{\amu} and forms a semi-lustrous solid under standard conditions (here \qty{273.15}{\kelvin} and \qty{1}{\bar}, see \citet{calvert_glossary_1990}) \citep{kaiho_physical_2015}. Its melting and boiling points are \qty{114}{\degreeCelsius} and \qty{184}{\degreeCelsius}, respectively, and its vapour pressure is \qty{0.031}{\kilo\pascal} and \qty{9.17}{\kilo\pascal} at \qty{25}{\degreeCelsius} and \qty{113.6}{\degreeCelsius}, respectively \citep{kaiho_physical_2015}. The atomic radius of iodine is \qty{140}{\pico\meter} and its first ionisation energy is \qty{1015}{\kilo\joule\per\mol} \citep{kaiho_physical_2015}. Iodine is important in the enviornment: in the atmosphere, it influences the chemistry of ozone and important radical species, and it may be cause the formation of particles that may act as nuclei for aerosol or clouds \citep{saiz-lopez_atmospheric_2012}. The former is important for the capability of the atmophere to oxidise and remove species emitted to it, while the latter is important because of its effect on radiative equilibrium of Earth.
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\section{Iodine in the environment}
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Iodine is litophilic and incompatible in Earth's astenosphere, and therefore concentrated in oceans and surface sediments \citep{kendrick_halogen_2024}. Marine sediments constitute the largest iodine reservoir \citep{kendrick_halogen_2024} with much higher concentrations of \qtyrange{20}{600}{\milli\gram\per\kilogram} compared to soil- (\qtyrange{0.5}{20}{\milli\gram\per\kilogram}) or rock (\qtyrange{0.08}{0.5}{\milli\gram\per\kilogram}) concentrations \citep{whitehead_distribution_1984}. Sedimented iodine may be recycled into the oceans through sedimentary brines \citep{muramatsu_recycling_2001, muramatsu_studies_2004} around techtonically active subduction zones \citep{carrano_influence_2020} through diagenesis processes involving thermal decompostion or microbiological reduction of buried organic matter \citep{kendrick_halogen_2024, muramatsu_recycling_2001}. Consequently, iodine concentrations in the oceans are approximately \qtyrange{45}{60}{\micro\gram\per\liter} \citep{whitehead_distribution_1984}, mostly in the form of \gls{IO3-f}, the thermodynamically most stable state of iodine in aqueous solution \citep{fuge_iodine_2015}. However, \gls{IO3-f} exhibits a nutrient-like profile \citep{carrano_influence_2020} being depleted at the surface, whereas \gls{I-f} is enriched in the surface \citep{elderfield_biophilic_1980}. Similarly, organic matter is enriched in the surface, so that the existence of some iodinated organics may be presumed \citep{saiz-lopez_atmospheric_2012}. Within the oceans, iodine is incorporated preferrentially in organic matter \citep{kendrick_halogen_2024} by micro- and macroalgae, and aerobic bacteria \citep{carpenter_biogeochemical_2015}: through faciliated diffusion (see detailed descriptions in \citet{kupper_iodide_2008, winter_exploring_2009, amachi_microbial_2008}), cells store iodine as \ce{\glssymbol{I-f}(aq)} or associated to organic molecules \citep{kupper_iodide_2008, amachi_microbial_2008}.
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\Gls{I-f} within the cell interior may act as an antioxidant \citep{kupper_iodide_2008}: upon oxidative stress, the \gls{I-f} reservoir is mobilised and cells emit \ce{\glssymbol{I-f}(aq)} and a range of \glspl{VOICa} \citep{kupper_iodide_2008, carpenter_biogeochemical_2015} that may volatilise to the atmosphere. Analogously, when oxidative stress occurs during air exposure at low tide, the hetergeneous surface reaction of \gls{I-f} and \gls{O3f} at the sea-water interface produces \gls{HOIf}, \gls{I2f} and \glspl{IO.f} directly emitted to the atmosphere \citep{carpenter_biogeochemical_2015, palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010, he_role_2021}. It is currently thought that the biggest source of inorganic iodine to the atmosphere is \gls{HOIf} produced via the same pathway, exceeding the emissions of \gls{I2f} by one order of magnitude \citep{carpenter_atmospheric_2013}.
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Nevertheless, the atmospheric iodine budget is currently not well-constrained \citep{saiz-lopez_atmospheric_2012}. \glspl{VOICa} (notably \ce{\glssymbol{CH3If}}) and inorganic iodine species (\ce{\glssymbol{HOIf}}, \ce{\glssymbol{I2f}}, \ce{\glssymbol{IO.f}}) emitted from the oceans constitute the biggest source of iodine to the atmosphere \citep{carpenter_biogeochemical_2015, carpenter_atmospheric_2013}, with estimated input $\approx\qty{550}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Most \glspl{VOICa} are photolabile with lifetimes on the order of minutes to days \citep{bloss_kinetics_2001}. Other natural sources of iodine to the amtosphere include soils and plants \citep{whitehead_distribution_1984, carpenter_biogeochemical_2015, fuge_iodine_2015}, terrestrial water systems \citep{whitehead_distribution_1984}, and volcanoes or salt lakes \citep{carpenter_biogeochemical_2015}. The additional input from terrestrial sources into the atmosphere is $\approx\qtyrange{80}{110}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Anthropogenic sources include direct emissions from fossil fuel burning \citep{fuge_iodine_2015} and pesticide use \citep{zheng_accelerated_2003, whitehead_distribution_1984}. There are indirect anthropogenic effects as well: ice core data indicates that the sea-air flux of iodine has tripled between 1950 and 2010 as a consequence of increased anthropogenic ozone pollution of the troposphere \citep{cuevas_rapid_2018}. Sinks of atmospheric iodine include wet- and dry deposition \citep{fuge_iodine_2015}, and direct uptake through plants \citep{fuge_iodine_2015}. Overall, this leads to boundary layer mixing ratios of $\chi_{\ce{\glssymbol{I2f}(g)}}\leq\qty{93}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{IO.f}(g)}}\leq\qtyrange{3}{20}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{HOIf}(g)}}\leq\qty{1}{\pptv}$ \citep{he_role_2021} and $\chi_{\ce{\glssymbol{I.f}(g)}}\leq\qtyrange{0.1}{22}{\pptv}$ \citep{carpenter_biogeochemical_2015, he_role_2021}.
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\section{Iodine Chemistry in the Atmosphere}
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The importance of the marine iodine source is likely also reflected in aerosol composition: above marine areas, aerosol is enriched in iodine relative to seawater content by a factor of \qtyrange{100}{1000}{} \citep{carpenter_biogeochemical_2015}. Iodine may be transported into the aerosol phase through bubble-bursting of iodine-rich surface ocean waters \citep{saiz-lopez_atmospheric_2012}, or through the formation of aerosol via \glspl{IOPa} \citep{odowd_marine_2002}. Likely, low-volatility iodinated organics may also condense into the aerosol phase. Overall, various iodinated species may be present in aerosol including \gls{I-f}, \gls{IO3-f}, \gls{HOIf} and \gls{SOIa} \citep{saiz-lopez_atmospheric_2012}. \Citet{saiz-lopez_atmospheric_2012, gilfedder_iodine_2008} report that \gls{SOIa} is very frequent in aerosol and may constitute the largest reservoir of iodine in aerosol. There appear to be two principal pathways of \gls{SOIa} accomodation: direct accumulation from sea spray enriched in iodinated organics, and the reaction of \gls{HOIf} with aerosol organics. \Gls{HOIf} may also be highly reactive towards other species, likely due to its affinity for nucelophilic attacks on susceptible species. In general however, \gls{HOIf} or other likewise reduced iodine species such as \gls{I-f} should be oxidised to \gls{IO3-f} \citep{gilfedder_iodine_2008}, the thermodynamically most stable form of iodine in aqueous solution. Consequently, the accumulated form of iodine in condensed aerosol phases is often thought to be \gls{IO3-f} \citep{gilfedder_iodine_2008, saiz-lopez_atmospheric_2012}. However, observations in the troposphere indicate higher aerosol contents of \gls{I-f} than \gls{IO3-f} \citep{gilfedder_iodine_2008}, or high variability in the \gls{I-f}/\gls{IO3-f} ratio \citep{saiz-lopez_atmospheric_2012}. This indicates the presence of a mechanism reducing \gls{IO3-f} in the troposphere.
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Hetergeneous aerosol chemistry of iodine is closely linked to homogeneous chemistry of iodine through many iodine species. Generally, atmospheric iodine chemistry is initiated mostly through \gls{RISa} such as \glspl{I.f} or \glspl{IO.f}. Briefly, homogeneous iodine chemistry involves catalytic destruction of troposheric ozone via various pathways involving \glspl{HOxf} and \glspl{NOxf} as well as other halogen atoms in the atmosphere \citep{saiz-lopez_reactive_2012}. This process is photochemically driven and initiated with \glssymbol{IO.f} and \glssymbol{I.f}. \citet{saiz-lopez_reactive_2012} have outlined the mechanism: the intial step is the production of \glspl{I.f} from \glspl{RInf} or \gls{I2f}. The \glspl{I.f} react with \gls{O3f} to produce \glspl{IO.f} that in turn recombine to again produce \glspl{I.f}:
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\begin{reactions}
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\RI{}(g) + ${h\nu}$ &-> R^{\bullet}(g) + \glssymbol{I.f}(g)\\
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\glssymbol{I2f}(g) + ${h\nu}$ &-> 2 \glssymbol{I.f}(g)\\
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\glssymbol{I.f}(g) + \glssymbol{O3f}(g) &-> \glssymbol{IO.f}(g) + \glssymbol{O2f}(g) \label{reac: intro: iodine radical ozone loss}\\
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2\glssymbol{IO.f} &-> 2\glssymbol{I.f}(g) + \glssymbol{O2f}(g)\label{reac: intro: 2IO to 2I and O2}
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\end{reactions}
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The net outcome is ozone destruction with \ce{2\glssymbol{O3f}(g) -> 3\glssymbol{O2f}(g)}, although reaction \ref{reac: intro: 2IO to 2I and O2} has other channels that may involve \glssymbol{HOxf} and \glssymbol{NOxf} cycles. Importantly, the \gls{IO.f} has a lifetime against photolysis in the boundary layer on the order of seconds \citep{bloss_kinetics_2001}. Likewise, the effective lifetime of \gls{Ix.f} against uptake in aerosol is on the order of hours \citep{dix_detection_2013}: sustained presence of \glspl{IO.f} in the atmosphere therefore requires an effective recycling mechanism for \ce{\glssymbol{IO.f}}.
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Additionally, iodine may be involved in the oxidation of atmospheric organic molecules or mercury, allowing the latter to enter the food chain as highly poisonous methylmercury \citep{steffen_synthesis_2008, saiz-lopez_reactive_2012, saiz-lopez_atmospheric_2012}, and likely leading to enhanced condensation of organics into the aerosol phase through the former. Further, through formation of \glspl{IOPa}, iodine oxides may lead to the production of \glspl{UFAPa} \citep{carpenter_biogeochemical_2015}. Volatile species may condense on \glspl{UFAPa} that can grow up to the point of becoming \glspl{CCNa} \citep{saiz-lopez_atmospheric_2012}. Recent evidence shows that nucleation via iodine oxoacids to produce \glspl{IOPa} is highly efficient and sometimes competitive with sulfuric acid-ammonium driven nucleation \citep{he_role_2021}. Moreover, heterogeneous iodine chemistry on pre-existing frozen or liquid salt particles may lead to sudden increases in gas phase iodine species \citep{saiz-lopez_reactive_2012}. Importantly, the reaction of \gls{Br-f} with \gls{O3f} on frozen salt solutions occurs in the brine pertaining to the bulk ice phase, rather than \emph{within} the bulk ice phase \citep{oldridge_formation_2011}: such brines are formed when freezing solutions exclude solutes --- the heterogeneous reaction of \gls{O3f} with \gls{I-f} on frozen aerosol is here assumed to behave similarly. In other words, the heterogeneous reaction of \gls{O3f} with aerosol surfaces is assumed to be similar for frozen and liquid aerosol particles.
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Other heterogeneous effects may lead to substantial iodine emissions through the reaction of ozone with dissolved \gls{I-f} in ocean and aerosols \citep{palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010}. In the upper troposphere and lower stratosphere, heterogeneous recycling of iodine species is highly important: Model calculations by \citet{saiz-lopez_injection_2015} show that from the lower troposphere, convection may transport inorganic- and organic iodine species to the lower stratosphere, causing a \gls{Iyf} injection of \qtyrange{0.25}{0.7}{\pptv} \citep{saiz-lopez_injection_2015}. Measurements by \citet{koenig_quantitative_2020} are in agreement with this, indicating an injection of \qty{0.77\pm0.10}{\pptv} of \glssymbol{Iyf} into the lower stratosphere. Associated therewith is a mixing ratio of $\chi_{\ce{\glssymbol{IO.f}(g)}}=\qty{0.06\pm0.03}{\pptv}$ even for aged stratospheric air. \Citet{koenig_quantitative_2020} also observed that increases in altitude across the troposphere are associated with (1) an increase in particulate iodine and a decrease in gas phase iodine; and (2) a shift of \gls{I-f}-\gls{IO3-f} speciation in the condensed phase towards \gls{IO3-f}. Simulations could reproduce observed $\chi_{\ce{\glssymbol{IO.f}(g)}}$ only when a recycling scheme for iodine on ice particles was applied, and when the proper partioning between condensed- and gas phase was applied. This indicates that, as for the troposphere, a recycling mechanism producing gas phase \glspl{IO.f} must exist. There is also evidence that \gls{IO3-f} should be reduced to \gls{I-f}: \citet{pillar-little_conversion_2013} have established a pathway through which \gls{I-f} and \gls{O3f} cause volatilization of \ce{\glssymbol{I2f}(g)} and \ce{\glssymbol{HOIf}(g)} from watery microdroplets. However, it is still unclear \emph{how} the necessary \gls{I-f} is formed, given that most iodine should be present as \gls{IO3-f}. Consequently, an important question to answer is: how is \glssymbol{IO3-f} reduced to species --- most likely \glssymbol{I-f} --- that may, directly of after reacting, volatilise to the gas phase?
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\section{Reduction of Iodate}
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\Citet{saunders_insights_2012} have shown that \gls{IO3-f} may be reduced when solutions of \gls{IO3-f} and \gls{HAa} are irradiated with \gls{UV-Aa} and \gls{VISa} light between $\gls{LAMBDAs}\geq\qty{310}{\nano\meter}$ and $\gls{LAMBDAs}\approx\qty{780}{\nano\meter}$. The light source was filtered to exclude \gls{IRa} light and lamp output below $\gls{LAMBDAs}=\qty{310}{\nano\meter}$ to simulate the \gls{UV-Aa}-\gls{VISa} solar spectrum in the lower troposphere. They found that the major product of this photochemically induced process was \gls{SOIa} and that the proportion of \gls{I-f} in the reactant solution remained constant at approximately \qty{20}{\percent}. Since \gls{HAa} is a \gls{CHROMOPHOREg}, the suggested mechanism involves photogeneration of solvated electrons \ce{e-(aq)} that, in dependence of \gls{pHs}, yield \gls{HOIf}: \ce{\glssymbol{IO3-f}(aq) + 4e-(aq) + 5\glssymbol{H+f}(aq) ->\glssymbol{HOIf}(aq) + 2\glssymbol{H2Of}(aq)}. From there, \gls{SOIa} may be created through the nucleophilic attack of \gls{HOIf} on diphenolic functional groups \citep{saunders_insights_2012}. Alternatively, \gls{I2f} may be produced through reaction \ref{reac: intro: HOI to I2}, as described by \citet{pillar-little_conversion_2013}:
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\begin{reaction}
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\glssymbol{HOIf}(aq) + \glssymbol{I-f} + \glssymbol{H+f}(aq) -> \glssymbol{I2f}(aq) + \glssymbol{H2Of}(l) \label{reac: intro: HOI to I2}
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\end{reaction}
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Since \gls{I2f} is insoluble \citep{saiz-lopez_atmospheric_2012}, there will be volatilisation of \gls{I2f} to the gas phase. Overall, the mechanism suggested by \citet{saunders_insights_2012} produces primarily \gls{HOIf} \gls{I2f} --- the production pathway of \gls{I-f} has not been elucidated. The presence of \gls{I-f}, however, appears necessary for the production of \ce{\glssymbol{I2f}(g)}. It is hypothetised that \gls{I-f} may be regenerated from \gls{SOIa} \citep{saunders_insights_2012, baker_marine_2005}. Finally, \citet{saunders_insights_2012} have reported oscillations in the release of \ce{\glssymbol{I2f}(g)}. This is likely associated with formation of \gls{H2O2f} as a byproduct of \gls{HAa} photolysis \citep{saunders_insights_2012}. Indeed, \citet{cooper_photochemical_1988} have shown that \gls{H2O2f} is a common product when irradiating aqueous solutions of \glspl{CHROMOPHOREg}. Given \gls{H2O2f}, oscillations in \ce{\glssymbol{I2f}}-\ce{\glssymbol{IO3-f}} are known as the \gls{BRAY-LIEBHAFSKY-MECHANISMa}, first described by \citet{bray_periodic_1921, bray_reactions_1931}: \gls{H2O2f} interacts with \gls{I2f} and \gls{IO3-f} via
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\begin{reactions}
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&2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 5\glssymbol{H2O2f}(aq) <=> \glssymbol{I2f}(aq) + 5\glssymbol{O2f}(g) + 6\glssymbol{H2Of}(l) \label{reac: oxidation of iodine through hydrogen peroxide}\\
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&\glssymbol{I2f}(aq) + 5\glssymbol{H2O2f}(aq) <=> 2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 4\glssymbol{H2Of}(l) \label{reac: reduction of iodate through hydrogen peroxide}
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\end{reactions}
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to yield a net catalytic decomposition of \gls{H2O2f} via
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\begin{reaction}
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2\glssymbol{H2O2f}(aq) -> 2\glssymbol{H2Of}(l) + \glssymbol{O2f}(g) \label{reac: net catalytic destruction of hydrogen peroxide through iodine-iodate system}
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\end{reaction}
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The oscillation reaction has a \emph{stable} regime --- here, all species reach steady state except \glssymbol{H2O2f}: likely, \glssymbol{O2f}\ce{(g)} volatilises and \gls{LE-CHATELIER-PRINCIPLEa} dictates that \gls{H2O2f} consequently depletes. The \emph{unstable} regime where either reaction \ref{reac: oxidation of iodine through hydrogen peroxide} or \ref{reac: reduction of iodate through hydrogen peroxide} occur preferrentially, leads to oscillations in \gls{I2f} and \gls{IO3-f}. These oscillations are modulated by initial \gls{pHs} \citep{bray_periodic_1921} and temperature. Including an organic reducing agent and a metal-ion catalyst results in the \gls{BRIGGS-RAUSCHER-MECHANISMa} after \citet{briggs_oscillating_1973}, elucidated by \citet{schmitz_kinetics_2012}: Briefly, in addition to reaction \ref{reac: reduction of iodate through hydrogen peroxide}, the presence of some organic species \ce{R-H2} will induce the following reactions:
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\begin{reactions}
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\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-H2(aq) &-> 5 R-HI + 3\glssymbol{H2Of}\\
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\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-HI(aq) &-> 5 R-I2 + 3\glssymbol{H2Of}\\
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R-I2 + R-H2 &<=> 2 R-HI
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\end{reactions}
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The backward reaction likely proceeds via the metal ion catalyst, although \citet{schmitz_kinetics_2012} reported the possibility of non-catalysed pathways.
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A lot has been learned so far: organic substances may lead to the reduction of \gls{IO3-f}, via \gls{CHROMOPHOREg} activity. Furthermore, observed oscillations in gas phase \ce{\glssymbol{I2f}} may be explained through \gls{BRAY-LIEBHAFSKY-MECHANISMa}-\gls{BRIGGS-RAUSCHER-MECHANISMa} mechanisms. However, the suitability of \glspl{HAa} to represent organic aerosol has been questioned: \citet{graber_atmospheric_2006} suggested that humic-like substances found in aerosol particles may differ substantially from humic substances found in soil. More specifically, \citet{graber_atmospheric_2006} argue that terrestrial sources --- from which the \gls{HAa} used by \citet{saunders_insights_2012} likely originate --- may not be the origin of the majority of humic-like substances in aerosol. Differences may be found in terms of molecular weight, aromatic moiety content, surface properties and other properties \citep{graber_atmospheric_2006}. Although \glspl{HAa} as organics have profen useful to elucidate the mechanisms of \glssymbol{I2f} recycling, quantitatively constraining this recycling better requires more realistic organics. Another important question to answer, therefore, is: are there proxies that represent organics in aerosol more accurately, and to which the same \gls{CHROMOPHOREg}-dependent pathway of iodine recycling applies?
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\section{Reduction of Iodate: Proxies for Secondary Organic Aerosol}
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\Citet{guenther_global_1995} modelled global natural \gls{VOCa} emissions in 1990. They found a total flux of $\qty{1150}{\tera\gramCarbon\per\year}$, of which \qty{44}{\percent} (\qty{503}{\tera\gramCarbon\per\year}) was \gls{ISOPRENEf} and \qty{11}{\percent} (\qty{127}{\tera\gramCarbon\per\year}) were monoterpenes such as \gls{A-PINENEf}. Thereof, approximately \qty{75}{\percent} orginated from forests. In 2006, The annual atmospheric \gls{VOCa} injection was further specified in 2012 when \citet{guenther_model_2012} reported the following emissions of \glspl{VOCa} for the year 2000: total emissions were \qty{1089}{\tera\gramCarbon\per\year}, of which \gls{ISOPRENEf} emissions were \qty{49.1}{\percent} (\qty{535}{\tera\gramCarbon\per\year}) and the monoterpenes \gls{A-PINENEf}, \gls{B-PINENEf} and \gls{LIMONENEf} contributed \qty{6.7}{\percent} (\qty{66.1}{\tera\gramCarbon\per\year}), \qty{1.7}{\percent} (\qty{18.9}{\tera\gramCarbon\per\year}) and \qty{1.0}{\percent} (\qty{11.4}{\tera\gramCarbon\per\year}), respectively. \gls{ISOPRENEf} and monoterpene emissions are biogenic and mostly linked to vegetation --- overall they contributed approximately \qty{65}{\percent} to global \gls{VOCa} emissions in 2000 \citep{guenther_model_2012}, rendering them a major source of atmospheric \glspl{VOCa}.
|
||||
|
||||
Organic matter in aerosol is present either as \gls{POAa} or \gls{SOAa}. \gls{POAa} and \gls{SOAa} comprise the largest share of \emph{fine} particles with diameters $d\leq\qty{2.5}{\micro\meter}$. On the other hand, large particles with diameters $d>\qty{2.5}{\micro\meter}$ are mostly comprised of particles formed mechanically, including soil and mineral dust, sea salt particles and plant particles \citep{jziemann_kinetics_2012}. \gls{POAa} requires no chemical reactions to condense to the aerosol phase. Conversely, \gls{SOAa} is created when volatile precursor species are chemically altered to lower volatilities, and consequently condense to the aerosol phase. Likely, \gls{SOAa} constitues a large fraction of organic aerosol \cite{bianchi_highly_2019, hallquist_formation_2009}. As a general rule of thumb, higher oxygen content of a molecule indicates \emph{lower} volatility. Therefore, oxidation reactions are highly important in \gls{SOAa} formation because oxidation effectively \emph{decreases} volatility. Recent work summarised by \citet{bianchi_highly_2019} suggests that there exists class of of low-volatile species referred to as \glspl{HOMa} with low volatility. Such \glspl{HOMa} are formed through \emph{autooxidation} reactions involving peroxy radicals: this process is detailed by \citet{bianchi_highly_2019}, and the subtle but important difference between \glspl{HOMa} and molecules with high oxygen content is laid out. Briefly, \glspl{HOMa} are species of very low vapour pressure so that condensation onto existing particles is very probable and almost irreversible \citep{bianchi_highly_2019}. High yields of \glspl{HOMa} have been observed for \gls{ISOPRENEf} and the monoterpenes \gls{A-PINENEf} and especially \gls{LIMONENEf} \citep{bianchi_highly_2019}, with total yields of \qty{4}{\percent} (\gls{ISOPRENEf}), \qtyrange{7.0\pm3.5}{3.4\pm1.0}{\percent} (\gls{A-PINENEf}) and \qty{17.0\pm8.5}{\percent} (\gls{LIMONENEf}), respectively \citep{bianchi_highly_2019, jokinen_production_2015, ng_secondary_2008, ehn_large_2014, kirkby_ion-induced_2016}. It may therefore be assumed that derivatives --- or more precisely oxidation products --- of monoterpenes or \gls{ISOPRENEf} are common in \gls{SOAa}. Building on the work of \citet{saunders_insights_2012}, chosing an oxidation product of \gls{ISOPRENEf} or monoterpenes as the investigated organics may constitute a more realistc proxy for aerosol organics.
|
||||
|
||||
Recently, \citet{reza_iodine_2024} have performed similar experiments as \citet{saunders_insights_2012}, but using organic species better representing \gls{VOCa} oxidation. Recent observations have shown elevated concentrations of \ce{\glssymbol{IO.f}(g)} in dust layers above the Atacama and Sechura deserts: \citet{koenig_ozone_2021} measured a ten-fold enhancement of \gls{IO.f} concentrations compared to the regional background signal of \qtyrange{0.10}{0.25}{\pptv}. Because iron is hypothetised to catalyse photochemistry in dust particles, and since it is the most abundant transition metal in dust minerals \citep{aal-abadleh_perspective_2023}, iron may serve as a proxy for dust when investigating the reduction of \gls{IO3-f}. In a series of \gls{CWFTRa} experiments, \citet{reza_iodine_2024} used a \gls{CE-DOASa} to detect \glssymbol{I2f}\ce{(g)} and a \gls{ToF I-CIMSa} to detect \glspl{OVOCa} associated with \gls{IO3-f} reduction in thin aqueous films. The films were inserted into the \gls{CWFTRa} and consisted of an organic or inorganic matrix and \gls{IO3-f}.
|
||||
The organic matrices included \gls{IRON-3-CITRATEa}, \gls{CAa} and \gls{BTCAa}. \gls{CAa} was found in aerosol \citep{lienhard_measurements_2012} and is a proxy for oxygenated organic species. \gls{IRON-3-CITRATEa}, as a known photoactive compound, is considered a suitable proxy for \ce{Fe}(\toRoman{3}) carboxylate complexes found in the atmosphere \citep{reza_iodine_2024}. Importantly, \gls{CAa} has well-characterised hygroscopic properties \citep{reza_iodine_2024} so that this matrix can be used to control against \glspl{MATRIX-EFFECT-(CHEM)g} of organics that are due to iron when using \gls{IRON-3-CITRATEa}. These matrices were mixed with a solution of \gls{NaIO3f} to introduce \gls{IO3-f} at a concentration of $\approx\qty{30}{\milli\Molar}$. The results show that irradiation with \gls{VISa} for films containing \gls{IRON-3-CITRATEa} led to the reduction of $\approx\qty{40}{\percent}$ of the initially present \gls{IO3-f}. Likely, \gls{IRON-3-CITRATEa} undergoes a \gls{LMCTa} induced through irradiance with a photon at $\lambda<\qty{500}{\nano\meter}$ to yield \gls{CITRATEa} radicals and solvated electrons \ce{e-(aq)}, as described by \citet{saunders_insights_2012}. Likely, reduction of \gls{IO3-f} is driven through these solvated electrons. Furthermore, \citet{reza_iodine_2024} report that the speciation of the \glspl{CHROMOPHOREg} may include iodine-containing compounds.
|
||||
|
||||
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|
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|
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\begin{document}
|
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|
||||
\pagestyle{mainbody}
|
||||
|
||||
\chapter{Introduction}
|
||||
\thispagestyle{mainbody}
|
||||
|
||||
|
||||
Iodine is the heaviest stable halogen element with atomic number \qty{53}{}. It has an average atomic weight of \qty{126.904}{\amu} and forms a semi-lustrous solid under standard conditions (here \qty{273.15}{\kelvin} and \qty{1}{\bar}, see \citet{calvert_glossary_1990}) \citep{kaiho_physical_2015}. Its melting and boiling points are \qty{114}{\degreeCelsius} and \qty{184}{\degreeCelsius}, respectively, and its vapour pressure is \qty{0.031}{\kilo\pascal} and \qty{9.17}{\kilo\pascal} at \qty{25}{\degreeCelsius} and \qty{113.6}{\degreeCelsius}, respectively \citep{kaiho_physical_2015}. The atomic radius of iodine is \qty{140}{\pico\meter} and its first ionisation energy is \qty{1015}{\kilo\joule\per\mol} \citep{kaiho_physical_2015}. Iodine is important in the enviornment: in the atmosphere, it influences the chemistry of ozone and important radical species, and it may be cause the formation of particles that may act as nuclei for aerosol or clouds \citep{saiz-lopez_atmospheric_2012}. The former is important for the capability of the atmophere to oxidise and remove species emitted to it, while the latter is important because of its effect on radiative equilibrium of Earth.
|
||||
|
||||
\section{Iodine in the environment}
|
||||
|
||||
Iodine is litophilic and incompatible in Earth's astenosphere, and therefore concentrated in oceans and surface sediments \citep{kendrick_halogen_2024}. Marine sediments constitute the largest iodine reservoir \citep{kendrick_halogen_2024} with much higher concentrations of \qtyrange{20}{600}{\milli\gram\per\kilogram} compared to soil- (\qtyrange{0.5}{20}{\milli\gram\per\kilogram}) or rock (\qtyrange{0.08}{0.5}{\milli\gram\per\kilogram}) concentrations \citep{whitehead_distribution_1984}. Sedimented iodine may be recycled into the oceans through sedimentary brines \citep{muramatsu_recycling_2001, muramatsu_studies_2004} around techtonically active subduction zones \citep{carrano_influence_2020} through diagenesis processes involving thermal decompostion or microbiological reduction of buried organic matter \citep{kendrick_halogen_2024, muramatsu_recycling_2001}. Consequently, iodine concentrations in the oceans are approximately \qtyrange{45}{60}{\micro\gram\per\liter} \citep{whitehead_distribution_1984}, mostly in the form of \gls{IO3-f}, the thermodynamically most stable state of iodine in aqueous solution \citep{fuge_iodine_2015}. However, \gls{IO3-f} exhibits a nutrient-like profile \citep{carrano_influence_2020} being depleted at the surface, whereas \gls{I-f} is enriched in the surface \citep{elderfield_biophilic_1980}. Similarly, organic matter is enriched in the surface, so that the existence of some iodinated organics may be presumed \citep{saiz-lopez_atmospheric_2012}. Within the oceans, iodine is incorporated preferrentially in organic matter \citep{kendrick_halogen_2024} by micro- and macroalgae, and aerobic bacteria \citep{carpenter_biogeochemical_2015}: through faciliated diffusion (see detailed descriptions in \citet{kupper_iodide_2008, winter_exploring_2009, amachi_microbial_2008}), cells store iodine as \ce{\glssymbol{I-f}(aq)} or associated to organic molecules \citep{kupper_iodide_2008, amachi_microbial_2008}.
|
||||
\Gls{I-f} within the cell interior may act as an antioxidant \citep{kupper_iodide_2008}: upon oxidative stress, the \gls{I-f} reservoir is mobilised and cells emit \ce{\glssymbol{I-f}(aq)} and a range of \glspl{VOICa} \citep{kupper_iodide_2008, carpenter_biogeochemical_2015} that may volatilise to the atmosphere. Analogously, when oxidative stress occurs during air exposure at low tide, the hetergeneous surface reaction of \gls{I-f} and \gls{O3f} at the sea-water interface produces \gls{HOIf}, \gls{I2f} and \glspl{IO.f} directly emitted to the atmosphere \citep{carpenter_biogeochemical_2015, palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010, he_role_2021}. It is currently thought that the biggest source of inorganic iodine to the atmosphere is \gls{HOIf} produced via the same pathway, exceeding the emissions of \gls{I2f} by one order of magnitude \citep{carpenter_atmospheric_2013}.
|
||||
Nevertheless, the atmospheric iodine budget is currently not well-constrained \citep{saiz-lopez_atmospheric_2012}. \glspl{VOICa} (notably \ce{\glssymbol{CH3If}}) and inorganic iodine species (\ce{\glssymbol{HOIf}}, \ce{\glssymbol{I2f}}, \ce{\glssymbol{IO.f}}) emitted from the oceans constitute the biggest source of iodine to the atmosphere \citep{carpenter_biogeochemical_2015, carpenter_atmospheric_2013}, with estimated input $\approx\qty{550}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Most \glspl{VOICa} are photolabile with lifetimes on the order of minutes to days \citep{bloss_kinetics_2001}. Other natural sources of iodine to the amtosphere include soils and plants \citep{whitehead_distribution_1984, carpenter_biogeochemical_2015, fuge_iodine_2015}, terrestrial water systems \citep{whitehead_distribution_1984}, and volcanoes or salt lakes \citep{carpenter_biogeochemical_2015}. The additional input from terrestrial sources into the atmosphere is $\approx\qtyrange{80}{110}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Anthropogenic sources include direct emissions from fossil fuel burning \citep{fuge_iodine_2015} and pesticide use \citep{zheng_accelerated_2003, whitehead_distribution_1984}. There are indirect anthropogenic effects as well: ice core data indicates that the sea-air flux of iodine has tripled between 1950 and 2010 as a consequence of increased anthropogenic ozone pollution of the troposphere \citep{cuevas_rapid_2018}. Sinks of atmospheric iodine include wet- and dry deposition \citep{fuge_iodine_2015}, and direct uptake through plants \citep{fuge_iodine_2015}. Overall, this leads to boundary layer mixing ratios of $\chi_{\ce{\glssymbol{I2f}(g)}}\leq\qty{93}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{IO.f}(g)}}\leq\qtyrange{3}{20}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{HOIf}(g)}}\leq\qty{1}{\pptv}$ \citep{he_role_2021} and $\chi_{\ce{\glssymbol{I.f}(g)}}\leq\qtyrange{0.1}{22}{\pptv}$ \citep{carpenter_biogeochemical_2015, he_role_2021}.
|
||||
|
||||
\section{Iodine Chemistry in the Atmosphere}
|
||||
|
||||
The importance of the marine iodine source is likely also reflected in aerosol composition: above marine areas, aerosol is enriched in iodine relative to seawater content by a factor of \qtyrange{100}{1000}{} \citep{carpenter_biogeochemical_2015}. Iodine may be transported into the aerosol phase through bubble-bursting of iodine-rich surface ocean waters \citep{saiz-lopez_atmospheric_2012}, or through the formation of aerosol via \glspl{IOPa} \citep{odowd_marine_2002}. Likely, low-volatility iodinated organics may also condense into the aerosol phase. Overall, various iodinated species may be present in aerosol including \gls{I-f}, \gls{IO3-f}, \gls{HOIf} and \gls{SOIa} \citep{saiz-lopez_atmospheric_2012}. \Citet{saiz-lopez_atmospheric_2012, gilfedder_iodine_2008} report that \gls{SOIa} is very frequent in aerosol and may constitute the largest reservoir of iodine in aerosol. There appear to be two principal pathways of \gls{SOIa} accomodation: direct accumulation from sea spray enriched in iodinated organics, and the reaction of \gls{HOIf} with aerosol organics. \Gls{HOIf} may also be highly reactive towards other species, likely due to its affinity for nucelophilic attacks on susceptible species. In general however, \gls{HOIf} or other likewise reduced iodine species such as \gls{I-f} should be oxidised to \gls{IO3-f} \citep{gilfedder_iodine_2008}, the thermodynamically most stable form of iodine in aqueous solution. Consequently, the accumulated form of iodine in condensed aerosol phases is often thought to be \gls{IO3-f} \citep{gilfedder_iodine_2008, saiz-lopez_atmospheric_2012}. However, observations in the troposphere indicate higher aerosol contents of \gls{I-f} than \gls{IO3-f} \citep{gilfedder_iodine_2008}, or high variability in the \gls{I-f}/\gls{IO3-f} ratio \citep{saiz-lopez_atmospheric_2012}. This indicates the presence of a mechanism reducing \gls{IO3-f} in the troposphere.
|
||||
|
||||
Hetergeneous aerosol chemistry of iodine is closely linked to homogeneous chemistry of iodine through many iodine species. Generally, atmospheric iodine chemistry is initiated mostly through \gls{RISa} such as \glspl{I.f} or \glspl{IO.f}. Briefly, homogeneous iodine chemistry involves catalytic destruction of troposheric ozone via various pathways involving \glspl{HOxf} and \glspl{NOxf} as well as other halogen atoms in the atmosphere \citep{saiz-lopez_reactive_2012}. This process is photochemically driven and initiated with \glssymbol{IO.f} and \glssymbol{I.f}. \citet{saiz-lopez_reactive_2012} have outlined the mechanism: the intial step is the production of \glspl{I.f} from \glspl{RInf} or \gls{I2f}. The \glspl{I.f} react with \gls{O3f} to produce \glspl{IO.f} that in turn recombine to again produce \glspl{I.f}:
|
||||
|
||||
\begin{reactions}
|
||||
\RI{}(g) + ${h\nu}$ &-> R^{\bullet}(g) + \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I2f}(g) + ${h\nu}$ &-> 2 \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I.f}(g) + \glssymbol{O3f}(g) &-> \glssymbol{IO.f}(g) + \glssymbol{O2f}(g) \label{reac: intro: iodine radical ozone loss}\\
|
||||
2\glssymbol{IO.f} &-> 2\glssymbol{I.f}(g) + \glssymbol{O2f}(g)\label{reac: intro: 2IO to 2I and O2}
|
||||
\end{reactions}
|
||||
The net outcome is ozone destruction with \ce{2\glssymbol{O3f}(g) -> 3\glssymbol{O2f}(g)}, although reaction \ref{reac: intro: 2IO to 2I and O2} has other channels that may involve \glssymbol{HOxf} and \glssymbol{NOxf} cycles. Importantly, the \gls{IO.f} has a lifetime against photolysis in the boundary layer on the order of seconds \citep{bloss_kinetics_2001}. Likewise, the effective lifetime of \gls{Ix.f} against uptake in aerosol is on the order of hours \citep{dix_detection_2013}: sustained presence of \glspl{IO.f} in the atmosphere therefore requires an effective recycling mechanism for \ce{\glssymbol{IO.f}}.
|
||||
|
||||
Additionally, iodine may be involved in the oxidation of atmospheric organic molecules or mercury, allowing the latter to enter the food chain as highly poisonous methylmercury \citep{steffen_synthesis_2008, saiz-lopez_reactive_2012, saiz-lopez_atmospheric_2012}, and likely leading to enhanced condensation of organics into the aerosol phase through the former. Further, through formation of \glspl{IOPa}, iodine oxides may lead to the production of \glspl{UFAPa} \citep{carpenter_biogeochemical_2015}. Volatile species may condense on \glspl{UFAPa} that can grow up to the point of becoming \glspl{CCNa} \citep{saiz-lopez_atmospheric_2012}. Recent evidence shows that nucleation via iodine oxoacids to produce \glspl{IOPa} is highly efficient and sometimes competitive with sulfuric acid-ammonium driven nucleation \citep{he_role_2021}. Moreover, heterogeneous iodine chemistry on pre-existing frozen or liquid salt particles may lead to sudden increases in gas phase iodine species \citep{saiz-lopez_reactive_2012}. Importantly, the reaction of \gls{Br-f} with \gls{O3f} on frozen salt solutions occurs in the brine pertaining to the bulk ice phase, rather than \emph{within} the bulk ice phase \citep{oldridge_formation_2011}: such brines are formed when freezing solutions exclude solutes --- the heterogeneous reaction of \gls{O3f} with \gls{I-f} on frozen aerosol is here assumed to behave similarly. In other words, the heterogeneous reaction of \gls{O3f} with aerosol surfaces is assumed to be similar for frozen and liquid aerosol particles.
|
||||
|
||||
Other heterogeneous effects may lead to substantial iodine emissions through the reaction of ozone with dissolved \gls{I-f} in ocean and aerosols \citep{palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010}. In the upper troposphere and lower stratosphere, heterogeneous recycling of iodine species is highly important: Model calculations by \citet{saiz-lopez_injection_2015} show that from the lower troposphere, convection may transport inorganic- and organic iodine species to the lower stratosphere, causing a \gls{Iyf} injection of \qtyrange{0.25}{0.7}{\pptv} \citep{saiz-lopez_injection_2015}. Measurements by \citet{koenig_quantitative_2020} are in agreement with this, indicating an injection of \qty{0.77\pm0.10}{\pptv} of \glssymbol{Iyf} into the lower stratosphere. Associated therewith is a mixing ratio of $\chi_{\ce{\glssymbol{IO.f}(g)}}=\qty{0.06\pm0.03}{\pptv}$ even for aged stratospheric air. \Citet{koenig_quantitative_2020} also observed that increases in altitude across the troposphere are associated with (1) an increase in particulate iodine and a decrease in gas phase iodine; and (2) a shift of \gls{I-f}-\gls{IO3-f} speciation in the condensed phase towards \gls{IO3-f}. Simulations could reproduce observed $\chi_{\ce{\glssymbol{IO.f}(g)}}$ only when a recycling scheme for iodine on ice particles was applied, and when the proper partioning between condensed- and gas phase was applied. This indicates that, as for the troposphere, a recycling mechanism producing gas phase \glspl{IO.f} must exist. There is also evidence that \gls{IO3-f} should be reduced to \gls{I-f}: \citet{pillar-little_conversion_2013} have established a pathway through which \gls{I-f} and \gls{O3f} cause volatilization of \ce{\glssymbol{I2f}(g)} and \ce{\glssymbol{HOIf}(g)} from watery microdroplets. However, it is still unclear \emph{how} the necessary \gls{I-f} is formed, given that most iodine should be present as \gls{IO3-f}. Consequently, an important question to answer is: how is \glssymbol{IO3-f} reduced to species --- most likely \glssymbol{I-f} --- that may, directly of after reacting, volatilise to the gas phase?
|
||||
|
||||
\section{Reduction of Iodate}
|
||||
|
||||
\Citet{saunders_insights_2012} have shown that \gls{IO3-f} may be reduced when solutions of \gls{IO3-f} and \gls{HAa} are irradiated with \gls{UV-Aa} and \gls{VISa} light between $\gls{LAMBDAs}\geq\qty{310}{\nano\meter}$ and $\gls{LAMBDAs}\approx\qty{780}{\nano\meter}$. The light source was filtered to exclude \gls{IRa} light and lamp output below $\gls{LAMBDAs}=\qty{310}{\nano\meter}$ to simulate the \gls{UV-Aa}-\gls{VISa} solar spectrum in the lower troposphere. They found that the major product of this photochemically induced process was \gls{SOIa} and that the proportion of \gls{I-f} in the reactant solution remained constant at approximately \qty{20}{\percent}. Since \gls{HAa} is a \gls{CHROMOPHOREg}, the suggested mechanism involves photogeneration of solvated electrons \ce{e-(aq)} that, in dependence of \gls{pHs}, yield \gls{HOIf}: \ce{\glssymbol{IO3-f}(aq) + 4e-(aq) + 5\glssymbol{H+f}(aq) ->\glssymbol{HOIf}(aq) + 2\glssymbol{H2Of}(aq)}. From there, \gls{SOIa} may be created through the nucleophilic attack of \gls{HOIf} on diphenolic functional groups \citep{saunders_insights_2012}. Alternatively, \gls{I2f} may be produced through reaction \ref{reac: intro: HOI to I2}, as described by \citet{pillar-little_conversion_2013}:
|
||||
|
||||
\begin{reaction}
|
||||
\glssymbol{HOIf}(aq) + \glssymbol{I-f} + \glssymbol{H+f}(aq) -> \glssymbol{I2f}(aq) + \glssymbol{H2Of}(l) \label{reac: intro: HOI to I2}
|
||||
\end{reaction}
|
||||
Since \gls{I2f} is insoluble \citep{saiz-lopez_atmospheric_2012}, there will be volatilisation of \gls{I2f} to the gas phase. Overall, the mechanism suggested by \citet{saunders_insights_2012} produces primarily \gls{HOIf} \gls{I2f} --- the production pathway of \gls{I-f} has not been elucidated. The presence of \gls{I-f}, however, appears necessary for the production of \ce{\glssymbol{I2f}(g)}. It is hypothetised that \gls{I-f} may be regenerated from \gls{SOIa} \citep{saunders_insights_2012, baker_marine_2005}. Finally, \citet{saunders_insights_2012} have reported oscillations in the release of \ce{\glssymbol{I2f}(g)}. This is likely associated with formation of \gls{H2O2f} as a byproduct of \gls{HAa} photolysis \citep{saunders_insights_2012}. Indeed, \citet{cooper_photochemical_1988} have shown that \gls{H2O2f} is a common product when irradiating aqueous solutions of \glspl{CHROMOPHOREg}. Given \gls{H2O2f}, oscillations in \ce{\glssymbol{I2f}}-\ce{\glssymbol{IO3-f}} are known as the \gls{BRAY-LIEBHAFSKY-MECHANISMa}, first described by \citet{bray_periodic_1921, bray_reactions_1931}: \gls{H2O2f} interacts with \gls{I2f} and \gls{IO3-f} via
|
||||
|
||||
\begin{reactions}
|
||||
&2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 5\glssymbol{H2O2f}(aq) <=> \glssymbol{I2f}(aq) + 5\glssymbol{O2f}(g) + 6\glssymbol{H2Of}(l) \label{reac: oxidation of iodine through hydrogen peroxide}\\
|
||||
&\glssymbol{I2f}(aq) + 5\glssymbol{H2O2f}(aq) <=> 2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 4\glssymbol{H2Of}(l) \label{reac: reduction of iodate through hydrogen peroxide}
|
||||
\end{reactions}
|
||||
to yield a net catalytic decomposition of \gls{H2O2f} via
|
||||
|
||||
\begin{reaction}
|
||||
2\glssymbol{H2O2f}(aq) -> 2\glssymbol{H2Of}(l) + \glssymbol{O2f}(g) \label{reac: net catalytic destruction of hydrogen peroxide through iodine-iodate system}
|
||||
\end{reaction}
|
||||
The oscillation reaction has a \emph{stable} regime --- here, all species reach steady state except \glssymbol{H2O2f}: likely, \glssymbol{O2f}\ce{(g)} volatilises and \gls{LE-CHATELIER-PRINCIPLEa} dictates that \gls{H2O2f} consequently depletes. The \emph{unstable} regime where either reaction \ref{reac: oxidation of iodine through hydrogen peroxide} or \ref{reac: reduction of iodate through hydrogen peroxide} occur preferrentially, leads to oscillations in \gls{I2f} and \gls{IO3-f}. These oscillations are modulated by initial \gls{pHs} \citep{bray_periodic_1921} and temperature. Including an organic reducing agent and a metal-ion catalyst results in the \gls{BRIGGS-RAUSCHER-MECHANISMa} after \citet{briggs_oscillating_1973}, elucidated by \citet{schmitz_kinetics_2012}: Briefly, in addition to reaction \ref{reac: reduction of iodate through hydrogen peroxide}, the presence of some organic species \ce{R-H2} will induce the following reactions:
|
||||
|
||||
\begin{reactions}
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-H2(aq) &-> 5 R-HI + 3\glssymbol{H2Of}\\
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-HI(aq) &-> 5 R-I2 + 3\glssymbol{H2Of}\\
|
||||
R-I2 + R-H2 &<=> 2 R-HI
|
||||
\end{reactions}
|
||||
The backward reaction likely proceeds via the metal ion catalyst, although \citet{schmitz_kinetics_2012} reported the possibility of non-catalysed pathways.
|
||||
|
||||
A lot has been learned so far: organic substances may lead to the reduction of \gls{IO3-f}, via \gls{CHROMOPHOREg} activity. Furthermore, observed oscillations in gas phase \ce{\glssymbol{I2f}} may be explained through \gls{BRAY-LIEBHAFSKY-MECHANISMa}-\gls{BRIGGS-RAUSCHER-MECHANISMa} mechanisms. However, the suitability of \glspl{HAa} to represent organic aerosol has been questioned: \citet{graber_atmospheric_2006} suggested that humic-like substances found in aerosol particles may differ substantially from humic substances found in soil. More specifically, \citet{graber_atmospheric_2006} argue that terrestrial sources --- from which the \gls{HAa} used by \citet{saunders_insights_2012} likely originate --- may not be the origin of the majority of humic-like substances in aerosol. Differences may be found in terms of molecular weight, aromatic moiety content, surface properties and other properties \citep{graber_atmospheric_2006}. Although \glspl{HAa} as organics have profen useful to elucidate the mechanisms of \glssymbol{I2f} recycling, quantitatively constraining this recycling better requires more realistic organics. Another important question to answer, therefore, is: are there proxies that represent organics in aerosol more accurately, and to which the same \gls{CHROMOPHOREg}-dependent pathway of iodine recycling applies?
|
||||
|
||||
\section{Reduction of Iodate: Proxies for Secondary Organic Aerosol}
|
||||
|
||||
\Citet{guenther_global_1995} modelled global natural \gls{VOCa} emissions in 1990. They found a total flux of $\qty{1150}{\tera\gramCarbon\per\year}$, of which \qty{44}{\percent} (\qty{503}{\tera\gramCarbon\per\year}) was \gls{ISOPRENEf} and \qty{11}{\percent} (\qty{127}{\tera\gramCarbon\per\year}) were monoterpenes such as \gls{A-PINENEf}. Thereof, approximately \qty{75}{\percent} orginated from forests. In 2006, The annual atmospheric \gls{VOCa} injection was further specified in 2012 when \citet{guenther_model_2012} reported the following emissions of \glspl{VOCa} for the year 2000: total emissions were \qty{1089}{\tera\gramCarbon\per\year}, of which \gls{ISOPRENEf} emissions were \qty{49.1}{\percent} (\qty{535}{\tera\gramCarbon\per\year}) and the monoterpenes \gls{A-PINENEf}, \gls{B-PINENEf} and \gls{LIMONENEf} contributed \qty{6.7}{\percent} (\qty{66.1}{\tera\gramCarbon\per\year}), \qty{1.7}{\percent} (\qty{18.9}{\tera\gramCarbon\per\year}) and \qty{1.0}{\percent} (\qty{11.4}{\tera\gramCarbon\per\year}), respectively. \gls{ISOPRENEf} and monoterpene emissions are biogenic and mostly linked to vegetation --- overall they contributed approximately \qty{65}{\percent} to global \gls{VOCa} emissions in 2000 \citep{guenther_model_2012}, rendering them a major source of atmospheric \glspl{VOCa}.
|
||||
|
||||
Organic matter in aerosol is present either as \gls{POAa} or \gls{SOAa}. \gls{POAa} and \gls{SOAa} comprise the largest share of \emph{fine} particles with diameters $d\leq\qty{2.5}{\micro\meter}$. On the other hand, large particles with diameters $d>\qty{2.5}{\micro\meter}$ are mostly comprised of particles formed mechanically, including soil and mineral dust, sea salt particles and plant particles \citep{jziemann_kinetics_2012}. \gls{POAa} requires no chemical reactions to condense to the aerosol phase. Conversely, \gls{SOAa} is created when volatile precursor species are chemically altered to lower volatilities, and consequently condense to the aerosol phase. Likely, \gls{SOAa} constitues a large fraction of organic aerosol \cite{bianchi_highly_2019, hallquist_formation_2009}. As a general rule of thumb, higher oxygen content of a molecule indicates \emph{lower} volatility. Therefore, oxidation reactions are highly important in \gls{SOAa} formation because oxidation effectively \emph{decreases} volatility. Recent work summarised by \citet{bianchi_highly_2019} suggests that there exists class of of low-volatile species referred to as \glspl{HOMa} with low volatility. Such \glspl{HOMa} are formed through \emph{autooxidation} reactions involving peroxy radicals: this process is detailed by \citet{bianchi_highly_2019}, and the subtle but important difference between \glspl{HOMa} and molecules with high oxygen content is laid out. Briefly, \glspl{HOMa} are species of very low vapour pressure so that condensation onto existing particles is very probable and almost irreversible \citep{bianchi_highly_2019}. High yields of \glspl{HOMa} have been observed for \gls{ISOPRENEf} and the monoterpenes \gls{A-PINENEf} and especially \gls{LIMONENEf} \citep{bianchi_highly_2019}, with total yields of \qty{4}{\percent} (\gls{ISOPRENEf}), \qtyrange{7.0\pm3.5}{3.4\pm1.0}{\percent} (\gls{A-PINENEf}) and \qty{17.0\pm8.5}{\percent} (\gls{LIMONENEf}), respectively \citep{bianchi_highly_2019, jokinen_production_2015, ng_secondary_2008, ehn_large_2014, kirkby_ion-induced_2016}. It may therefore be assumed that derivatives --- or more precisely oxidation products --- of monoterpenes or \gls{ISOPRENEf} are common in \gls{SOAa}. Building on the work of \citet{saunders_insights_2012}, chosing an oxidation product of \gls{ISOPRENEf} or monoterpenes as the investigated organics may constitute a more realistc proxy for aerosol organics.
|
||||
|
||||
Recently, \citet{reza_iodine_2024} have performed similar experiments as \citet{saunders_insights_2012}, but using organic species better representing \gls{VOCa} oxidation. Recent observations have shown elevated concentrations of \ce{\glssymbol{IO.f}(g)} in dust layers above the Atacama and Sechura deserts: \citet{koenig_ozone_2021} measured a ten-fold enhancement of \gls{IO.f} concentrations compared to the regional background signal of \qtyrange{0.10}{0.25}{\pptv}. Because iron is hypothetised to catalyse photochemistry in dust particles, and since it is the most abundant transition metal in dust minerals \citep{aal-abadleh_perspective_2023}, iron may serve as a proxy for dust when investigating the reduction of \gls{IO3-f}. In a series of \gls{CWFTRa} experiments, \citet{reza_iodine_2024} used a \gls{CE-DOASa} to detect \glssymbol{I2f}\ce{(g)} and a \gls{ToF I-CIMSa} to detect \glspl{OVOCa} associated with \gls{IO3-f} reduction in thin aqueous films. The films were inserted into the \gls{CWFTRa} and consisted of an organic or inorganic matrix and \gls{IO3-f}.
|
||||
The organic matrices included \gls{IRON-3-CITRATEa}, \gls{CAa} and \gls{BTCAa}. \gls{CAa} was found in aerosol \citep{lienhard_measurements_2012} and is a proxy for oxygenated organic species. \gls{IRON-3-CITRATEa}, as a known photoactive compound, is considered a suitable proxy for \ce{Fe}(\toRoman{3}) carboxylate complexes found in the atmosphere \citep{reza_iodine_2024}. Importantly, \gls{CAa} has well-characterised hygroscopic properties \citep{reza_iodine_2024} so that this matrix can be used to control against \glspl{MATRIX-EFFECT-(CHEM)g} of organics that are due to iron when using \gls{IRON-3-CITRATEa}. These matrices were mixed with a solution of \gls{NaIO3f} to introduce \gls{IO3-f} at a concentration of $\approx\qty{30}{\milli\Molar}$. The results show that irradiation with \gls{VISa} for films containing \gls{IRON-3-CITRATEa} led to the reduction of $\approx\qty{40}{\percent}$ of the initially present \gls{IO3-f}. Likely, \gls{IRON-3-CITRATEa} undergoes a \gls{LMCTa} induced through irradiance with a photon at $\lambda<\qty{500}{\nano\meter}$ to yield \gls{CITRATEa} radicals and solvated electrons \ce{e-(aq)}, as described by \citet{saunders_insights_2012}. Likely, reduction of \gls{IO3-f} is driven through these solvated electrons. Furthermore, \citet{reza_iodine_2024} report that the speciation of the \glspl{CHROMOPHOREg} may include iodine-containing compounds.
|
||||
|
||||
\end{document}
|
||||
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|
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|
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|
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|
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|
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|
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|
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|
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% !TeX program = lualatex
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% SUBFILE MODE
|
||||
\documentclass[../main/main.tex]{subfiles}
|
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\graphicspath{{../graphics/}}
|
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%% ------------------------------------------------------------------%
|
||||
%% DOCUMENT
|
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|
||||
|
||||
\begin{document}
|
||||
|
||||
\pagestyle{mainbody}
|
||||
|
||||
\chapter{Introduction}
|
||||
\thispagestyle{mainbody}
|
||||
|
||||
|
||||
Iodine is the heaviest stable halogen element with atomic number \qty{53}{}. It has an average atomic weight of \qty{126.904}{\amu} and forms a semi-lustrous solid under standard conditions (here \qty{273.15}{\kelvin} and \qty{1}{\bar}, see \citet{calvert_glossary_1990}) \citep{kaiho_physical_2015}. Its melting and boiling points are \qty{114}{\degreeCelsius} and \qty{184}{\degreeCelsius}, respectively, and its vapour pressure is \qty{0.031}{\kilo\pascal} and \qty{9.17}{\kilo\pascal} at \qty{25}{\degreeCelsius} and \qty{113.6}{\degreeCelsius}, respectively \citep{kaiho_physical_2015}. The atomic radius of iodine is \qty{140}{\pico\meter} and its first ionisation energy is \qty{1015}{\kilo\joule\per\mol} \citep{kaiho_physical_2015}. Iodine is important in the enviornment: in the atmosphere, it influences the chemistry of ozone and important radical species, and it may be cause the formation of particles that may act as nuclei for aerosol or clouds \citep{saiz-lopez_atmospheric_2012}. The former is important for the capability of the atmophere to oxidise and remove species emitted to it, while the latter is important because of its effect on radiative equilibrium of Earth.
|
||||
|
||||
\section{Iodine in the environment}
|
||||
|
||||
Iodine is litophilic and incompatible in Earth's astenosphere, and therefore concentrated in oceans and surface sediments \citep{kendrick_halogen_2024}. Marine sediments constitute the largest iodine reservoir \citep{kendrick_halogen_2024} with much higher concentrations of \qtyrange{20}{600}{\milli\gram\per\kilogram} compared to soil- (\qtyrange{0.5}{20}{\milli\gram\per\kilogram}) or rock (\qtyrange{0.08}{0.5}{\milli\gram\per\kilogram}) concentrations \citep{whitehead_distribution_1984}. Sedimented iodine may be recycled into the oceans through sedimentary brines \citep{muramatsu_recycling_2001, muramatsu_studies_2004} around techtonically active subduction zones \citep{carrano_influence_2020} through diagenesis processes involving thermal decompostion or microbiological reduction of buried organic matter \citep{kendrick_halogen_2024, muramatsu_recycling_2001}. Consequently, iodine concentrations in the oceans are approximately \qtyrange{45}{60}{\micro\gram\per\liter} \citep{whitehead_distribution_1984}, mostly in the form of \gls{IO3-f}, the thermodynamically most stable state of iodine in aqueous solution \citep{fuge_iodine_2015}. However, \gls{IO3-f} exhibits a nutrient-like profile \citep{carrano_influence_2020} being depleted at the surface, whereas \gls{I-f} is enriched in the surface \citep{elderfield_biophilic_1980}. Similarly, organic matter is enriched in the surface, so that the existence of some iodinated organics may be presumed \citep{saiz-lopez_atmospheric_2012}. Within the oceans, iodine is incorporated preferrentially in organic matter \citep{kendrick_halogen_2024} by micro- and macroalgae, and aerobic bacteria \citep{carpenter_biogeochemical_2015}: through faciliated diffusion (see detailed descriptions in \citet{kupper_iodide_2008, winter_exploring_2009, amachi_microbial_2008}), cells store iodine as \ce{\glssymbol{I-f}(aq)} or associated to organic molecules \citep{kupper_iodide_2008, amachi_microbial_2008}.
|
||||
\Gls{I-f} within the cell interior may act as an antioxidant \citep{kupper_iodide_2008}: upon oxidative stress, the \gls{I-f} reservoir is mobilised and cells emit \ce{\glssymbol{I-f}(aq)} and a range of \glspl{VOICa} \citep{kupper_iodide_2008, carpenter_biogeochemical_2015} that may volatilise to the atmosphere. Analogously, when oxidative stress occurs during air exposure at low tide, the hetergeneous surface reaction of \gls{I-f} and \gls{O3f} at the sea-water interface produces \gls{HOIf}, \gls{I2f} and \glspl{IO.f} directly emitted to the atmosphere \citep{carpenter_biogeochemical_2015, palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010, he_role_2021}. It is currently thought that the biggest source of inorganic iodine to the atmosphere is \gls{HOIf} produced via the same pathway, exceeding the emissions of \gls{I2f} by one order of magnitude \citep{carpenter_atmospheric_2013}.
|
||||
Nevertheless, the atmospheric iodine budget is currently not well-constrained \citep{saiz-lopez_atmospheric_2012}. \glspl{VOICa} (notably \ce{\glssymbol{CH3If}}) and inorganic iodine species (\ce{\glssymbol{HOIf}}, \ce{\glssymbol{I2f}}, \ce{\glssymbol{IO.f}}) emitted from the oceans constitute the biggest source of iodine to the atmosphere \citep{carpenter_biogeochemical_2015, carpenter_atmospheric_2013}, with estimated input $\approx\qty{550}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Most \glspl{VOICa} are photolabile with lifetimes on the order of minutes to days \citep{bloss_kinetics_2001}. Other natural sources of iodine to the amtosphere include soils and plants \citep{whitehead_distribution_1984, carpenter_biogeochemical_2015, fuge_iodine_2015}, terrestrial water systems \citep{whitehead_distribution_1984}, and volcanoes or salt lakes \citep{carpenter_biogeochemical_2015}. The additional input from terrestrial sources into the atmosphere is $\approx\qtyrange{80}{110}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Anthropogenic sources include direct emissions from fossil fuel burning \citep{fuge_iodine_2015} and pesticide use \citep{zheng_accelerated_2003, whitehead_distribution_1984}. There are indirect anthropogenic effects as well: ice core data indicates that the sea-air flux of iodine has tripled between 1950 and 2010 as a consequence of increased anthropogenic ozone pollution of the troposphere \citep{cuevas_rapid_2018}. Sinks of atmospheric iodine include wet- and dry deposition \citep{fuge_iodine_2015}, and direct uptake through plants \citep{fuge_iodine_2015}. Overall, this leads to boundary layer mixing ratios of $\chi_{\ce{\glssymbol{I2f}(g)}}\leq\qty{93}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{IO.f}(g)}}\leq\qtyrange{3}{20}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{HOIf}(g)}}\leq\qty{1}{\pptv}$ \citep{he_role_2021} and $\chi_{\ce{\glssymbol{I.f}(g)}}\leq\qtyrange{0.1}{22}{\pptv}$ \citep{carpenter_biogeochemical_2015, he_role_2021}.
|
||||
|
||||
\section{Iodine Chemistry in the Atmosphere}
|
||||
|
||||
The importance of the marine iodine source is likely also reflected in aerosol composition: above marine areas, aerosol is enriched in iodine relative to seawater content by a factor of \qtyrange{100}{1000}{} \citep{carpenter_biogeochemical_2015}. Iodine may be transported into the aerosol phase through bubble-bursting of iodine-rich surface ocean waters \citep{saiz-lopez_atmospheric_2012}, or through the formation of aerosol via \glspl{IOPa} \citep{odowd_marine_2002}. Likely, low-volatility iodinated organics may also condense into the aerosol phase. Overall, various iodinated species may be present in aerosol including \gls{I-f}, \gls{IO3-f}, \gls{HOIf} and \gls{SOIa} \citep{saiz-lopez_atmospheric_2012}. \Citet{saiz-lopez_atmospheric_2012, gilfedder_iodine_2008} report that \gls{SOIa} is very frequent in aerosol and may constitute the largest reservoir of iodine in aerosol. There appear to be two principal pathways of \gls{SOIa} accomodation: direct accumulation from sea spray enriched in iodinated organics, and the reaction of \gls{HOIf} with aerosol organics. \Gls{HOIf} may also be highly reactive towards other species, likely due to its affinity for nucelophilic attacks on susceptible species. In general however, \gls{HOIf} or other likewise reduced iodine species such as \gls{I-f} should be oxidised to \gls{IO3-f} \citep{gilfedder_iodine_2008}, the thermodynamically most stable form of iodine in aqueous solution. Consequently, the accumulated form of iodine in condensed aerosol phases is often thought to be \gls{IO3-f} \citep{gilfedder_iodine_2008, saiz-lopez_atmospheric_2012}. However, observations in the troposphere indicate higher aerosol contents of \gls{I-f} than \gls{IO3-f} \citep{gilfedder_iodine_2008}, or high variability in the \gls{I-f}/\gls{IO3-f} ratio \citep{saiz-lopez_atmospheric_2012}. This indicates the presence of a mechanism reducing \gls{IO3-f} in the troposphere.
|
||||
|
||||
Hetergeneous aerosol chemistry of iodine is closely linked to homogeneous chemistry of iodine through many iodine species. Generally, atmospheric iodine chemistry is initiated mostly through \gls{RISa} such as \glspl{I.f} or \glspl{IO.f}. Briefly, homogeneous iodine chemistry involves catalytic destruction of troposheric ozone via various pathways involving \glspl{HOxf} and \glspl{NOxf} as well as other halogen atoms in the atmosphere \citep{saiz-lopez_reactive_2012}. This process is photochemically driven and initiated with \glssymbol{IO.f} and \glssymbol{I.f}. \citet{saiz-lopez_reactive_2012} have outlined the mechanism: the intial step is the production of \glspl{I.f} from \glspl{RInf} or \gls{I2f}. The \glspl{I.f} react with \gls{O3f} to produce \glspl{IO.f} that in turn recombine to again produce \glspl{I.f}:
|
||||
|
||||
\begin{reactions}
|
||||
\RI{}(g) + ${h\nu}$ &-> R^{\bullet}(g) + \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I2f}(g) + ${h\nu}$ &-> 2 \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I.f}(g) + \glssymbol{O3f}(g) &-> \glssymbol{IO.f}(g) + \glssymbol{O2f}(g) \label{reac: intro: iodine radical ozone loss}\\
|
||||
2\glssymbol{IO.f} &-> 2\glssymbol{I.f}(g) + \glssymbol{O2f}(g)\label{reac: intro: 2IO to 2I and O2}
|
||||
\end{reactions}
|
||||
The net outcome is ozone destruction with \ce{2\glssymbol{O3f}(g) -> 3\glssymbol{O2f}(g)}, although reaction \ref{reac: intro: 2IO to 2I and O2} has other channels that may involve \glssymbol{HOxf} and \glssymbol{NOxf} cycles. Importantly, the \gls{IO.f} has a lifetime against photolysis in the boundary layer on the order of seconds \citep{bloss_kinetics_2001}. Likewise, the effective lifetime of \gls{Ix.f} against uptake in aerosol is on the order of hours \citep{dix_detection_2013}: sustained presence of \glspl{IO.f} in the atmosphere therefore requires an effective recycling mechanism for \ce{\glssymbol{IO.f}}.
|
||||
|
||||
Additionally, iodine may be involved in the oxidation of atmospheric organic molecules or mercury, allowing the latter to enter the food chain as highly poisonous methylmercury \citep{steffen_synthesis_2008, saiz-lopez_reactive_2012, saiz-lopez_atmospheric_2012}, and likely leading to enhanced condensation of organics into the aerosol phase through the former. Further, through formation of \glspl{IOPa}, iodine oxides may lead to the production of \glspl{UFAPa} \citep{carpenter_biogeochemical_2015}. Volatile species may condense on \glspl{UFAPa} that can grow up to the point of becoming \glspl{CCNa} \citep{saiz-lopez_atmospheric_2012}. Recent evidence shows that nucleation via iodine oxoacids to produce \glspl{IOPa} is highly efficient and sometimes competitive with sulfuric acid-ammonium driven nucleation \citep{he_role_2021}. Moreover, heterogeneous iodine chemistry on pre-existing frozen or liquid salt particles may lead to sudden increases in gas phase iodine species \citep{saiz-lopez_reactive_2012}. Importantly, the reaction of \gls{Br-f} with \gls{O3f} on frozen salt solutions occurs in the brine pertaining to the bulk ice phase, rather than \emph{within} the bulk ice phase \citep{oldridge_formation_2011}: such brines are formed when freezing solutions exclude solutes --- the heterogeneous reaction of \gls{O3f} with \gls{I-f} on frozen aerosol is here assumed to behave similarly. In other words, the heterogeneous reaction of \gls{O3f} with aerosol surfaces is assumed to be similar for frozen and liquid aerosol particles.
|
||||
|
||||
Other heterogeneous effects may lead to substantial iodine emissions through the reaction of ozone with dissolved \gls{I-f} in ocean and aerosols \citep{palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010}. In the upper troposphere and lower stratosphere, heterogeneous recycling of iodine species is highly important: Model calculations by \citet{saiz-lopez_injection_2015} show that from the lower troposphere, convection may transport inorganic- and organic iodine species to the lower stratosphere, causing a \gls{Iyf} injection of \qtyrange{0.25}{0.7}{\pptv} \citep{saiz-lopez_injection_2015}. Measurements by \citet{koenig_quantitative_2020} are in agreement with this, indicating an injection of \qty{0.77\pm0.10}{\pptv} of \glssymbol{Iyf} into the lower stratosphere. Associated therewith is a mixing ratio of $\chi_{\ce{\glssymbol{IO.f}(g)}}=\qty{0.06\pm0.03}{\pptv}$ even for aged stratospheric air. \Citet{koenig_quantitative_2020} also observed that increases in altitude across the troposphere are associated with (1) an increase in particulate iodine and a decrease in gas phase iodine; and (2) a shift of \gls{I-f}-\gls{IO3-f} speciation in the condensed phase towards \gls{IO3-f}. Simulations could reproduce observed $\chi_{\ce{\glssymbol{IO.f}(g)}}$ only when a recycling scheme for iodine on ice particles was applied, and when the proper partioning between condensed- and gas phase was applied. This indicates that, as for the troposphere, a recycling mechanism producing gas phase \glspl{IO.f} must exist. There is also evidence that \gls{IO3-f} should be reduced to \gls{I-f}: \citet{pillar-little_conversion_2013} have established a pathway through which \gls{I-f} and \gls{O3f} cause volatilization of \ce{\glssymbol{I2f}(g)} and \ce{\glssymbol{HOIf}(g)} from watery microdroplets. However, it is still unclear \emph{how} the necessary \gls{I-f} is formed, given that most iodine should be present as \gls{IO3-f}. Consequently, an important question to answer is: how is \glssymbol{IO3-f} reduced to species --- most likely \glssymbol{I-f} --- that may, directly of after reacting, volatilise to the gas phase?
|
||||
|
||||
\section{Reduction of Iodate}
|
||||
|
||||
\Citet{saunders_insights_2012} have shown that \gls{IO3-f} may be reduced when solutions of \gls{IO3-f} and \gls{HAa} are irradiated with \gls{UV-Aa} and \gls{VISa} light between $\gls{LAMBDAs}\geq\qty{310}{\nano\meter}$ and $\gls{LAMBDAs}\approx\qty{780}{\nano\meter}$. The light source was filtered to exclude \gls{IRa} light and lamp output below $\gls{LAMBDAs}=\qty{310}{\nano\meter}$ to simulate the \gls{UV-Aa}-\gls{VISa} solar spectrum in the lower troposphere. They found that the major product of this photochemically induced process was \gls{SOIa} and that the proportion of \gls{I-f} in the reactant solution remained constant at approximately \qty{20}{\percent}. Since \gls{HAa} is a \gls{CHROMOPHOREg}, the suggested mechanism involves photogeneration of solvated electrons \ce{e-(aq)} that, in dependence of \gls{pHs}, yield \gls{HOIf}: \ce{\glssymbol{IO3-f}(aq) + 4e-(aq) + 5\glssymbol{H+f}(aq) ->\glssymbol{HOIf}(aq) + 2\glssymbol{H2Of}(aq)}. From there, \gls{SOIa} may be created through the nucleophilic attack of \gls{HOIf} on diphenolic functional groups \citep{saunders_insights_2012}. Alternatively, \gls{I2f} may be produced through reaction \ref{reac: intro: HOI to I2}, as described by \citet{pillar-little_conversion_2013}:
|
||||
|
||||
\begin{reaction}
|
||||
\glssymbol{HOIf}(aq) + \glssymbol{I-f} + \glssymbol{H+f}(aq) -> \glssymbol{I2f}(aq) + \glssymbol{H2Of}(l) \label{reac: intro: HOI to I2}
|
||||
\end{reaction}
|
||||
Since \gls{I2f} is insoluble \citep{saiz-lopez_atmospheric_2012}, there will be volatilisation of \gls{I2f} to the gas phase. Overall, the mechanism suggested by \citet{saunders_insights_2012} produces primarily \gls{HOIf} \gls{I2f} --- the production pathway of \gls{I-f} has not been elucidated. The presence of \gls{I-f}, however, appears necessary for the production of \ce{\glssymbol{I2f}(g)}. It is hypothetised that \gls{I-f} may be regenerated from \gls{SOIa} \citep{saunders_insights_2012, baker_marine_2005}. Finally, \citet{saunders_insights_2012} have reported oscillations in the release of \ce{\glssymbol{I2f}(g)}. This is likely associated with formation of \gls{H2O2f} as a byproduct of \gls{HAa} photolysis \citep{saunders_insights_2012}. Indeed, \citet{cooper_photochemical_1988} have shown that \gls{H2O2f} is a common product when irradiating aqueous solutions of \glspl{CHROMOPHOREg}. Given \gls{H2O2f}, oscillations in \ce{\glssymbol{I2f}}-\ce{\glssymbol{IO3-f}} are known as the \gls{BRAY-LIEBHAFSKY-MECHANISMa}, first described by \citet{bray_periodic_1921, bray_reactions_1931}: \gls{H2O2f} interacts with \gls{I2f} and \gls{IO3-f} via
|
||||
|
||||
\begin{reactions}
|
||||
&2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 5\glssymbol{H2O2f}(aq) <=> \glssymbol{I2f}(aq) + 5\glssymbol{O2f}(g) + 6\glssymbol{H2Of}(l) \label{reac: oxidation of iodine through hydrogen peroxide}\\
|
||||
&\glssymbol{I2f}(aq) + 5\glssymbol{H2O2f}(aq) <=> 2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 4\glssymbol{H2Of}(l) \label{reac: reduction of iodate through hydrogen peroxide}
|
||||
\end{reactions}
|
||||
to yield a net catalytic decomposition of \gls{H2O2f} via
|
||||
|
||||
\begin{reaction}
|
||||
2\glssymbol{H2O2f}(aq) -> 2\glssymbol{H2Of}(l) + \glssymbol{O2f}(g) \label{reac: net catalytic destruction of hydrogen peroxide through iodine-iodate system}
|
||||
\end{reaction}
|
||||
The oscillation reaction has a \emph{stable} regime --- here, all species reach steady state except \glssymbol{H2O2f}: likely, \glssymbol{O2f}\ce{(g)} volatilises and \gls{LE-CHATELIER-PRINCIPLEa} dictates that \gls{H2O2f} consequently depletes. The \emph{unstable} regime where either reaction \ref{reac: oxidation of iodine through hydrogen peroxide} or \ref{reac: reduction of iodate through hydrogen peroxide} occur preferrentially, leads to oscillations in \gls{I2f} and \gls{IO3-f}. These oscillations are modulated by initial \gls{pHs} \citep{bray_periodic_1921} and temperature. Including an organic reducing agent and a metal-ion catalyst results in the \gls{BRIGGS-RAUSCHER-MECHANISMa} after \citet{briggs_oscillating_1973}, elucidated by \citet{schmitz_kinetics_2012}: Briefly, in addition to reaction \ref{reac: reduction of iodate through hydrogen peroxide}, the presence of some organic species \ce{R-H2} will induce the following reactions:
|
||||
|
||||
\begin{reactions}
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-H2(aq) &-> 5 R-HI + 3\glssymbol{H2Of}\\
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-HI(aq) &-> 5 R-I2 + 3\glssymbol{H2Of}\\
|
||||
R-I2 + R-H2 &<=> 2 R-HI
|
||||
\end{reactions}
|
||||
The backward reaction likely proceeds via the metal ion catalyst, although \citet{schmitz_kinetics_2012} reported the possibility of non-catalysed pathways.
|
||||
|
||||
A lot has been learned so far: organic substances may lead to the reduction of \gls{IO3-f}, via \gls{CHROMOPHOREg} activity. Furthermore, observed oscillations in gas phase \ce{\glssymbol{I2f}} may be explained through \gls{BRAY-LIEBHAFSKY-MECHANISMa}-\gls{BRIGGS-RAUSCHER-MECHANISMa} mechanisms. However, the suitability of \glspl{HAa} to represent organic aerosol has been questioned: \citet{graber_atmospheric_2006} suggested that humic-like substances found in aerosol particles may differ substantially from humic substances found in soil. More specifically, \citet{graber_atmospheric_2006} argue that terrestrial sources --- from which the \gls{HAa} used by \citet{saunders_insights_2012} likely originate --- may not be the origin of the majority of humic-like substances in aerosol. Differences may be found in terms of molecular weight, aromatic moiety content, surface properties and other properties \citep{graber_atmospheric_2006}. Although \glspl{HAa} as organics have profen useful to elucidate the mechanisms of \glssymbol{I2f} recycling, quantitatively constraining this recycling better requires more realistic organics. Another important question to answer, therefore, is: are there proxies that represent organics in aerosol more accurately, and to which the same \gls{CHROMOPHOREg}-dependent pathway of iodine recycling applies?
|
||||
|
||||
\section{Reduction of Iodate: Proxies for Secondary Organic Aerosol}
|
||||
|
||||
\Citet{guenther_global_1995} modelled global natural \gls{VOCa} emissions in 1990. They found a total flux of $\qty{1150}{\tera\gramCarbon\per\year}$, of which \qty{44}{\percent} (\qty{503}{\tera\gramCarbon\per\year}) was \gls{ISOPRENEf} and \qty{11}{\percent} (\qty{127}{\tera\gramCarbon\per\year}) were monoterpenes such as \gls{A-PINENEf}. Thereof, approximately \qty{75}{\percent} orginated from forests. In 2006, The annual atmospheric \gls{VOCa} injection was further specified in 2012 when \citet{guenther_model_2012} reported the following emissions of \glspl{VOCa} for the year 2000: total emissions were \qty{1089}{\tera\gramCarbon\per\year}, of which \gls{ISOPRENEf} emissions were \qty{49.1}{\percent} (\qty{535}{\tera\gramCarbon\per\year}) and the monoterpenes \gls{A-PINENEf}, \gls{B-PINENEf} and \gls{LIMONENEf} contributed \qty{6.7}{\percent} (\qty{66.1}{\tera\gramCarbon\per\year}), \qty{1.7}{\percent} (\qty{18.9}{\tera\gramCarbon\per\year}) and \qty{1.0}{\percent} (\qty{11.4}{\tera\gramCarbon\per\year}), respectively. \gls{ISOPRENEf} and monoterpene emissions are biogenic and mostly linked to vegetation --- overall they contributed approximately \qty{65}{\percent} to global \gls{VOCa} emissions in 2000 \citep{guenther_model_2012}, rendering them a major source of atmospheric \glspl{VOCa}.
|
||||
|
||||
Organic matter in aerosol is present either as \gls{POAa} or \gls{SOAa}. \gls{POAa} and \gls{SOAa} comprise the largest share of \emph{fine} particles with diameters $d\leq\qty{2.5}{\micro\meter}$. On the other hand, large particles with diameters $d>\qty{2.5}{\micro\meter}$ are mostly comprised of particles formed mechanically, including soil and mineral dust, sea salt particles and plant particles \citep{jziemann_kinetics_2012}. \gls{POAa} requires no chemical reactions to condense to the aerosol phase. Conversely, \gls{SOAa} is created when volatile precursor species are chemically altered to lower volatilities, and consequently condense to the aerosol phase. Likely, \gls{SOAa} constitues a large fraction of organic aerosol \cite{bianchi_highly_2019, hallquist_formation_2009}. As a general rule of thumb, higher oxygen content of a molecule indicates \emph{lower} volatility. Therefore, oxidation reactions are highly important in \gls{SOAa} formation because oxidation effectively \emph{decreases} volatility. Recent work summarised by \citet{bianchi_highly_2019} suggests that there exists class of of low-volatile species referred to as \glspl{HOMa} with low volatility. Such \glspl{HOMa} are formed through \emph{autooxidation} reactions involving peroxy radicals: this process is detailed by \citet{bianchi_highly_2019}, and the subtle but important difference between \glspl{HOMa} and molecules with high oxygen content is laid out. Briefly, \glspl{HOMa} are species of very low vapour pressure so that condensation onto existing particles is very probable and almost irreversible \citep{bianchi_highly_2019}. High yields of \glspl{HOMa} have been observed for \gls{ISOPRENEf} and the monoterpenes \gls{A-PINENEf} and especially \gls{LIMONENEf} \citep{bianchi_highly_2019}, with total yields of \qty{4}{\percent} (\gls{ISOPRENEf}), \qtyrange{7.0\pm3.5}{3.4\pm1.0}{\percent} (\gls{A-PINENEf}) and \qty{17.0\pm8.5}{\percent} (\gls{LIMONENEf}), respectively \citep{bianchi_highly_2019, jokinen_production_2015, ng_secondary_2008, ehn_large_2014, kirkby_ion-induced_2016}. It may therefore be assumed that derivatives --- or more precisely oxidation products --- of monoterpenes or \gls{ISOPRENEf} are common in \gls{SOAa}. Building on the work of \citet{saunders_insights_2012}, chosing an oxidation product of \gls{ISOPRENEf} or monoterpenes as the investigated organics may constitute a more realistc proxy for aerosol organics.
|
||||
|
||||
Recently, \citet{reza_iodine_2024} have performed similar experiments as \citet{saunders_insights_2012}, but using organic species better representing \gls{VOCa} oxidation. Recent observations have shown elevated concentrations of \ce{\glssymbol{IO.f}(g)} in dust layers above the Atacama and Sechura deserts: \citet{koenig_ozone_2021} measured a ten-fold enhancement of \gls{IO.f} concentrations compared to the regional background signal of \qtyrange{0.10}{0.25}{\pptv}. Because iron is hypothetised to catalyse photochemistry in dust particles, and since it is the most abundant transition metal in dust minerals \citep{aal-abadleh_perspective_2023}, iron may serve as a proxy for dust when investigating the reduction of \gls{IO3-f}. In a series of \gls{CWFTRa} experiments, \citet{reza_iodine_2024} used a \gls{CE-DOASa} to detect \glssymbol{I2f}\ce{(g)} and a \gls{ToF I-CIMSa} to detect \glspl{OVOCa} associated with \gls{IO3-f} reduction in thin aqueous films. The films were inserted into the \gls{CWFTRa} and consisted of an organic or inorganic matrix and \gls{IO3-f}.
|
||||
The organic matrices included \gls{IRON-3-CITRATEa}, \gls{CAa} and \gls{BTCAa}. \gls{CAa} was found in aerosol \citep{lienhard_measurements_2012} and is a proxy for oxygenated organic species. \gls{IRON-3-CITRATEa}, as a known photoactive compound, is considered a suitable proxy for \ce{Fe}(\toRoman{3}) carboxylate complexes found in the atmosphere \citep{reza_iodine_2024}. Importantly, \gls{CAa} has well-characterised hygroscopic properties \citep{reza_iodine_2024} so that this matrix can be used to control against \glspl{MATRIX-EFFECT-(CHEM)g} of organics that are due to iron when using \gls{IRON-3-CITRATEa}. These matrices were mixed with a solution of \gls{NaIO3f} to introduce \gls{IO3-f} at a concentration of $\approx\qty{30}{\milli\Molar}$. The results show that irradiation with \gls{VISa} for films containing \gls{IRON-3-CITRATEa} led to the reduction of $\approx\qty{40}{\percent}$ of the initially present \gls{IO3-f}. Likely, \gls{IRON-3-CITRATEa} undergoes a \gls{LMCTa} induced through irradiance with a photon at $\lambda<\qty{500}{\nano\meter}$ to yield \gls{CITRATEa} radicals and solvated electrons \ce{e-(aq)}, as described by \citet{saunders_insights_2012}. Likely, reduction of \gls{IO3-f} is driven through these solvated electrons. Furthermore, \citet{reza_iodine_2024} report that the speciation of the \glspl{CHROMOPHOREg} may include iodine-containing compounds.
|
||||
|
||||
\end{document}
|
||||
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|
||||
% makeindex style file created by the glossaries package
|
||||
% for document 'methods' on 2026-8-11
|
||||
actual '?'
|
||||
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|
||||
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|
||||
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|
||||
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|
||||
preamble "\\glossarysection[\\glossarytoctitle]{\\glossarytitle}\\glossarypreamble\n\\begin{theglossary}\\glossaryheader\n"
|
||||
postamble "\%\n\\end{theglossary}\\glossarypostamble\n"
|
||||
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|
||||
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|
||||
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|
||||
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|
||||
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|
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|
||||
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|
||||
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||||
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|
||||
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||||
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||||
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|
||||
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|
||||
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|
||||
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|
||||
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|
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||||
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||||
% !TeX program = lualatex
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% SUBFILE MODE
|
||||
\documentclass[../main/main.tex]{subfiles}
|
||||
\graphicspath{{../graphics/}}
|
||||
|
||||
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||||
%% ------------------------------------------------------------------%
|
||||
%% DOCUMENT
|
||||
|
||||
|
||||
\begin{document}
|
||||
|
||||
\pagestyle{mainbody}
|
||||
|
||||
\chapter{Methods}
|
||||
\thispagestyle{mainbody}
|
||||
|
||||
We use a sequential workflow outlined in figure \ref{methods: fig: overview over workflow}.
|
||||
|
||||
\begin{figure}[h]
|
||||
\centering
|
||||
\includegraphics{flowcharts/method_overview.pdf}
|
||||
\caption[Overview over Workflow]{\textbf{Overview over Workflow}. The initial step consists of producing a filter containing \gls{VOCa} in the \gls{OFRa}, which is subsequently extracted to produce a solution. }
|
||||
\label{methods: fig: overview over workflow}
|
||||
\end{figure}
|
||||
|
||||
\section{Oxidation Flow Reactor}
|
||||
|
||||
\begin{figure}[h]
|
||||
\centering
|
||||
\includegraphics{flowcharts/OFR_Flowchart.pdf}
|
||||
\caption[Overview over OFR Flowchart]{\textbf{Overview over OFR Flowchart}. Flow Chart displaying the functionality of the OFR Setup, including various flows, instruments, diverse valves and other things.}
|
||||
\end{figure}
|
||||
|
||||
\section{Filter TOC Measurement}
|
||||
|
||||
\begin{figure}
|
||||
\centering
|
||||
\includegraphics{processes/solution_creation.pdf}
|
||||
\caption[Procedure to create solutions]{Procedure to create solutions. Beaker apapted from: Diogo Losch De Oliveira (2026). Beakers [Illustration]. CC-BY 4.0. SciDraw.io. https://scidraw.io/drawing/beakers-ba8583ed, accessed 10. August 16:16}
|
||||
\label{methods: fig: solution preparation}
|
||||
\end{figure}
|
||||
|
||||
\section{Preparation of coating solution}
|
||||
|
||||
|
||||
\section{Coated Wall Flow Tube experiment}
|
||||
|
||||
\section{Data Analysis}
|
||||
|
||||
\end{document}
|
||||
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||||
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|
||||
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||||
\begin{document}
|
||||
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||||
\pagestyle{mainbody}
|
||||
|
||||
\chapter{Introduction}
|
||||
\thispagestyle{mainbody}
|
||||
|
||||
|
||||
Iodine is the heaviest stable halogen element with atomic number \qty{53}{}. It has an average atomic weight of \qty{126.904}{\amu} and forms a semi-lustrous solid under standard conditions (here \qty{273.15}{\kelvin} and \qty{1}{\bar}, see \citet{calvert_glossary_1990}) \citep{kaiho_physical_2015}. Its melting and boiling points are \qty{114}{\degreeCelsius} and \qty{184}{\degreeCelsius}, respectively, and its vapour pressure is \qty{0.031}{\kilo\pascal} and \qty{9.17}{\kilo\pascal} at \qty{25}{\degreeCelsius} and \qty{113.6}{\degreeCelsius}, respectively \citep{kaiho_physical_2015}. The atomic radius of iodine is \qty{140}{\pico\meter} and its first ionisation energy is \qty{1015}{\kilo\joule\per\mol} \citep{kaiho_physical_2015}. Iodine is important in the enviornment: in the atmosphere, it influences the chemistry of ozone and important radical species, and it may be cause the formation of particles that may act as nuclei for aerosol or clouds \citep{saiz-lopez_atmospheric_2012}. The former is important for the capability of the atmophere to oxidise and remove species emitted to it, while the latter is important because of its effect on radiative equilibrium of Earth.
|
||||
|
||||
\section{Iodine in the environment}
|
||||
|
||||
Iodine is litophilic and incompatible in Earth's astenosphere, and therefore concentrated in oceans and surface sediments \citep{kendrick_halogen_2024}. Marine sediments constitute the largest iodine reservoir \citep{kendrick_halogen_2024} with much higher concentrations of \qtyrange{20}{600}{\milli\gram\per\kilogram} compared to soil- (\qtyrange{0.5}{20}{\milli\gram\per\kilogram}) or rock (\qtyrange{0.08}{0.5}{\milli\gram\per\kilogram}) concentrations \citep{whitehead_distribution_1984}. Sedimented iodine may be recycled into the oceans through sedimentary brines \citep{muramatsu_recycling_2001, muramatsu_studies_2004} around techtonically active subduction zones \citep{carrano_influence_2020} through diagenesis processes involving thermal decompostion or microbiological reduction of buried organic matter \citep{kendrick_halogen_2024, muramatsu_recycling_2001}. Consequently, iodine concentrations in the oceans are approximately \qtyrange{45}{60}{\micro\gram\per\liter} \citep{whitehead_distribution_1984}, mostly in the form of \gls{IO3-f}, the thermodynamically most stable state of iodine in aqueous solution \citep{fuge_iodine_2015}. However, \gls{IO3-f} exhibits a nutrient-like profile \citep{carrano_influence_2020} being depleted at the surface, whereas \gls{I-f} is enriched in the surface \citep{elderfield_biophilic_1980}. Similarly, organic matter is enriched in the surface, so that the existence of some iodinated organics may be presumed \citep{saiz-lopez_atmospheric_2012}. Within the oceans, iodine is incorporated preferrentially in organic matter \citep{kendrick_halogen_2024} by micro- and macroalgae, and aerobic bacteria \citep{carpenter_biogeochemical_2015}: through faciliated diffusion (see detailed descriptions in \citet{kupper_iodide_2008, winter_exploring_2009, amachi_microbial_2008}), cells store iodine as \ce{\glssymbol{I-f}(aq)} or associated to organic molecules \citep{kupper_iodide_2008, amachi_microbial_2008}.
|
||||
\Gls{I-f} within the cell interior may act as an antioxidant \citep{kupper_iodide_2008}: upon oxidative stress, the \gls{I-f} reservoir is mobilised and cells emit \ce{\glssymbol{I-f}(aq)} and a range of \glspl{VOICa} \citep{kupper_iodide_2008, carpenter_biogeochemical_2015} that may volatilise to the atmosphere. Analogously, when oxidative stress occurs during air exposure at low tide, the hetergeneous surface reaction of \gls{I-f} and \gls{O3f} at the sea-water interface produces \gls{HOIf}, \gls{I2f} and \glspl{IO.f} directly emitted to the atmosphere \citep{carpenter_biogeochemical_2015, palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010, he_role_2021}. It is currently thought that the biggest source of inorganic iodine to the atmosphere is \gls{HOIf} produced via the same pathway, exceeding the emissions of \gls{I2f} by one order of magnitude \citep{carpenter_atmospheric_2013}.
|
||||
Nevertheless, the atmospheric iodine budget is currently not well-constrained \citep{saiz-lopez_atmospheric_2012}. \glspl{VOICa} (notably \ce{\glssymbol{CH3If}}) and inorganic iodine species (\ce{\glssymbol{HOIf}}, \ce{\glssymbol{I2f}}, \ce{\glssymbol{IO.f}}) emitted from the oceans constitute the biggest source of iodine to the atmosphere \citep{carpenter_biogeochemical_2015, carpenter_atmospheric_2013}, with estimated input $\approx\qty{550}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Most \glspl{VOICa} are photolabile with lifetimes on the order of minutes to days \citep{bloss_kinetics_2001}. Other natural sources of iodine to the amtosphere include soils and plants \citep{whitehead_distribution_1984, carpenter_biogeochemical_2015, fuge_iodine_2015}, terrestrial water systems \citep{whitehead_distribution_1984}, and volcanoes or salt lakes \citep{carpenter_biogeochemical_2015}. The additional input from terrestrial sources into the atmosphere is $\approx\qtyrange{80}{110}{\giga\gram\per\year}$ \citep{saiz-lopez_atmospheric_2012}. Anthropogenic sources include direct emissions from fossil fuel burning \citep{fuge_iodine_2015} and pesticide use \citep{zheng_accelerated_2003, whitehead_distribution_1984}. There are indirect anthropogenic effects as well: ice core data indicates that the sea-air flux of iodine has tripled between 1950 and 2010 as a consequence of increased anthropogenic ozone pollution of the troposphere \citep{cuevas_rapid_2018}. Sinks of atmospheric iodine include wet- and dry deposition \citep{fuge_iodine_2015}, and direct uptake through plants \citep{fuge_iodine_2015}. Overall, this leads to boundary layer mixing ratios of $\chi_{\ce{\glssymbol{I2f}(g)}}\leq\qty{93}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{IO.f}(g)}}\leq\qtyrange{3}{20}{\pptv}$ \citep{carpenter_biogeochemical_2015}, $\chi_{\ce{\glssymbol{HOIf}(g)}}\leq\qty{1}{\pptv}$ \citep{he_role_2021} and $\chi_{\ce{\glssymbol{I.f}(g)}}\leq\qtyrange{0.1}{22}{\pptv}$ \citep{carpenter_biogeochemical_2015, he_role_2021}.
|
||||
|
||||
\section{Iodine Chemistry in the Atmosphere}
|
||||
|
||||
The importance of the marine iodine source is likely also reflected in aerosol composition: above marine areas, aerosol is enriched in iodine relative to seawater content by a factor of \qtyrange{100}{1000}{} \citep{carpenter_biogeochemical_2015}. Iodine may be transported into the aerosol phase through bubble-bursting of iodine-rich surface ocean waters \citep{saiz-lopez_atmospheric_2012}, or through the formation of aerosol via \glspl{IOPa} \citep{odowd_marine_2002}. Likely, low-volatility iodinated organics may also condense into the aerosol phase. Overall, various iodinated species may be present in aerosol including \gls{I-f}, \gls{IO3-f}, \gls{HOIf} and \gls{SOIa} \citep{saiz-lopez_atmospheric_2012}. \Citet{saiz-lopez_atmospheric_2012, gilfedder_iodine_2008} report that \gls{SOIa} is very frequent in aerosol and may constitute the largest reservoir of iodine in aerosol. There appear to be two principal pathways of \gls{SOIa} accomodation: direct accumulation from sea spray enriched in iodinated organics, and the reaction of \gls{HOIf} with aerosol organics. \Gls{HOIf} may also be highly reactive towards other species, likely due to its affinity for nucelophilic attacks on susceptible species. In general however, \gls{HOIf} or other likewise reduced iodine species such as \gls{I-f} should be oxidised to \gls{IO3-f} \citep{gilfedder_iodine_2008}, the thermodynamically most stable form of iodine in aqueous solution. Consequently, the accumulated form of iodine in condensed aerosol phases is often thought to be \gls{IO3-f} \citep{gilfedder_iodine_2008, saiz-lopez_atmospheric_2012}. However, observations in the troposphere indicate higher aerosol contents of \gls{I-f} than \gls{IO3-f} \citep{gilfedder_iodine_2008}, or high variability in the \gls{I-f}/\gls{IO3-f} ratio \citep{saiz-lopez_atmospheric_2012}. This indicates the presence of a mechanism reducing \gls{IO3-f} in the troposphere.
|
||||
|
||||
Hetergeneous aerosol chemistry of iodine is closely linked to homogeneous chemistry of iodine through many iodine species. Generally, atmospheric iodine chemistry is initiated mostly through \gls{RISa} such as \glspl{I.f} or \glspl{IO.f}. Briefly, homogeneous iodine chemistry involves catalytic destruction of troposheric ozone via various pathways involving \glspl{HOxf} and \glspl{NOxf} as well as other halogen atoms in the atmosphere \citep{saiz-lopez_reactive_2012}. This process is photochemically driven and initiated with \glssymbol{IO.f} and \glssymbol{I.f}. \citet{saiz-lopez_reactive_2012} have outlined the mechanism: the intial step is the production of \glspl{I.f} from \glspl{RInf} or \gls{I2f}. The \glspl{I.f} react with \gls{O3f} to produce \glspl{IO.f} that in turn recombine to again produce \glspl{I.f}:
|
||||
|
||||
\begin{reactions}
|
||||
\RI{}(g) + ${h\nu}$ &-> R^{\bullet}(g) + \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I2f}(g) + ${h\nu}$ &-> 2 \glssymbol{I.f}(g)\\
|
||||
\glssymbol{I.f}(g) + \glssymbol{O3f}(g) &-> \glssymbol{IO.f}(g) + \glssymbol{O2f}(g) \label{reac: intro: iodine radical ozone loss}\\
|
||||
2\glssymbol{IO.f} &-> 2\glssymbol{I.f}(g) + \glssymbol{O2f}(g)\label{reac: intro: 2IO to 2I and O2}
|
||||
\end{reactions}
|
||||
The net outcome is ozone destruction with \ce{2\glssymbol{O3f}(g) -> 3\glssymbol{O2f}(g)}, although reaction \ref{reac: intro: 2IO to 2I and O2} has other channels that may involve \glssymbol{HOxf} and \glssymbol{NOxf} cycles. Importantly, the \gls{IO.f} has a lifetime against photolysis in the boundary layer on the order of seconds \citep{bloss_kinetics_2001}. Likewise, the effective lifetime of \gls{Ix.f} against uptake in aerosol is on the order of hours \citep{dix_detection_2013}: sustained presence of \glspl{IO.f} in the atmosphere therefore requires an effective recycling mechanism for \ce{\glssymbol{IO.f}}.
|
||||
|
||||
Additionally, iodine may be involved in the oxidation of atmospheric organic molecules or mercury, allowing the latter to enter the food chain as highly poisonous methylmercury \citep{steffen_synthesis_2008, saiz-lopez_reactive_2012, saiz-lopez_atmospheric_2012}, and likely leading to enhanced condensation of organics into the aerosol phase through the former. Further, through formation of \glspl{IOPa}, iodine oxides may lead to the production of \glspl{UFAPa} \citep{carpenter_biogeochemical_2015}. Volatile species may condense on \glspl{UFAPa} that can grow up to the point of becoming \glspl{CCNa} \citep{saiz-lopez_atmospheric_2012}. Recent evidence shows that nucleation via iodine oxoacids to produce \glspl{IOPa} is highly efficient and sometimes competitive with sulfuric acid-ammonium driven nucleation \citep{he_role_2021}. Moreover, heterogeneous iodine chemistry on pre-existing frozen or liquid salt particles may lead to sudden increases in gas phase iodine species \citep{saiz-lopez_reactive_2012}. Importantly, the reaction of \gls{Br-f} with \gls{O3f} on frozen salt solutions occurs in the brine pertaining to the bulk ice phase, rather than \emph{within} the bulk ice phase \citep{oldridge_formation_2011}: such brines are formed when freezing solutions exclude solutes --- the heterogeneous reaction of \gls{O3f} with \gls{I-f} on frozen aerosol is here assumed to behave similarly. In other words, the heterogeneous reaction of \gls{O3f} with aerosol surfaces is assumed to be similar for frozen and liquid aerosol particles.
|
||||
|
||||
Other heterogeneous effects may lead to substantial iodine emissions through the reaction of ozone with dissolved \gls{I-f} in ocean and aerosols \citep{palmer_iodine_2005, liu_kinetics_2001, sakamoto_direct_2009, hayase_heterogeneous_2010}. In the upper troposphere and lower stratosphere, heterogeneous recycling of iodine species is highly important: Model calculations by \citet{saiz-lopez_injection_2015} show that from the lower troposphere, convection may transport inorganic- and organic iodine species to the lower stratosphere, causing a \gls{Iyf} injection of \qtyrange{0.25}{0.7}{\pptv} \citep{saiz-lopez_injection_2015}. Measurements by \citet{koenig_quantitative_2020} are in agreement with this, indicating an injection of \qty{0.77\pm0.10}{\pptv} of \glssymbol{Iyf} into the lower stratosphere. Associated therewith is a mixing ratio of $\chi_{\ce{\glssymbol{IO.f}(g)}}=\qty{0.06\pm0.03}{\pptv}$ even for aged stratospheric air. \Citet{koenig_quantitative_2020} also observed that increases in altitude across the troposphere are associated with (1) an increase in particulate iodine and a decrease in gas phase iodine; and (2) a shift of \gls{I-f}-\gls{IO3-f} speciation in the condensed phase towards \gls{IO3-f}. Simulations could reproduce observed $\chi_{\ce{\glssymbol{IO.f}(g)}}$ only when a recycling scheme for iodine on ice particles was applied, and when the proper partioning between condensed- and gas phase was applied. This indicates that, as for the troposphere, a recycling mechanism producing gas phase \glspl{IO.f} must exist. There is also evidence that \gls{IO3-f} should be reduced to \gls{I-f}: \citet{pillar-little_conversion_2013} have established a pathway through which \gls{I-f} and \gls{O3f} cause volatilization of \ce{\glssymbol{I2f}(g)} and \ce{\glssymbol{HOIf}(g)} from watery microdroplets. However, it is still unclear \emph{how} the necessary \gls{I-f} is formed, given that most iodine should be present as \gls{IO3-f}. Consequently, an important question to answer is: how is \glssymbol{IO3-f} reduced to species --- most likely \glssymbol{I-f} --- that may, directly of after reacting, volatilise to the gas phase?
|
||||
|
||||
\section{Reduction of Iodate}
|
||||
|
||||
\Citet{saunders_insights_2012} have shown that \gls{IO3-f} may be reduced when solutions of \gls{IO3-f} and \gls{HAa} are irradiated with \gls{UV-Aa} and \gls{VISa} light between $\gls{LAMBDAs}\geq\qty{310}{\nano\meter}$ and $\gls{LAMBDAs}\approx\qty{780}{\nano\meter}$. The light source was filtered to exclude \gls{IRa} light and lamp output below $\gls{LAMBDAs}=\qty{310}{\nano\meter}$ to simulate the \gls{UV-Aa}-\gls{VISa} solar spectrum in the lower troposphere. They found that the major product of this photochemically induced process was \gls{SOIa} and that the proportion of \gls{I-f} in the reactant solution remained constant at approximately \qty{20}{\percent}. Since \gls{HAa} is a \gls{CHROMOPHOREg}, the suggested mechanism involves photogeneration of solvated electrons \ce{e-(aq)} that, in dependence of \gls{pHs}, yield \gls{HOIf}: \ce{\glssymbol{IO3-f}(aq) + 4e-(aq) + 5\glssymbol{H+f}(aq) ->\glssymbol{HOIf}(aq) + 2\glssymbol{H2Of}(aq)}. From there, \gls{SOIa} may be created through the nucleophilic attack of \gls{HOIf} on diphenolic functional groups \citep{saunders_insights_2012}. Alternatively, \gls{I2f} may be produced through reaction \ref{reac: intro: HOI to I2}, as described by \citet{pillar-little_conversion_2013}:
|
||||
|
||||
\begin{reaction}
|
||||
\glssymbol{HOIf}(aq) + \glssymbol{I-f} + \glssymbol{H+f}(aq) -> \glssymbol{I2f}(aq) + \glssymbol{H2Of}(l) \label{reac: intro: HOI to I2}
|
||||
\end{reaction}
|
||||
Since \gls{I2f} is insoluble \citep{saiz-lopez_atmospheric_2012}, there will be volatilisation of \gls{I2f} to the gas phase. Overall, the mechanism suggested by \citet{saunders_insights_2012} produces primarily \gls{HOIf} \gls{I2f} --- the production pathway of \gls{I-f} has not been elucidated. The presence of \gls{I-f}, however, appears necessary for the production of \ce{\glssymbol{I2f}(g)}. It is hypothetised that \gls{I-f} may be regenerated from \gls{SOIa} \citep{saunders_insights_2012, baker_marine_2005}. Finally, \citet{saunders_insights_2012} have reported oscillations in the release of \ce{\glssymbol{I2f}(g)}. This is likely associated with formation of \gls{H2O2f} as a byproduct of \gls{HAa} photolysis \citep{saunders_insights_2012}. Indeed, \citet{cooper_photochemical_1988} have shown that \gls{H2O2f} is a common product when irradiating aqueous solutions of \glspl{CHROMOPHOREg}. Given \gls{H2O2f}, oscillations in \ce{\glssymbol{I2f}}-\ce{\glssymbol{IO3-f}} are known as the \gls{BRAY-LIEBHAFSKY-MECHANISMa}, first described by \citet{bray_periodic_1921, bray_reactions_1931}: \gls{H2O2f} interacts with \gls{I2f} and \gls{IO3-f} via
|
||||
|
||||
\begin{reactions}
|
||||
&2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 5\glssymbol{H2O2f}(aq) <=> \glssymbol{I2f}(aq) + 5\glssymbol{O2f}(g) + 6\glssymbol{H2Of}(l) \label{reac: oxidation of iodine through hydrogen peroxide}\\
|
||||
&\glssymbol{I2f}(aq) + 5\glssymbol{H2O2f}(aq) <=> 2\glssymbol{IO3-f}(aq) + 2\glssymbol{H+f}(aq) + 4\glssymbol{H2Of}(l) \label{reac: reduction of iodate through hydrogen peroxide}
|
||||
\end{reactions}
|
||||
to yield a net catalytic decomposition of \gls{H2O2f} via
|
||||
|
||||
\begin{reaction}
|
||||
2\glssymbol{H2O2f}(aq) -> 2\glssymbol{H2Of}(l) + \glssymbol{O2f}(g) \label{reac: net catalytic destruction of hydrogen peroxide through iodine-iodate system}
|
||||
\end{reaction}
|
||||
The oscillation reaction has a \emph{stable} regime --- here, all species reach steady state except \glssymbol{H2O2f}: likely, \glssymbol{O2f}\ce{(g)} volatilises and \gls{LE-CHATELIER-PRINCIPLEa} dictates that \gls{H2O2f} consequently depletes. The \emph{unstable} regime where either reaction \ref{reac: oxidation of iodine through hydrogen peroxide} or \ref{reac: reduction of iodate through hydrogen peroxide} occur preferrentially, leads to oscillations in \gls{I2f} and \gls{IO3-f}. These oscillations are modulated by initial \gls{pHs} \citep{bray_periodic_1921} and temperature. Including an organic reducing agent and a metal-ion catalyst results in the \gls{BRIGGS-RAUSCHER-MECHANISMa} after \citet{briggs_oscillating_1973}, elucidated by \citet{schmitz_kinetics_2012}: Briefly, in addition to reaction \ref{reac: reduction of iodate through hydrogen peroxide}, the presence of some organic species \ce{R-H2} will induce the following reactions:
|
||||
|
||||
\begin{reactions}
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-H2(aq) &-> 5 R-HI + 3\glssymbol{H2Of}\\
|
||||
\glssymbol{H+f}(aq) + \glssymbol{IO3-f}(aq) + 2\glssymbol{I2f}(aq) + 5 R-HI(aq) &-> 5 R-I2 + 3\glssymbol{H2Of}\\
|
||||
R-I2 + R-H2 &<=> 2 R-HI
|
||||
\end{reactions}
|
||||
The backward reaction likely proceeds via the metal ion catalyst, although \citet{schmitz_kinetics_2012} reported the possibility of non-catalysed pathways.
|
||||
|
||||
A lot has been learned so far: organic substances may lead to the reduction of \gls{IO3-f}, via \gls{CHROMOPHOREg} activity. Furthermore, observed oscillations in gas phase \ce{\glssymbol{I2f}} may be explained through \gls{BRAY-LIEBHAFSKY-MECHANISMa}-\gls{BRIGGS-RAUSCHER-MECHANISMa} mechanisms. However, the suitability of \glspl{HAa} to represent organic aerosol has been questioned: \citet{graber_atmospheric_2006} suggested that humic-like substances found in aerosol particles may differ substantially from humic substances found in soil. More specifically, \citet{graber_atmospheric_2006} argue that terrestrial sources --- from which the \gls{HAa} used by \citet{saunders_insights_2012} likely originate --- may not be the origin of the majority of humic-like substances in aerosol. Differences may be found in terms of molecular weight, aromatic moiety content, surface properties and other properties \citep{graber_atmospheric_2006}. Although \glspl{HAa} as organics have profen useful to elucidate the mechanisms of \glssymbol{I2f} recycling, quantitatively constraining this recycling better requires more realistic organics. Another important question to answer, therefore, is: are there proxies that represent organics in aerosol more accurately, and to which the same \gls{CHROMOPHOREg}-dependent pathway of iodine recycling applies?
|
||||
|
||||
\section{Reduction of Iodate: Proxies for Secondary Organic Aerosol}
|
||||
|
||||
\Citet{guenther_global_1995} modelled global natural \gls{VOCa} emissions in 1990. They found a total flux of $\qty{1150}{\tera\gramCarbon\per\year}$, of which \qty{44}{\percent} (\qty{503}{\tera\gramCarbon\per\year}) was \gls{ISOPRENEf} and \qty{11}{\percent} (\qty{127}{\tera\gramCarbon\per\year}) were monoterpenes such as \gls{A-PINENEf}. Thereof, approximately \qty{75}{\percent} orginated from forests. In 2006, The annual atmospheric \gls{VOCa} injection was further specified in 2012 when \citet{guenther_model_2012} reported the following emissions of \glspl{VOCa} for the year 2000: total emissions were \qty{1089}{\tera\gramCarbon\per\year}, of which \gls{ISOPRENEf} emissions were \qty{49.1}{\percent} (\qty{535}{\tera\gramCarbon\per\year}) and the monoterpenes \gls{A-PINENEf}, \gls{B-PINENEf} and \gls{LIMONENEf} contributed \qty{6.7}{\percent} (\qty{66.1}{\tera\gramCarbon\per\year}), \qty{1.7}{\percent} (\qty{18.9}{\tera\gramCarbon\per\year}) and \qty{1.0}{\percent} (\qty{11.4}{\tera\gramCarbon\per\year}), respectively. \gls{ISOPRENEf} and monoterpene emissions are biogenic and mostly linked to vegetation --- overall they contributed approximately \qty{65}{\percent} to global \gls{VOCa} emissions in 2000 \citep{guenther_model_2012}, rendering them a major source of atmospheric \glspl{VOCa}.
|
||||
|
||||
Organic matter in aerosol is present either as \gls{POAa} or \gls{SOAa}. \gls{POAa} and \gls{SOAa} comprise the largest share of \emph{fine} particles with diameters $d\leq\qty{2.5}{\micro\meter}$. On the other hand, large particles with diameters $d>\qty{2.5}{\micro\meter}$ are mostly comprised of particles formed mechanically, including soil and mineral dust, sea salt particles and plant particles \citep{jziemann_kinetics_2012}. \gls{POAa} requires no chemical reactions to condense to the aerosol phase. Conversely, \gls{SOAa} is created when volatile precursor species are chemically altered to lower volatilities, and consequently condense to the aerosol phase. Likely, \gls{SOAa} constitues a large fraction of organic aerosol \cite{bianchi_highly_2019, hallquist_formation_2009}. As a general rule of thumb, higher oxygen content of a molecule indicates \emph{lower} volatility. Therefore, oxidation reactions are highly important in \gls{SOAa} formation because oxidation effectively \emph{decreases} volatility. Recent work summarised by \citet{bianchi_highly_2019} suggests that there exists class of of low-volatile species referred to as \glspl{HOMa} with low volatility. Such \glspl{HOMa} are formed through \emph{autooxidation} reactions involving peroxy radicals: this process is detailed by \citet{bianchi_highly_2019}, and the subtle but important difference between \glspl{HOMa} and molecules with high oxygen content is laid out. Briefly, \glspl{HOMa} are species of very low vapour pressure so that condensation onto existing particles is very probable and almost irreversible \citep{bianchi_highly_2019}. High yields of \glspl{HOMa} have been observed for \gls{ISOPRENEf} and the monoterpenes \gls{A-PINENEf} and especially \gls{LIMONENEf} \citep{bianchi_highly_2019}, with total yields of \qty{4}{\percent} (\gls{ISOPRENEf}), \qtyrange{7.0\pm3.5}{3.4\pm1.0}{\percent} (\gls{A-PINENEf}) and \qty{17.0\pm8.5}{\percent} (\gls{LIMONENEf}), respectively \citep{bianchi_highly_2019, jokinen_production_2015, ng_secondary_2008, ehn_large_2014, kirkby_ion-induced_2016}. It may therefore be assumed that derivatives --- or more precisely oxidation products --- of monoterpenes or \gls{ISOPRENEf} are common in \gls{SOAa}. Building on the work of \citet{saunders_insights_2012}, chosing an oxidation product of \gls{ISOPRENEf} or monoterpenes as the investigated organics may constitute a more realistc proxy for aerosol organics.
|
||||
|
||||
Recently, \citet{reza_iodine_2024} have performed similar experiments as \citet{saunders_insights_2012}, but using organic species better representing \gls{VOCa} oxidation. Recent observations have shown elevated concentrations of \ce{\glssymbol{IO.f}(g)} in dust layers above the Atacama and Sechura deserts: \citet{koenig_ozone_2021} measured a ten-fold enhancement of \gls{IO.f} concentrations compared to the regional background signal of \qtyrange{0.10}{0.25}{\pptv}. Because iron is hypothetised to catalyse photochemistry in dust particles, and since it is the most abundant transition metal in dust minerals \citep{aal-abadleh_perspective_2023}, iron may serve as a proxy for dust when investigating the reduction of \gls{IO3-f}. In a series of \gls{CWFTRa} experiments, \citet{reza_iodine_2024} used a \gls{CE-DOASa} to detect \glssymbol{I2f}\ce{(g)} and a \gls{ToF I-CIMSa} to detect \glspl{OVOCa} associated with \gls{IO3-f} reduction in thin aqueous films. The films were inserted into the \gls{CWFTRa} and consisted of an organic or inorganic matrix and \gls{IO3-f}.
|
||||
The organic matrices included \gls{IRON-3-CITRATEa}, \gls{CAa} and \gls{BTCAa}. \gls{CAa} was found in aerosol \citep{lienhard_measurements_2012} and is a proxy for oxygenated organic species. \gls{IRON-3-CITRATEa}, as a known photoactive compound, is considered a suitable proxy for \ce{Fe}(\toRoman{3}) carboxylate complexes found in the atmosphere \citep{reza_iodine_2024}. Importantly, \gls{CAa} has well-characterised hygroscopic properties \citep{reza_iodine_2024} so that this matrix can be used to control against \glspl{MATRIX-EFFECT-(CHEM)g} of organics that are due to iron when using \gls{IRON-3-CITRATEa}. These matrices were mixed with a solution of \gls{NaIO3f} to introduce \gls{IO3-f} at a concentration of $\approx\qty{30}{\milli\Molar}$. The results show that irradiation with \gls{VISa} for films containing \gls{IRON-3-CITRATEa} led to the reduction of $\approx\qty{40}{\percent}$ of the initially present \gls{IO3-f}. Likely, \gls{IRON-3-CITRATEa} undergoes a \gls{LMCTa} induced through irradiance with a photon at $\lambda<\qty{500}{\nano\meter}$ to yield \gls{CITRATEa} radicals and solvated electrons \ce{e-(aq)}, as described by \citet{saunders_insights_2012}. Likely, reduction of \gls{IO3-f} is driven through these solvated electrons. Furthermore, \citet{reza_iodine_2024} report that the speciation of the \glspl{CHROMOPHOREg} may include iodine-containing compounds.
|
||||
|
||||
\end{document}
|
||||
@@ -0,0 +1,5 @@
|
||||
%% CUSTOM MATH COMMANDS
|
||||
|
||||
\newcommand{\der}[1]{\textnormal{d}{#1}}
|
||||
\newcommand{\derf}[2]{\frac{\der{#1}}{\der{#2}}}
|
||||
\newcommand{\RI}[1]{\ce{RI}_{{#1}}}
|
||||
@@ -0,0 +1,473 @@
|
||||
%% ------------------------------------------------------------------%
|
||||
%% ACCRONYMS
|
||||
|
||||
\newglossaryentry{CWFTRa}{
|
||||
type=\acronymtype,
|
||||
first={coated wall flow tube reactor (CWFTR)\glsadd{CWFTRg}},
|
||||
name={CWFTR},
|
||||
description={Coated Wall Flow Tube Reactor},
|
||||
see=[see Glossary:]{CWFTRg}
|
||||
}
|
||||
|
||||
\newglossaryentry{vHPOa}{
|
||||
type=\acronymtype,
|
||||
first={vanadium-dependent haloperoxidase (vHPO)},
|
||||
name={vHPO},
|
||||
description={Vanadium-dependent haloperoxidase}
|
||||
}
|
||||
|
||||
\newglossaryentry{IOPa}{
|
||||
type=\acronymtype,
|
||||
first={iodine oxide particle (IOP)},
|
||||
firstplural={iodine oxide particles (IOPs)},
|
||||
name={IOP},
|
||||
description={Iodine oxide particle}
|
||||
}
|
||||
|
||||
\newglossaryentry{IUPACa}{
|
||||
type=\acronymtype,
|
||||
first={International Union of Pure and Applied Chemistry (IUPAC)},
|
||||
name={IUPAC},
|
||||
description={International Union of Pure and Applied Chemistry}
|
||||
}
|
||||
|
||||
\newglossaryentry{UFAPa}{
|
||||
type=\acronymtype,
|
||||
first={ultrafine aerosol particle (UFAP)},
|
||||
firstplural={ultrafine aerosol particles (UFAPs)},
|
||||
name={UFAP},
|
||||
description={ultrafine aerosol particle}
|
||||
}
|
||||
|
||||
\newglossaryentry{SOAa}{
|
||||
type=\acronymtype,
|
||||
first={secondary organic aerosol (SOA)},
|
||||
name={SOA},
|
||||
description={secondary organic aerosol}
|
||||
}
|
||||
|
||||
\newglossaryentry{POAa}{
|
||||
type=\acronymtype,
|
||||
first={primary organic aerosol (POA)},
|
||||
name={POA},
|
||||
description={primary organic aerosol}
|
||||
}
|
||||
|
||||
\newglossaryentry{OFRa}{
|
||||
type=\acronymtype,
|
||||
first={oxidation flow reactor (OFR)},
|
||||
firstplural={oxidation flow reactors (OFRs)},
|
||||
name={OFR},
|
||||
description={oxidation flow reactor}
|
||||
}
|
||||
|
||||
\newglossaryentry{CCNa}{
|
||||
type=\acronymtype,
|
||||
first={cloud condensation nucleus (CNN)},
|
||||
firstplural={cloud condensation nuclei (CNN)},
|
||||
name={CNN},
|
||||
description={cloud condensation nucleus}
|
||||
}
|
||||
|
||||
\newglossaryentry{DOASa}{
|
||||
type=\acronymtype,
|
||||
first={differential optical absorbtion spectroscopy (DOAS)\glsadd{DOASg}},
|
||||
name={DOAS},
|
||||
description={Differential Optical Absorbtion Spectroscopy},
|
||||
see=[see Glossary:]{DOASg}
|
||||
}
|
||||
|
||||
\newglossaryentry{CE-DOASa}{
|
||||
type=\acronymtype,
|
||||
first={cavity-enhanced differential optical absorbtion spectroscopy (CE-DOAS)\glsadd{CE-DOASg}},
|
||||
name={CE-DOAS},
|
||||
description={Cavity-Enhanced Differential Optical Absorbtion Spectroscopy},
|
||||
see=[see Glossary:]{CE-DOASg}
|
||||
}
|
||||
|
||||
\newglossaryentry{UV-Aa}{
|
||||
type=\acronymtype,
|
||||
first={UV-A},
|
||||
name={UV-A},
|
||||
description={Ultraviolet-A light},
|
||||
}
|
||||
|
||||
\newglossaryentry{UVa}{
|
||||
type=\acronymtype,
|
||||
first={UV},
|
||||
name={UV},
|
||||
description={Ultraviolet light},
|
||||
}
|
||||
|
||||
\newglossaryentry{VISa}{
|
||||
type=\acronymtype,
|
||||
first={visible (VIS)},
|
||||
name={VIS},
|
||||
description={Visible light}
|
||||
}
|
||||
|
||||
\newglossaryentry{IRa}{
|
||||
type=\acronymtype,
|
||||
first={infra red (IR)},
|
||||
name={IR},
|
||||
description={Infra red}
|
||||
}
|
||||
|
||||
\newglossaryentry{IRON-3-CITRATEa}{
|
||||
type=\acronymtype,
|
||||
first={iron(\toRoman{3})-citrate},
|
||||
name={Fe-Cit},
|
||||
description={iron(\toRoman{3})-citrate}
|
||||
}
|
||||
|
||||
\newglossaryentry{CITRATEa}{
|
||||
type=\acronymtype,
|
||||
first={citrate (Cit)},
|
||||
name={Cit},
|
||||
description={Citrate}
|
||||
}
|
||||
|
||||
\newglossaryentry{ATDa}{
|
||||
type=\acronymtype,
|
||||
first={Arizona test dust (ATD)},
|
||||
name={ATD},
|
||||
description={Arizona test dust}
|
||||
}
|
||||
|
||||
\newglossaryentry{ABSa}{
|
||||
type=\acronymtype,
|
||||
first={ammonium bisulfate (ABS) \glssymbol{ABSf}},
|
||||
name={ABS},
|
||||
description={Ammonium bisulfate}
|
||||
}
|
||||
|
||||
\newglossaryentry{CAa}{
|
||||
type=\acronymtype,
|
||||
first={citric acid (CA)},
|
||||
name={CA},
|
||||
description={Citric acid}
|
||||
}
|
||||
|
||||
\newglossaryentry{BTCAa}{
|
||||
type=\acronymtype,
|
||||
first={1,2,3,4 butanetetracarboxylic acid (BTCA)},
|
||||
name={BTCA},
|
||||
description={1,2,3,4 butanetetracarboxylic acid}
|
||||
}
|
||||
|
||||
\newglossaryentry{ALWa}{
|
||||
type=\acronymtype,
|
||||
first={aerosol liquid water (ALW)\glsadd{ALWs}},
|
||||
name={ALW},
|
||||
description={Aerosol liquid water}
|
||||
}
|
||||
|
||||
\newglossaryentry{RHa}{
|
||||
type=\acronymtype,
|
||||
first={relative humidity (RH)\glsadd{RHs}},
|
||||
name={RH},
|
||||
description={Relative humidity}
|
||||
}
|
||||
|
||||
\newglossaryentry{VOCa}{
|
||||
type=\acronymtype,
|
||||
first={volatile organic compound (VOC)},
|
||||
firstplural={volatile organic compounds (VOCs)},
|
||||
name={VOC},
|
||||
description={Volatile Organic Compound}
|
||||
}
|
||||
|
||||
\newglossaryentry{VOICa}{
|
||||
type=\acronymtype,
|
||||
first={volatile organic iodine compound (VOIC)\glsadd{RInf}},
|
||||
firstplural={volatile organic iodine compounds (VOICs)},
|
||||
name={VOIC},
|
||||
description={Volatile organic iodine compound}
|
||||
}
|
||||
|
||||
\newglossaryentry{OVOCa}{
|
||||
type=\acronymtype,
|
||||
first={oxygenated volatile organic compound (OVOC)},
|
||||
firstplural={oxygenated volatile organic compounds (OVOCs)},
|
||||
name={OVOC},
|
||||
description={oxygenated volatile organic compound}
|
||||
}
|
||||
|
||||
\newglossaryentry{I-OVOCa}{
|
||||
type=\acronymtype,
|
||||
first={iodine oxygenated volatile organic compound (I-OVOC)},
|
||||
firstplural={iodine oxygenated volatile organic compounds (I-OVOCs)},
|
||||
name={I-OVOC},
|
||||
description={iodine oxygenated volatile organic compound}
|
||||
}
|
||||
|
||||
\newglossaryentry{NDIRMa}{
|
||||
type=\acronymtype,
|
||||
first={non-dispersive infrared monitor (NDIRM)},
|
||||
firstplural={non-dispersive infrared monitors (NDIRMs)},
|
||||
name={NDIRM},
|
||||
description={non-dispersive infrared monitor}
|
||||
}
|
||||
|
||||
\newglossaryentry{ToF CIMSa}{
|
||||
type=\acronymtype,
|
||||
first={time-of-flight (ToF) chemical ionization mass spectrometer (CIMS) (ToF I-CIMS)},
|
||||
firstplural={time-of-flight (ToF) chemical ionization mass spectrometers (CIMSs) (ToF I-CIMSs)},
|
||||
name={ToF CIMS},
|
||||
description={time-of-flight chemical ionization mass spectrometer}
|
||||
}
|
||||
|
||||
\newglossaryentry{PSIa}{
|
||||
type=\acronymtype,
|
||||
first={Paul-Scherrer Institute (PSI)},
|
||||
name={PSI},
|
||||
description={Paul-Scherrer Institute}
|
||||
}
|
||||
|
||||
\newglossaryentry{LMCTa}{
|
||||
type=\acronymtype,
|
||||
first={ligand-to-metal charge transfer (LMCT)},
|
||||
name={LMCT},
|
||||
description={Bla Bla bla}
|
||||
}
|
||||
|
||||
\newglossaryentry{ROSa}{
|
||||
type=\acronymtype,
|
||||
first={reactive oxygen species (ROS)\glsadd{ROSg}},
|
||||
name={ROS},
|
||||
see=[see Glossary:]{ROSg},
|
||||
description={Bla Bla bla}
|
||||
}
|
||||
|
||||
\newglossaryentry{BRAY-LIEBHAFSKY-MECHANISMa}{
|
||||
type=\acronymtype,
|
||||
first={Bray-Liebhafsky mechanism (BLM)\glsadd{BRAY-LIEBHAFSKY-MECHANISMg}},
|
||||
name={BLM},
|
||||
see=[see Glossary:]{BRAY-LIEBHAFSKY-MECHANISMg},
|
||||
description={Bla Bla bla}
|
||||
}
|
||||
|
||||
\newglossaryentry{BRIGGS-RAUSCHER-MECHANISMa}{
|
||||
type=\acronymtype,
|
||||
first={Briggs-Rauscher mechanism (BRM)\glsadd{BRIGGS-RAUSCHER-MECHANISMg}},
|
||||
name={BRM},
|
||||
see=[see Glossary:]{BRIGGS-RAUSCHER-MECHANISMg},
|
||||
description={Bla Bla bla}
|
||||
}
|
||||
|
||||
\newglossaryentry{LE-CHATELIER-PRINCIPLEa}{
|
||||
type=\acronymtype,
|
||||
first={Le Chatelier's principle (LCP)\glsadd{LE-CHATELIER-PRINCIPLEg}},
|
||||
name={LCP},
|
||||
see=[see Glossary:]{LE-CHATELIER-PRINCIPLEg},
|
||||
description={Bla Bla bla}
|
||||
}
|
||||
|
||||
\newglossaryentry{SOIa}{
|
||||
type=\acronymtype,
|
||||
first={soluble organic iodine (SOI)},
|
||||
name={SOI},
|
||||
description={Soluble organic iodine}
|
||||
}
|
||||
|
||||
\newglossaryentry{RISa}{
|
||||
type=\acronymtype,
|
||||
first={reactive iodine species (RIS)},
|
||||
name={RIS},
|
||||
description={Reactive Iodine Species}
|
||||
}
|
||||
|
||||
\newglossaryentry{HAa}{
|
||||
type=\acronymtype,
|
||||
first={humic acid (HA)},
|
||||
name={HA},
|
||||
description={Humic acid}
|
||||
}
|
||||
|
||||
\newglossaryentry{HOMa}{
|
||||
type=\acronymtype,
|
||||
first={highly oxidised organic molecule (HOM)},
|
||||
firstplural={highly oxidised organic molecules (HOMs)},
|
||||
name={HOM},
|
||||
description={Highly oxidised organic molecule}
|
||||
}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% GLOSSARY ENTRIES
|
||||
|
||||
\newglossaryentry{DIFFUSIONg}{
|
||||
text={diffusion},
|
||||
name={diffusion},
|
||||
description={Blablabla},
|
||||
sort={diffusion},
|
||||
user1={diffusion},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{MOLECULAR-DIFFUSIONg}{
|
||||
text={molecular diffusion},
|
||||
name={molecular diffusion},
|
||||
parent={DIFFUSIONg},
|
||||
description={An imbalance between free radicals and antioxidants, leading to damage to the organism through the oxidation of the radicals with non-antioxidant tissue.},
|
||||
sort={Diffusion!molecular},
|
||||
user1={molecular},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{EDDY-DIFFUSIONg}{
|
||||
text={eddy diffusion},
|
||||
name={eddy diffusion},
|
||||
parent={DIFFUSIONg},
|
||||
description={An imbalance between free radicals and antioxidants, leading to damage to the organism through the oxidation of the radicals with non-antioxidant tissue.},
|
||||
sort={Diffusion!eddy},
|
||||
user1={eddy},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{DOASg}{
|
||||
first={differential optical absorption spectroscopy (DOAS)},
|
||||
text={DOAS},
|
||||
name={DOAS},
|
||||
short={DOAS},
|
||||
description={Description},
|
||||
sort={Spectroscopy!differential optical absorption},
|
||||
user1={differential optical absorbtion},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{CE-DOASg}{
|
||||
text={CE-DOAS},
|
||||
name={CE-DOAS},
|
||||
parent={DOASg},
|
||||
see={DOASg},
|
||||
description={Bla},
|
||||
sort={Spectroscopy!differential optical absorbtion!cavity-enhanced},
|
||||
user1={cavity-enhanced},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{MATRIX-(CHEM)g}{
|
||||
first={matrix\glsadd{MATRIX-EFFECT-(CHEM)g}},
|
||||
firstplural={matrices\glsadd{MATRIX-EFFECT-(CHEM)g}},
|
||||
text={matrix},
|
||||
name={Matrix (chem.)},
|
||||
plural={matrices},
|
||||
description={The components of a solution that are not specifically alanysed but that may significantly alter the behaviour of the substance to be analysed, for instance through matrix effects.},
|
||||
see={MATRIX-EFFECT-(CHEM)g},
|
||||
sort={matrix},
|
||||
user1={film},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{MATRIX-EFFECT-(CHEM)g}{
|
||||
text={matrix effect},
|
||||
name={matrix effect},
|
||||
parent={MATRIX-(CHEM)g},
|
||||
plural={matrix effects},
|
||||
description={The effect that matrix has on the analysis and its outcome},
|
||||
sort={matrix!effect},
|
||||
user1={effect},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{CWFTRg}{
|
||||
first={coated wall flow tube reactor (CWFTR)},
|
||||
firstplural={coated wall flow tube reactors (CWFRTs)},
|
||||
text={CWFTR},
|
||||
name={CWFTR},
|
||||
description={blabla},
|
||||
sort={coated wall flow tube},
|
||||
user1={coated wall flow tube},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{CHROMOPHOREg}{
|
||||
text={chromophore},
|
||||
plural={chromophores},
|
||||
name={Chromophore},
|
||||
description={Describtoip},
|
||||
sort={chromophore},
|
||||
user1={Chromophore},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{ACTINIC-FLUXg}{
|
||||
text={actinic flux},
|
||||
plural={actinic fluxes},
|
||||
name={Actinic flux},
|
||||
description={Bla bla bla},
|
||||
sort={Actinic Flux},
|
||||
user1={Actinic},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{OXIDATIBVE-STRESSg}{
|
||||
text={oxidative stress},
|
||||
name={Oxidative stress},
|
||||
description={An imbalance between free radicals and antioxidants, leading to damage to the organism through the oxidation of the radicals with non-antioxidant tissue.},
|
||||
sort={Oxidative!stress},
|
||||
user1={stress},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{ROSg}{
|
||||
text={ROS},
|
||||
name={ROS},
|
||||
description={Bla bla bla},
|
||||
sort={ROS},
|
||||
user1={ROS},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{FENTON-CYCLEg}{
|
||||
text={fenton cycle},
|
||||
name={Fenton cylce},
|
||||
description={Bla bla bla},
|
||||
sort={fenton cycle},
|
||||
user1={fenton cycle},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{BRAY-LIEBHAFSKY-MECHANISMg}{
|
||||
text={Bray-Liebhafsky mechanism},
|
||||
name={Bray-Liebhafsky mechanism},
|
||||
description={Bla bla bla},
|
||||
sort={Bray-Liebhafsky mechanism},
|
||||
user1={Bray-Liebhafsky mechanism},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{BRIGGS-RAUSCHER-MECHANISMg}{
|
||||
text={Briggs-Rauscher mechanism},
|
||||
name={Briggs-Rauscher mechanism},
|
||||
description={Bla bla bla},
|
||||
sort={Briggs-Rauscher mechanism},
|
||||
user1={Briggs-Rauscher mechanism},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
|
||||
\newglossaryentry{LE-CHATELIER-PRINCIPLEg}{
|
||||
text={Le Chatelier's principle},
|
||||
first={Le Chatelier's principle (LCP)},
|
||||
name={Le Chatelier's principle (LCP)},
|
||||
description={Bla bla bla},
|
||||
sort={Le Chatelier's principle},
|
||||
user1={Le Chatelier's principle},
|
||||
type=main,
|
||||
category=main
|
||||
}
|
||||
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@@ -0,0 +1,421 @@
|
||||
%% ------------------------------------------------------------------%
|
||||
%% LANGUAGE, FONT, SIZE, GEOMETRY ENCODINGS
|
||||
|
||||
\usepackage[a4paper,
|
||||
top=2cm,
|
||||
bottom=2cm,
|
||||
left=1.5cm,
|
||||
right=1.5cm,
|
||||
marginparwidth=1.75cm]{geometry} % Geometry
|
||||
|
||||
\usepackage[utf8]{inputenc}
|
||||
\usepackage[T1]{fontenc}
|
||||
\usepackage[english]{babel} % Language
|
||||
\usepackage{csquotes} % Quotation
|
||||
|
||||
\usepackage{fontspec}
|
||||
\usepackage{amsmath}
|
||||
\usepackage{mathtools}
|
||||
\usepackage[colon=literal]{unicode-math}
|
||||
|
||||
% Font Selection
|
||||
\setmainfont{STIX Two Text}
|
||||
\setmathfont{STIX Two Math}
|
||||
|
||||
\usepackage[skip=0pt, indent=15pt]{parskip}
|
||||
\usepackage{enumitem}
|
||||
%\setlength{\columnseprule}{0.5pt}
|
||||
\setlength{\columnsep}{3em}
|
||||
\setlist{leftmargin=1cm}
|
||||
\renewcommand\labelitemi{--}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% GRAPHICS PACKAGES
|
||||
|
||||
% graphics package and graphics paths
|
||||
\usepackage{graphicx}
|
||||
\graphicspath{{../graphics/}{../config/logos/}}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% PACKAGES
|
||||
|
||||
%\usepackage{amsfonts}
|
||||
%\usepackage{amsmath}
|
||||
%\usepackage{amssymb}
|
||||
\usepackage{amsthm}
|
||||
\usepackage{alphalph}
|
||||
\usepackage[toc,page]{appendix}
|
||||
\usepackage[affil-it]{authblk}
|
||||
\usepackage[backend=biber,
|
||||
style=authoryear,
|
||||
citestyle=authoryear,
|
||||
natbib,
|
||||
maxcitenames=1,
|
||||
maxbibnames=99,
|
||||
doi=false,
|
||||
isbn=false,
|
||||
url=false,
|
||||
eprint=false,
|
||||
giveninits=true]{biblatex}
|
||||
\usepackage{blindtext}
|
||||
\usepackage{commath}
|
||||
%\usepackage{dblfnote}
|
||||
\usepackage{dirtree}
|
||||
\usepackage{dirtytalk}
|
||||
|
||||
\usepackage{eso-pic}
|
||||
\usepackage{epstopdf}
|
||||
\epstopdfsetup{outdir=../graphics/}
|
||||
|
||||
\usepackage{etoolbox}
|
||||
\usepackage{fancyhdr}
|
||||
\usepackage{float}
|
||||
\usepackage[record=hybrid, acronym, symbols, automake, indexcrossrefs=true, autoseeindex=true, stylemods={longextra}]{glossaries-extra}
|
||||
\usepackage[colorlinks=true, linktoc=true, allcolors=black]{hyperref} % allcolors=black
|
||||
\usepackage{imakeidx}
|
||||
\usepackage{kantlipsum}
|
||||
\usepackage{lastpage}
|
||||
\usepackage[switch*, modulo]{lineno}
|
||||
\usepackage{mathtools}
|
||||
\usepackage[arrows=pgf-filled, version=4]{mhchem}
|
||||
\usepackage{multicol}
|
||||
\usepackage{nameref}
|
||||
\usepackage{setspace}
|
||||
\usepackage[free-standing-units=true]{siunitx}
|
||||
\usepackage{subcaption}
|
||||
\usepackage{scrwfile}
|
||||
\usepackage{tabularray}
|
||||
\usepackage{tikz}
|
||||
\usepackage{tikz-3dplot}
|
||||
\usepackage[breakable, many]{tcolorbox}
|
||||
\usepackage[titles]{tocloft}
|
||||
\usepackage{verbatim}
|
||||
\usepackage{xcolor}
|
||||
|
||||
% Chemical equations and according setup: Needs to be loaded after \usepackage{mhchem}
|
||||
\usepackage{chemmacros}
|
||||
\chemsetup{
|
||||
formula=mhchem,
|
||||
reactions/tag-open=[R,
|
||||
reactions/tag-close=]
|
||||
}
|
||||
|
||||
\counterwithin{reaction}{section}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% TITLE FORMAT
|
||||
|
||||
% Formatting author and affiliation fonts
|
||||
\renewcommand\Authfont{\Large\normalfont}
|
||||
\renewcommand\Affilfont{\normalsize\normalfont}
|
||||
|
||||
\makeatletter
|
||||
\renewcommand{\maketitle}{
|
||||
\thispagestyle{empty}
|
||||
|
||||
\begin{minipage}[b]{0.3\textwidth}
|
||||
\centering
|
||||
\includegraphics[height=1.5cm]{ETH_Logo.pdf}
|
||||
\end{minipage}
|
||||
\hfill
|
||||
\begin{minipage}[b]{0.3\textwidth}
|
||||
\centering
|
||||
\includegraphics[height=1.5cm]{iac_logo.pdf}
|
||||
\end{minipage}
|
||||
\hfill
|
||||
\begin{minipage}[b]{0.3\textwidth}
|
||||
\centering
|
||||
\includegraphics[height=1.5cm]{PSI_Logo.pdf}
|
||||
\end{minipage}
|
||||
|
||||
\vspace*{6cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\textsc{\@subject}
|
||||
\end{flushleft}
|
||||
|
||||
\vspace*{-0.25cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\LARGE{\scshape{\@title}}
|
||||
\end{flushleft}
|
||||
|
||||
\vspace*{-0.25cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\Large\textsc{\@subtitle}
|
||||
\end{flushleft}
|
||||
|
||||
\vfill
|
||||
|
||||
\begin{flushleft}
|
||||
\large\@author
|
||||
\end{flushleft}
|
||||
|
||||
\vspace*{0.5cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\textnormal{Student-ID: 20-914-180}\\
|
||||
\textnormal{E-Mail: }\href{mailto:datschan@student.ethz.ch}{\small\texttt{datschan@student.ethz.ch}}
|
||||
\end{flushleft}
|
||||
|
||||
\vspace*{0.5cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\normalsize\textbf{Supervised By:}\\
|
||||
|
||||
\vspace*{0.25cm}
|
||||
|
||||
Prof. Dr. Markus Ammann\textsuperscript{2}\\
|
||||
Nicole Carina Leemann\textsuperscript{2}\\
|
||||
|
||||
\vspace*{0.25cm}
|
||||
|
||||
\normalsize\normalfont{\textsuperscript{2}Laboratory of Atmospheric Chemistry,\linebreak{Paul Scherrer Institut PSI}}
|
||||
\end{flushleft}
|
||||
|
||||
\vspace*{0.5cm}
|
||||
|
||||
\begin{flushleft}
|
||||
\Large\@date
|
||||
\end{flushleft}
|
||||
|
||||
\pagebreak
|
||||
|
||||
}\makeatother
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% FORMATTING
|
||||
|
||||
% Line Spacing
|
||||
\renewcommand{\baselinestretch}{1.0}
|
||||
|
||||
% Numbering
|
||||
\makeatletter
|
||||
\newcommand{\@alphalph}{}
|
||||
\let\@alphalph=\alphalph
|
||||
\makeatother
|
||||
\allowdisplaybreaks
|
||||
|
||||
% Tabularray Setup
|
||||
\UseTblrLibrary{booktabs}
|
||||
\DefTblrTemplate{caption-tag}{default}{\small\bfseries\scshape{Table \thetable}}
|
||||
\DefTblrTemplate{caption-text}{default}{\small\InsertTblrText{caption}}
|
||||
\DefTblrTemplate{caption-sep}{default}{\small\bfseries{:}\enskip}
|
||||
\SetTblrStyle{foot}{font={\normalfont\small}}
|
||||
\renewcommand\TblrOverlap[1]{#1}
|
||||
%\setlength{\DTbaselineskip}{}
|
||||
\SetTblrStyle{conthead-text}{font={\normalfont\small}}
|
||||
|
||||
% Section Title Formatting
|
||||
\setkomafont{chapter}{\normalfont\Large\bfseries}
|
||||
\setkomafont{section}{\normalfont\large\bfseries}
|
||||
\setkomafont{subsection}{\normalfont\normalsize\bfseries}
|
||||
\setkomafont{subsubsection}{\normalfont\normalsize\bfseries}
|
||||
\setkomafont{captionlabel}{\normalfont\small\bfseries\scshape}
|
||||
\setkomafont{caption}{\normalfont\small}
|
||||
\renewcaptionname{english}{\figurename}{Figure }
|
||||
\renewcaptionname{english}{\tablename}{Table }
|
||||
\patchcmd{\chapter}{\thispagestyle{plain}}{\thispagestyle{proposal}}{}{}
|
||||
|
||||
% Formatting for TOC
|
||||
\addtokomafont{chapterentry}{\normalfont\bfseries}
|
||||
|
||||
|
||||
% Roman Numbers
|
||||
\newcommand{\toRoman}[1]{\MakeUppercase{\romannumeral #1}}
|
||||
|
||||
% SI unit and SI settings (siunitx)
|
||||
\DeclareSIUnit\amu{u}
|
||||
\DeclareSIUnit\bar{bar}
|
||||
\DeclareSIUnit\year{yr}
|
||||
\DeclareSIUnit\month{m}
|
||||
\DeclareSIUnit\week{w}
|
||||
\DeclareSIUnit\day{d}
|
||||
\DeclareSIUnit\ppm{ppm}
|
||||
\DeclareSIUnit\ppt{ppt}
|
||||
\DeclareSIUnit\pptv{pptv}
|
||||
\DeclareSIUnit\atm{atm}
|
||||
\DeclareSIUnit\Molar{M}
|
||||
\DeclareSIUnit\gramCarbon{g\ce{C}}
|
||||
\DeclareSIUnit\permille{\text{\textperthousand}}
|
||||
\sisetup{separate-uncertainty, multi-part-units=single, range-units=single, range-phrase=\ensuremath{\ldots}}
|
||||
|
||||
% Bibliogrpahy Format
|
||||
\AtBeginBibliography{\small}
|
||||
\AtEveryBibitem{\clearfield{note}}
|
||||
|
||||
% Header and Footer Setup
|
||||
\fancypagestyle{mainbody}{
|
||||
\fancyhead[RO, LE]{D. Tschan}
|
||||
\fancyhead[LO, RE]{\textit\leftmark}
|
||||
\fancyfoot[RO, LE]{\thepage\text{ of }\pageref{LastPage}}
|
||||
\fancyfoot[CO, CE]{}
|
||||
\fancyfoot[LO, RE]{\textit\rightmark}
|
||||
}
|
||||
|
||||
\fancypagestyle{proposal}{
|
||||
\fancyhead[RO, LE]{D. Tschan}
|
||||
\fancyhead[LO, RE]{D-USYS Master Thesis Proposal}
|
||||
\fancyfoot[RO, LE]{\thepage\text{ of }\pageref{LastPage}}
|
||||
\fancyfoot[CO, CE]{}
|
||||
\fancyfoot[LO, RE]{\textit\leftmark}
|
||||
}
|
||||
|
||||
% Dirtree Setup
|
||||
\newcommand\mydirtree[1]{{\ttfamily\small\dirtree{#1}\par}}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% GLOSSARIES SETUP
|
||||
|
||||
% Create new glossary type
|
||||
\newglossary*{species}{species}
|
||||
|
||||
% Compile the glossaries
|
||||
\makeglossaries
|
||||
\makeindex[options=-s ../main/index.ist, name=main, intoc, columns=3]
|
||||
|
||||
% Also adds the actual entry in the glossary to the index
|
||||
\glssetcategoryattribute{main}{indexname}{textbf}
|
||||
\glssetcategoryattribute{main}{dualindex}{true}
|
||||
|
||||
% Formatting command...
|
||||
\GlsXtrEnableIndexFormatOverride
|
||||
|
||||
% Prevents character escaping
|
||||
\renewcommand*{\glsxtrautoindexesc}{}
|
||||
|
||||
% Sets the correct sorting in the index
|
||||
\renewcommand*{\glsxtrautoindexentry}[1]{\string\glsentryuseri{#1}}
|
||||
\renewcommand*{\glsxtrautoindexassignsort}[2]{%
|
||||
\glsletentryfield{#1}{#2}{user1}%
|
||||
}
|
||||
|
||||
% Sets the correct sorting in the index
|
||||
\renewcommand*{\glsxtrautoindexassignsort}[2]{%
|
||||
\ifglshasshort{#2}%
|
||||
{\glsletentryfield{#1}{#2}{sort}}%
|
||||
{\glsletentryfield{#1}{#2}{sort}}%
|
||||
}
|
||||
|
||||
\indexsetup{firstpagestyle=mainbody}
|
||||
|
||||
%% SYMBOLS
|
||||
|
||||
% Add glossary key 'unit' and 'formula'
|
||||
\glsaddkey{unit}{}{\glsentryunit}{\Glsentryunit}{\glsunit}{\Glsunit}{\GLSunit}
|
||||
\glsxtrprovidestoragekey{formula}{}{\Formula}
|
||||
|
||||
\GlsXtrLoadResources[
|
||||
src={../config/symbols}, % data in symbols.bib
|
||||
sort-field={desc}, % sort by name field
|
||||
sort={letter-nocase}, % case-insensitive letter sort
|
||||
type=symbols, % put these terms in the symbols list
|
||||
field-aliases={unit=symbol}, % convert unit key to symbol
|
||||
save-locations=false % don't save location lists
|
||||
]
|
||||
|
||||
%% CHEMICAL SPECIES
|
||||
|
||||
% \glsaddkey{formula}{}{\glsentryformula}{\Glsentryformula}{\glsformula}{\Glsformula}{\GLSformula}
|
||||
|
||||
\GlsXtrLoadResources[
|
||||
src={../config/species}, % data in symbols.bib
|
||||
sort-field={desc}, % sort by name field
|
||||
sort={letter-nocase}, % case-insensitive letter sort
|
||||
type=species, % put these terms in the symbols list
|
||||
field-aliases={formula=symbol}, % convert unit key to symbol
|
||||
save-locations=false % don't save location lists
|
||||
]
|
||||
|
||||
|
||||
% Enable hyperlinks for glossary
|
||||
\glsenablehyper
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% THEOREMS AND ENVIRONMENTS
|
||||
|
||||
% General modifications
|
||||
|
||||
\renewcommand{\qedsymbol}{\ensuremath{\blacksquare}}
|
||||
|
||||
% Color definitions
|
||||
|
||||
\definecolor{color_box}{HTML}{EEEEEE}
|
||||
\definecolor{color_box_lower}{HTML}{DDDDDD}
|
||||
\definecolor{definition_color_title}{HTML}{C63B3B}
|
||||
\definecolor{example_color_title}{HTML}{005B2F}
|
||||
\definecolor{theorem_color_title}{HTML}{AD4CBB}
|
||||
\definecolor{law_color_title}{HTML}{4C84BB}
|
||||
|
||||
% Definitions
|
||||
|
||||
\newcounter{def_custom}
|
||||
\newtcolorbox[use counter=def_custom,
|
||||
number within=section]
|
||||
{definition_custom}[2]{
|
||||
skin=bicolor,
|
||||
breakable=true,
|
||||
arc=0mm,
|
||||
boxrule=0pt,
|
||||
colback=color_box,
|
||||
colframe=definition_color_title,
|
||||
label={#2},
|
||||
title={\textcolor{white}{Definition~\thetcbcounter:\enskip\bfseries\itshape{#1}}},
|
||||
segmentation style={draw=none},
|
||||
colbacklower=color_box_lower
|
||||
}
|
||||
|
||||
% Examples
|
||||
|
||||
\newcounter{example_custom}
|
||||
\newtcolorbox[use counter=example_custom,
|
||||
number within=section]
|
||||
{example_custom}[2]{
|
||||
skin=bicolor,
|
||||
breakable=true,
|
||||
arc=0mm,
|
||||
boxrule=0pt,
|
||||
colback=color_box,
|
||||
colframe=example_color_title,
|
||||
label={#2},
|
||||
title={\textcolor{white}{Example~\thetcbcounter:\enskip\bfseries\itshape{#1}}},
|
||||
segmentation style={draw=none},
|
||||
colbacklower=color_box_lower
|
||||
}
|
||||
|
||||
% theorems
|
||||
|
||||
\newcounter{theorem_custom}
|
||||
\newtcolorbox[use counter=theorem_custom,
|
||||
number within=section]
|
||||
{theorem_custom}[2]{
|
||||
skin=bicolor,
|
||||
breakable=true,
|
||||
arc=0mm,
|
||||
boxrule=0pt,
|
||||
colback=color_box,
|
||||
colframe=theorem_color_title,
|
||||
label={#2},
|
||||
title={\textcolor{white}{Theorem~\thetcbcounter:\enskip\bfseries\itshape{#1}}},
|
||||
segmentation style={draw=none},
|
||||
colbacklower=color_box_lower
|
||||
}
|
||||
|
||||
% Law
|
||||
|
||||
\newcounter{law_custom}
|
||||
\newtcolorbox[use counter=law_custom,
|
||||
number within=section]
|
||||
{law_custom}[2]{
|
||||
skin=bicolor,
|
||||
breakable=true,
|
||||
arc=0mm,
|
||||
boxrule=0pt,
|
||||
colback=color_box,
|
||||
colframe=law_color_title,
|
||||
label={#2},
|
||||
title={\textcolor{white}{Law~\thetcbcounter:\enskip\bfseries\itshape{#1}}},
|
||||
segmentation style={draw=none},
|
||||
colbacklower=color_box_lower
|
||||
}
|
||||
@@ -0,0 +1,481 @@
|
||||
%% DEFINE THE SPECIES TO BE USED
|
||||
|
||||
% Compile via PDFLaTeX -> Bib2Gls (User) -> PDFLaTeX
|
||||
% 'formula' field is accessed via \glssymbol{...}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
|
||||
@entry{I2f,
|
||||
name={Molecular iodine},
|
||||
text={molecular iodine},
|
||||
formula={\ensuremath{\ce{I2}}},
|
||||
description={},
|
||||
first={molecular iodine (\ensuremath{\ce{I2}})}
|
||||
}
|
||||
|
||||
@entry{I-f,
|
||||
name={Iodide},
|
||||
text={iodide},
|
||||
formula={\ensuremath{\ce{I-}}},
|
||||
description={},
|
||||
first={iodide (\ensuremath{\ce{I-}})}
|
||||
}
|
||||
|
||||
@entry{I3-f,
|
||||
name={Triiodide},
|
||||
text={triiodide},
|
||||
formula={\ensuremath{\ce{I3-}}},
|
||||
description={},
|
||||
first={triiodide (\ensuremath{\ce{I3-}})}
|
||||
}
|
||||
|
||||
@entry{IO3-f,
|
||||
name={Iodate},
|
||||
text={iodate},
|
||||
formula={\ensuremath{\ce{IO3-}}},
|
||||
description={},
|
||||
first={iodate (\ensuremath{\ce{IO3-}})}
|
||||
}
|
||||
|
||||
@entry{O3f,
|
||||
name={Ozone},
|
||||
text={ozone},
|
||||
formula={\ensuremath{\ce{O3}}},
|
||||
description={},
|
||||
first={ozone (\ensuremath{\ce{O3}})}
|
||||
}
|
||||
|
||||
@entry{I.f,
|
||||
name={Iodine radical},
|
||||
text={iodine radical},
|
||||
plural={iodine radicals},
|
||||
formula={\ensuremath{\ce{I}^{\bullet}}},
|
||||
description={},
|
||||
first={iodine radical (\ensuremath{\ce{I}^{\bullet}})},
|
||||
firstplural={iodine radicals (\ensuremath{\ce{I}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{IO.f,
|
||||
name={Iodine monoxide radical},
|
||||
text={iodine monoxide radical},
|
||||
plural={iodine monoxide radicals},
|
||||
formula={\ensuremath{\ce{IO}^{\bullet}}},
|
||||
description={},
|
||||
first={iodine monoxide radical (\ensuremath{\ce{IO}^{\bullet}})},
|
||||
firstplural={iodine monoxide radicals (\ensuremath{\ce{IO}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{IO-f,
|
||||
name={Iodine oxide ion},
|
||||
text={iodine oxide ion},
|
||||
formula={\ensuremath{\ce{IO-}}},
|
||||
description={},
|
||||
first={iodine oxide ion (\ensuremath{\ce{IO-}})},
|
||||
firstplural={iodine oxide ions (\ensuremath{\ce{IO-}})}
|
||||
}
|
||||
|
||||
@entry{IO2f,
|
||||
name={Iodine dioxide},
|
||||
text={iodine dioxide},
|
||||
formula={\ensuremath{\ce{IO2}}},
|
||||
description={},
|
||||
first={iodine dioxide (\ensuremath{\ce{IO2}})},
|
||||
firstplural={iodine dioxides (\ensuremath{\ce{IO2}})}
|
||||
}
|
||||
|
||||
@entry{OIO.f,
|
||||
name={Iodine dioxide radical},
|
||||
text={iodine dioxide radical},
|
||||
formula={\ensuremath{\ce{OIO}^{\bullet}}},
|
||||
description={},
|
||||
first={iodine dioxide radical (\ensuremath{\ce{OIO}^{\bullet}})},
|
||||
firstplural={iodine dioxide radicals (\ensuremath{\ce{OIO}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{IOOO-f,
|
||||
name={Iodine trioxide ion},
|
||||
text={iodine trioxide ion},
|
||||
formula={\ensuremath{\ce{IOOO-}}},
|
||||
description={},
|
||||
first={iodine trioxide ion (\ensuremath{\ce{IOOO-}})},
|
||||
firstplural={iodine trioxide ions (\ensuremath{\ce{IOOO-}})}
|
||||
}
|
||||
|
||||
@entry{I2O2f,
|
||||
name={Diiodine dioxide},
|
||||
text={diiodine dioxide},
|
||||
formula={\ensuremath{\ce{I2O2}}},
|
||||
description={},
|
||||
first={diiodine dioxide (\ensuremath{\ce{I2O2}})},
|
||||
firstplural={diiodine dioxides (\ensuremath{\ce{I2O2}})}
|
||||
}
|
||||
|
||||
@entry{I2O3f,
|
||||
name={Diiodine trioxide},
|
||||
text={diiodine trioxide},
|
||||
formula={\ensuremath{\ce{I2O3}}},
|
||||
description={},
|
||||
first={diiodine trioxide (\ensuremath{\ce{I2O3}})},
|
||||
firstplural={diiodine trioxides (\ensuremath{\ce{I2O3}})}
|
||||
}
|
||||
|
||||
@entry{I2O4f,
|
||||
name={Diiodine tetroxide},
|
||||
text={diiodine tetroxide},
|
||||
formula={\ensuremath{\ce{I2O4}}},
|
||||
description={},
|
||||
first={diiodine tetrooxide (\ensuremath{\ce{I2O4}})},
|
||||
firstplural={diiodine tetroxides (\ensuremath{\ce{I2O4}})}
|
||||
}
|
||||
|
||||
@entry{I2O5f,
|
||||
name={Diiodine pentoxide},
|
||||
text={diiodine pentoxide},
|
||||
formula={\ensuremath{\ce{I2O5}}},
|
||||
description={},
|
||||
first={diiodine pentoxide (\ensuremath{\ce{I2O5}})},
|
||||
firstplural={diiodine pentoxides (\ensuremath{\ce{I2O5}})}
|
||||
}
|
||||
|
||||
@entry{IClf,
|
||||
name={Iodine chloride},
|
||||
text={iodine chloride},
|
||||
formula={\ensuremath{\ce{ICl}}},
|
||||
description={},
|
||||
first={iodine chloride (\ensuremath{\ce{ICl}})},
|
||||
firstplural={iodine chlorides (\ensuremath{\ce{ICl}})}
|
||||
}
|
||||
|
||||
|
||||
@entry{IBrf,
|
||||
name={Iodine bromide},
|
||||
text={iodine bromide},
|
||||
formula={\ensuremath{\ce{IBr}}},
|
||||
description={},
|
||||
first={Iodine bromide (\ensuremath{\ce{IBr}})},
|
||||
firstplural={iodine bromides (\ensuremath{\ce{IBr}})}
|
||||
}
|
||||
|
||||
@entry{Br-f,
|
||||
name={Bromide},
|
||||
text={bromide},
|
||||
formula={\ensuremath{\ce{Br-}}},
|
||||
description={},
|
||||
first={bromide (\ensuremath{\ce{Br-}})}
|
||||
}
|
||||
|
||||
@entry{IOClOf,
|
||||
name={Iodine chlorine dioxide},
|
||||
text={iodine chloride dioxide},
|
||||
formula={\ensuremath{\ce{IOClO}}},
|
||||
description={},
|
||||
first={iodine chlorine dioxide (\ensuremath{\ce{IOClO}})},
|
||||
firstplural={iodine chlorine dioxides (\ensuremath{\ce{IOClO}})}
|
||||
}
|
||||
|
||||
@entry{IOBrOf,
|
||||
name={Iodine bromine dioxide},
|
||||
text={iodine bromine dioxide},
|
||||
formula={\ensuremath{\ce{IOBrO}}},
|
||||
description={},
|
||||
first={iodine bromine dioxide (\ensuremath{\ce{IOBrO}})},
|
||||
firstplural={iodine bromine dioxides (\ensuremath{\ce{IOBrO}})}
|
||||
}
|
||||
|
||||
@entry{HOIf,
|
||||
name={Hypoiodous acid},
|
||||
text={hypoiodous acid},
|
||||
formula={\ensuremath{\ce{HOI}}},
|
||||
description={},
|
||||
first={hypoiodous acid (\ensuremath{\ce{HOI}})},
|
||||
firstplural={hypoiodous acids (\ensuremath{\ce{HOI}})}
|
||||
}
|
||||
|
||||
@entry{IONO2f,
|
||||
name={Iodine oxygen nitrite},
|
||||
text={iodine oxygen nitrite},
|
||||
formula={\ensuremath{\ce{IONO2}}},
|
||||
description={},
|
||||
first={iodine oxygen nitrite (\ensuremath{\ce{IONO2}})},
|
||||
firstplural={iodine oxygen nitrites (\ensuremath{\ce{IONO2}})}
|
||||
}
|
||||
|
||||
@entry{INO2f,
|
||||
name={Iodine nitrite},
|
||||
text={iodine nitrite},
|
||||
formula={\ensuremath{\ce{INO2}}},
|
||||
description={},
|
||||
first={iodine nitrite (\ensuremath{\ce{INO2}})},
|
||||
firstplural={iodine nitrites (\ensuremath{\ce{INO2}})}
|
||||
}
|
||||
|
||||
@entry{CO2f,
|
||||
name={Carbon dioxide},
|
||||
text={carbon dioxide},
|
||||
formula={\ensuremath{\ce{CO2}}},
|
||||
description={},
|
||||
first={carbon dioxide (\ensuremath{\ce{CO2}})},
|
||||
firstplural={carbon dioxides (\ensuremath{\ce{CO2}})}
|
||||
}
|
||||
|
||||
@entry{COf,
|
||||
name={Carbon monoxide},
|
||||
text={carbon monoxide},
|
||||
formula={\ensuremath{\ce{CO}}},
|
||||
description={},
|
||||
first={carbon monoxide (\ensuremath{\ce{CO}})},
|
||||
firstplural={carbon monoxide (\ensuremath{\ce{CO}})}
|
||||
}
|
||||
|
||||
@entry{NO2f,
|
||||
name={Nitrogen dioxide},
|
||||
text={nitrogen dioxide},
|
||||
formula={\ensuremath{\ce{NO2}}},
|
||||
description={},
|
||||
first={nitrogen dioxide (\ensuremath{\ce{NO2}})},
|
||||
firstplural={nitrogen dioxides (\ensuremath{\ce{NO2}})}
|
||||
}
|
||||
|
||||
@entry{NO3.f,
|
||||
name={Nitrogen trioxide radical},
|
||||
text={nitrogen trioxide radical},
|
||||
plural={nitrogen trioxide radicals},
|
||||
formula={\ensuremath{\ce{NO3}^{\bullet}}},
|
||||
description={},
|
||||
first={nitrogen troxide radical (\ensuremath{\ce{NO3}^{\bullet}})},
|
||||
firstplural={nitrogen trioxide radical (\ensuremath{\ce{NO3}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{NOf,
|
||||
name={Nitrogen monoxide},
|
||||
text={nitrogen monoxide},
|
||||
formula={\ensuremath{\ce{NO}}},
|
||||
description={},
|
||||
first={nitrogen monoxide (\ensuremath{\ce{NO}})},
|
||||
firstplural={nirogen monoxides (\ensuremath{\ce{NO}})}
|
||||
}
|
||||
|
||||
@entry{NOxf,
|
||||
name={Nitrous oxide},
|
||||
text={nitrous oxide},
|
||||
formula={\ensuremath{\ce{NO}_{x}}},
|
||||
description={Chemical family: \ensuremath{\ce{NO}_{x}\coloneqq\glssymbol{NO2f}+\glssymbol{NOf}}},
|
||||
first={nitrous oxide (\ensuremath{\ce{NO}_{x}})},
|
||||
firstplural={nitrous oxides (\ensuremath{\ce{NO}_{x}})}
|
||||
}
|
||||
|
||||
@entry{HO2.f,
|
||||
name={Peroxide radical},
|
||||
text={peroxide radical},
|
||||
plural={peroxide radicals},
|
||||
formula={\ensuremath{\ce{HO2}^{\bullet}}},
|
||||
description={},
|
||||
first={peroxide radical (\ensuremath{\ce{HO2}^{\bullet}})},
|
||||
firstplural={peroxide radicals (\ensuremath{\ce{HO2}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{HO2-f,
|
||||
name={Peroxide ion},
|
||||
text={peroxide ion},
|
||||
formula={\ensuremath{\ce{HO2-}}},
|
||||
description={},
|
||||
first={peroxide ion (\ensuremath{\ce{HO2-}})},
|
||||
firstplural={peroxide ions (\ensuremath{\ce{HO2-}})}
|
||||
}
|
||||
|
||||
@entry{HO2.-f,
|
||||
name={Peroxide ion radical},
|
||||
text={peroxide ion radical},
|
||||
plural={peroxide ion radicals},
|
||||
formula={\ensuremath{\ce{HO2}^{\bullet-}}},
|
||||
description={},
|
||||
first={peroxide ion radical (\ensuremath{\ce{HO2}^{\bullet-}})},
|
||||
firstplural={peroxide ion radicals (\ensuremath{\ce{HO2}^{\bullet-}})}
|
||||
}
|
||||
|
||||
@entry{OH.f,
|
||||
name={Hydroxyl radical},
|
||||
text={hydroxyl radical},
|
||||
plural={hydroxyl radicals},
|
||||
sort={hydroxyl radical},
|
||||
formula={\ensuremath{\ce{HO}^{\bullet}}},
|
||||
description={},
|
||||
first={hydroxyl radical (\ensuremath{\ce{HO}^{\bullet}})},
|
||||
firstplural={hydroxyl radicals (\ensuremath{\ce{HO}^{\bullet}})}
|
||||
}
|
||||
|
||||
@entry{OH-f,
|
||||
name={Hydroxyl ion},
|
||||
text={hydroxyl ion},
|
||||
sort={hydroxyl ion},
|
||||
formula={\ensuremath{\ce{OH-}}},
|
||||
description={},
|
||||
first={hydroxyl ion (\ensuremath{\ce{HO-}})},
|
||||
firstplural={hydroxyl ions (\ensuremath{\ce{HO-}})}
|
||||
}
|
||||
|
||||
@entry{HOxf,
|
||||
name={Hydrogen oxide radical},
|
||||
text={hydrogen oxide radical},
|
||||
text={hydrogen oxide radical},
|
||||
formula={\ensuremath{\ce{HO}_{x}}},
|
||||
description={Chemical family: \ensuremath{\ce{HO}_{x}\coloneqq\glssymbol{HO2.f}+\glssymbol{OH.f}}},
|
||||
first={hydrogen oxide radical (\ensuremath{\ce{HO}_{x}})},
|
||||
firstplural={hydrogen oxide radicals (\ensuremath{\ce{HO}_{x}})},
|
||||
plural={hydrogen oxide radicals (\ensuremath{\ce{HO}_{x}})}
|
||||
}
|
||||
|
||||
@entry{H2O2f,
|
||||
name={Hydrogen peroxide},
|
||||
text={hydrogen peroxide},
|
||||
formula={\ensuremath{\ce{H2O2}}},
|
||||
description={},
|
||||
first={hydrogen peroxide (\ensuremath{\ce{H2O2}})},
|
||||
firstplural={hydrogen peroxides (\ensuremath{\ce{H2O2}})}
|
||||
}
|
||||
|
||||
@entry{H2Of,
|
||||
name={Water (dihydrogen oxide)},
|
||||
text={water},
|
||||
sort={dihydrogen oxide},
|
||||
formula={\ensuremath{\ce{H2O}}},
|
||||
description={},
|
||||
first={water (\ensuremath{\ce{H2O}})},
|
||||
firstplural={waters (\ensuremath{\ce{H2O}})}
|
||||
}
|
||||
|
||||
@entry{NaIO3f,
|
||||
name={Sodium iodate},
|
||||
text={sodium iodate},
|
||||
formula={\ensuremath{\ce{NaIO3}}},
|
||||
description={},
|
||||
first={sodium iodate (\ensuremath{\ce{NaIO3}})}
|
||||
}
|
||||
|
||||
@entry{ABSf,
|
||||
name={Ammonium Bisulfate},
|
||||
text={ammonium bisulfate},
|
||||
formula={\ensuremath{\ce{(NH4)HSO4}}},
|
||||
description={(ABS)},
|
||||
first={}
|
||||
}
|
||||
|
||||
@entry{Fe2O3f,
|
||||
name={Iron(\toRoman{3}) oxide},
|
||||
text={iron(\toRoman{3}) oxide},
|
||||
formula={\ensuremath{\ce{Fe2O3}}},
|
||||
description={When occuring as a bulk crystal, this mineral is referred to as hematite.},
|
||||
first={hematite (iron(\toRoman{3}) oxide) (\ensuremath{\ce{Fe2O3}})}
|
||||
}
|
||||
|
||||
@entry{O2f,
|
||||
name={Molecular oxygen},
|
||||
text={molecular oxygen},
|
||||
formula={\ensuremath{\ce{O2}}},
|
||||
description={},
|
||||
sort={oxygen}
|
||||
}
|
||||
|
||||
@entry{O2-.f,
|
||||
name={Superoxide ion radical},
|
||||
text={superoxide ion radical},
|
||||
plural={superoxide ion radicals},
|
||||
formula={\ensuremath{\ce{O2}^{\bullet-}}},
|
||||
first={superoxide ion radical (\ensuremath{\ce{O2}^{\bullet-}})},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{O-3P.f,
|
||||
name={Oxygen radical (triplet-P)},
|
||||
text={oxygen radical (triplet-P)},
|
||||
plural={oxygen radicals (triplet-P)},
|
||||
formula={\ensuremath{^{\bullet}\ce{O}(^{3}\textnormal{P})}},
|
||||
first={oxygen radical (triplet-P)},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{O-1D.f,
|
||||
name={Oxygen radical (singlet-D)},
|
||||
text={oxygen radical (singlet-D)},
|
||||
plural={oxygen radicals (singlet-D)},
|
||||
formula={\ensuremath{^{\bullet}\ce{O}(^{1}D)}},
|
||||
first={oxygen radical (singlet-D) (\ensuremath{^{\bullet}\ce{O}(^{1}D)})},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{H+f,
|
||||
name={Hydrogen ion},
|
||||
text={hydrogen ion},
|
||||
formula={\ensuremath{\ce{H+}}},
|
||||
first={hydrogen ion (\ensuremath{\ce{H+}})},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{RInf,
|
||||
name={\gls{VOICa}},
|
||||
text={\gls{VOICa}},
|
||||
plural={\glspl{VOICa}},
|
||||
formula={\ensuremath{\RI{n}}},
|
||||
first={\gls{VOICa} (\ensuremath{\RI{n}})},
|
||||
firstplural={\glspl{VOICa} (\ensuremath{\RI{n}})},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{CH3If,
|
||||
name={Methyl iodide},
|
||||
text={methly iodide},
|
||||
formula={\ensuremath{\ce{CH3I}}},
|
||||
first={(\ensuremath{\ce{CH3I}})},
|
||||
description={}
|
||||
}
|
||||
|
||||
@entry{Iyf,
|
||||
name={Total inorganic iodine},
|
||||
text={total inorganic iodine},
|
||||
formula={\ensuremath{\ce{I}_{y}}},
|
||||
first={total inorganic iodine (\ensuremath{\ce{I}_{y}})},
|
||||
description={Chemical family: \ensuremath{\ce{I}_{y}\coloneqq\glssymbol{I.f}+\glssymbol{IO.f}+\glssymbol{IO2f}+\glssymbol{HOIf}+\ce{HI}+\ce{INO}+\ce{INO2}+\glssymbol{IONO2f}+2\glssymbol{I2f}+\ce{ICl}+\ce{IBr}+2\ce{I2O2}+2\ce{I2O3}+2\ce{I2O4}}}
|
||||
}
|
||||
|
||||
@entry{Ix.f,
|
||||
name={Iodine radical species},
|
||||
text={iodine radical species},
|
||||
formula={\ensuremath{\ce{I}_{x}}},
|
||||
first={iodine radical species (\ensuremath{\ce{I}_{x}})},
|
||||
description={Chemical family: \ensuremath{\ce{I}_{x}\coloneqq\glssymbol{I.f}+\glssymbol{IO.f}}}
|
||||
}
|
||||
|
||||
@entry{ISOPRENEf,
|
||||
name={isoprene},
|
||||
text={isoprene},
|
||||
formula={\ensuremath{\ce{C5H8}}},
|
||||
first={isoprene (2-metyhl-1,3-butadiene) (\ensuremath{\ce{CH2=C(CH3)-CH=CH2}})},
|
||||
description={2-metyhl-1,3-butadiene}
|
||||
}
|
||||
|
||||
@entry{A-PINENEf,
|
||||
name={\ensuremath{\alpha}-pinene},
|
||||
text={\ensuremath{\alpha}-pinene},
|
||||
formula={\ensuremath{\ce{C10H16}}},
|
||||
first={\ensuremath{\alpha}-pinene (2,6,6-trimethylbicyclo[3.1.1]hept-2-ene)},
|
||||
description={2,6,6-trimethylbicyclo[3.1.1]hept-2-ene. Two enantiomers exist.}
|
||||
}
|
||||
|
||||
@entry{B-PINENEf,
|
||||
name={\ensuremath{\beta}-pinene},
|
||||
text={\ensuremath{\beta}-pinene},
|
||||
formula={\ensuremath{\ce{C10H16}}},
|
||||
first={\ensuremath{\beta}-pinene (6,6-dimethyl-2-methylidenebicyclo[3.1.1]heptane)},
|
||||
description={6,6-dimethyl-2-methylidenebicyclo[3.1.1]heptane}
|
||||
}
|
||||
|
||||
@entry{LIMONENEf,
|
||||
name={Limonene},
|
||||
text={limonene},
|
||||
formula={\ensuremath{\ce{C10H16}}},
|
||||
first={limonene (1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene)},
|
||||
description={1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene}
|
||||
}
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
@@ -0,0 +1,58 @@
|
||||
%% DEFINE THE SYMBOLS TO BE USED
|
||||
|
||||
% Compile via PDFLaTeX -> Bib2Gls (User) -> PDFLaTeX
|
||||
% 'unit' field is accessed via \glssymbol{...}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
|
||||
@symbol{RHs,
|
||||
unit={\qty{}{\percent}},
|
||||
name={\ensuremath{\varphi}},
|
||||
description={Water content of gas relative to saturation water content, a function of temperature and pressure.},
|
||||
set-widest=True
|
||||
}
|
||||
|
||||
% atmospheric mixing ratio
|
||||
@symbol{CHIs,
|
||||
unit={\qty{}{\pptv}},
|
||||
name={\ensuremath{\chi}},
|
||||
description={atmospheric mixing ratio},
|
||||
}
|
||||
|
||||
@symbol{ALWs,
|
||||
unit={\qty{}{\liter\per\cubic\meter}},
|
||||
name={\ensuremath{\omega_{\textnormal{ALW}}}},
|
||||
description={\Glsfirst{ALWa}: the volume of liquid water in aerosol phase per volume of air.}
|
||||
}
|
||||
|
||||
@symbol{TAUs,
|
||||
unit={\qty{}{\second}},
|
||||
name={\ensuremath{\tau}},
|
||||
description={Chemical lifetime.}
|
||||
}
|
||||
|
||||
@symbol{pHs,
|
||||
unit={},
|
||||
name={\ensuremath{\textnormal{pH}}},
|
||||
description={Measure of acidity of a solution: \ensuremath{\textnormal{pH}\coloneqq-\log_{10}\left[\ce{H+(aq)}\right]}}
|
||||
}
|
||||
|
||||
@symbol{ABS-TEMPs,
|
||||
unit={\qty{}{\kelvin}},
|
||||
name={\ensuremath{\textnormal{T}}},
|
||||
description={Absolute thermodynamic temperature}
|
||||
}
|
||||
|
||||
@symbol{REL-TEMPs,
|
||||
unit={\qty{}{\degreeCelsius}},
|
||||
name={\ensuremath{\vartheta}},
|
||||
description={Relative temperature}
|
||||
}
|
||||
|
||||
@symbol{LAMBDAs,
|
||||
unit={\qty{}{\nano\meter}},
|
||||
name={\ensuremath{\lambda}},
|
||||
description={Wavelength}
|
||||
}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
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|
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|
||||
% !TeX program = lualatex
|
||||
|
||||
\documentclass[10pt]{scrreprt}
|
||||
\usepackage[utf8]{inputenc}
|
||||
\usepackage[T1]{fontenc}
|
||||
\usepackage[english]{babel} % Language
|
||||
\usepackage{csquotes} % Quotation
|
||||
\usepackage{fontspec}
|
||||
\usepackage{amsmath}
|
||||
\usepackage{accents}
|
||||
\usepackage{mathtools}
|
||||
\usepackage[colon=literal]{unicode-math}
|
||||
\setmainfont{STIX}
|
||||
\setmathfont{STIX Two Math}
|
||||
\usepackage{graphicx}
|
||||
\usepackage{alphalph}
|
||||
\usepackage{commath}
|
||||
\usepackage{mathtools}
|
||||
\usepackage[arrows=pgf-filled, version=4]{mhchem}
|
||||
\usepackage[free-standing-units=true]{siunitx}
|
||||
\usepackage{xcolor}
|
||||
|
||||
% Roman Numbers
|
||||
\newcommand{\toRoman}[1]{\MakeUppercase{\romannumeral #1}}
|
||||
|
||||
% SI unit and SI settings (siunitx)
|
||||
\DeclareSIUnit\amu{u}
|
||||
\DeclareSIUnit\bar{bar}
|
||||
\DeclareSIUnit\year{yr}
|
||||
\DeclareSIUnit\month{m}
|
||||
\DeclareSIUnit\week{w}
|
||||
\DeclareSIUnit\day{d}
|
||||
\DeclareSIUnit\ppm{ppm}
|
||||
\DeclareSIUnit\ppt{ppt}
|
||||
\DeclareSIUnit\pptv{pptv}
|
||||
\DeclareSIUnit\atm{atm}
|
||||
\DeclareSIUnit\Molar{M}
|
||||
\DeclareSIUnit\gramCarbon{g\ce{C}}
|
||||
\DeclareSIUnit\permille{\text{\textperthousand}}
|
||||
\sisetup{separate-uncertainty, multi-part-units=single, range-units=single, range-phrase=\ensuremath{\ldots}}
|
||||
|
||||
|
||||
\newcommand{\der}[1]{\ensuremath{\textnormal{d}\,{#1}}}
|
||||
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|
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|
After Width: | Height: | Size: 741 KiB |
Whitespace-only changes.
@@ -0,0 +1,6 @@
|
||||
headings_flag 1
|
||||
heading_prefix "{\\bfseries "
|
||||
heading_suffix "}\\nopagebreak\n"
|
||||
delim_0 " \\dotfill "
|
||||
delim_1 " \\dotfill "
|
||||
delim_2 " \\dotfill "
|
||||
@@ -0,0 +1 @@
|
||||
\glossaryentry{PP?\glossentry{PP}|setentrycounter[]{page}"\glsnumberformat}{4}
|
||||
@@ -0,0 +1,29 @@
|
||||
% makeindex style file created by the glossaries package
|
||||
% for document 'main' on 2026-8-10
|
||||
actual '?'
|
||||
encap '|'
|
||||
level '!'
|
||||
quote '"'
|
||||
keyword "\\glossaryentry"
|
||||
preamble "\\glossarysection[\\glossarytoctitle]{\\glossarytitle}\\glossarypreamble\n\\begin{theglossary}\\glossaryheader\n"
|
||||
postamble "\%\n\\end{theglossary}\\glossarypostamble\n"
|
||||
group_skip "\\glsgroupskip\n"
|
||||
item_0 "\%\n"
|
||||
item_1 "\%\n"
|
||||
item_2 "\%\n"
|
||||
item_01 "\%\n"
|
||||
item_x1 "\\relax \\glsresetentrylist\n"
|
||||
item_12 "\%\n"
|
||||
item_x2 "\\relax \\glsresetentrylist\n"
|
||||
delim_0 "\{\\glossaryentrynumbers\{\\relax "
|
||||
delim_1 "\{\\glossaryentrynumbers\{\\relax "
|
||||
delim_2 "\{\\glossaryentrynumbers\{\\relax "
|
||||
delim_t "\}\}"
|
||||
delim_n "\\delimN "
|
||||
delim_r "\\delimR "
|
||||
headings_flag 1
|
||||
heading_prefix "\\glsgroupheading\{"
|
||||
heading_suffix "\}\\relax \\glsresetentrylist "
|
||||
symhead_positive "glssymbols"
|
||||
numhead_positive "glsnumbers"
|
||||
page_compositor "."
|
||||
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+191
@@ -0,0 +1,191 @@
|
||||
% !TeX program = lualatex
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
%% DOCUMENTS SETTINGS
|
||||
\documentclass[
|
||||
12pt,
|
||||
twoside,
|
||||
fleqn,
|
||||
method=right]{scrreprt}
|
||||
|
||||
%% PREAMBLE
|
||||
\input{../config/preamble.tex}
|
||||
\usepackage{subfiles}
|
||||
|
||||
%% BIB RESOURCE
|
||||
\addbibresource{../config/literature.bib}
|
||||
|
||||
%% GLOSSARY
|
||||
\input{../config/glossary}
|
||||
|
||||
%% CUSTOM COMMANDS
|
||||
\input{../config/commands.tex}
|
||||
|
||||
%% TITLE DEFINITION
|
||||
|
||||
% Add background image
|
||||
\let\omaketitle\maketitle
|
||||
\makeatletter
|
||||
\newcommand{\mainmaketitle}{\AddToShipoutPictureBG*{\includegraphics[scale=1]{title_page.png}}\omaketitle}
|
||||
\makeatother
|
||||
|
||||
\author[1]{David Immanuel Tschan}
|
||||
\affil[1]{Institute of Amtospheric and Climate Science,\linebreak{Department of Environmental Sciences, ETH Zürich}}
|
||||
|
||||
|
||||
\subject{Master Thesis}
|
||||
\title{Photochemical reduction of Iodate through
|
||||
Iron-containing Complexes in Secondary Organic
|
||||
Aerosol from Monoterpene Oxidation}
|
||||
\subtitle{}
|
||||
\date{20.05.2026 --- 02.12.2026}
|
||||
\publishers{Unpublished: 1st Edition}
|
||||
|
||||
\makeindex[options=-s index.ist, intoc, name=main, columns=3]
|
||||
\makeglossaries
|
||||
\indexsetup{firstpagestyle=mainbody}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
|
||||
|
||||
\begin{document}
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% FRONTMATTER
|
||||
|
||||
\pagestyle{mainbody}
|
||||
|
||||
\mainmaketitle
|
||||
%\pagebreak
|
||||
|
||||
\thispagestyle{empty}
|
||||
\small{Title page image courtesy to \href{https://unsplash.com/@asoggetti}{Alessio Soggetti} from \href{https://unsplash.com/photos/mountains-covered-with-fogs-gdE-5Oui1Y0?utm_source=unsplash&utm_medium=referral&utm_content=creditCopyText}{unsplash.com}, accessed on 26.05.2026 10:00.
|
||||
|
||||
|
||||
The font used in figures including technical drawings (figs. ...) was accessed from \href{https://github.com/hikikomori82/osifont}{https://github.com/hikikomori82/osifont} on 06.08.2026 09:25 and is distributed under the GNU GPL V3 + FE license.
|
||||
|
||||
Beaker in figure \ref{methods: fig: solution preparation} was adapted from Diogo Losch De Oliveira (2026). Beakers [Illustration]. CC-BY 4.0. SciDraw.io. https://scidraw.io/drawing/beakers-ba8583ed. Accessed 10.08.2026 16:16}
|
||||
\pagebreak
|
||||
|
||||
\pagestyle{mainbody}
|
||||
|
||||
\tableofcontents
|
||||
\listoftables
|
||||
\listoffigures
|
||||
\clearpage
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% MAINMATTER
|
||||
|
||||
\modulolinenumbers[1]
|
||||
\linenumbers
|
||||
\doublespacing
|
||||
|
||||
\subfile{../chapters/introduction.tex}
|
||||
\subfile{../chapters/methods.tex}
|
||||
%\subfile{../chapters/results.tex}
|
||||
%\subfile{../chapters/discussion.tex}
|
||||
%\subfile{../chapters/conclusion.tex}
|
||||
%\subfile{../chapters/acknowledgements.tex}
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% BACKMATTER
|
||||
\singlespacing
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% BIBLIOGRAPHY
|
||||
\printbibliography[heading=bibintoc]
|
||||
\clearpage
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% ACRONYMS
|
||||
|
||||
%% Formatting for acronyms
|
||||
\renewcommand{\glsnamefont}[1]{\normalfont\textbf{#1}}
|
||||
|
||||
% print acronyms
|
||||
\setabbreviationstyle[acronym]{long-short}
|
||||
\printglossary[type=\acronymtype, style=index]
|
||||
\thispagestyle{proposal}
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% SYMBOLS
|
||||
|
||||
% Formatting for symbols
|
||||
\renewcommand{\glsnamefont}[1]{\normalfont{#1}}
|
||||
|
||||
% change column headers:
|
||||
\renewcommand{\entryname}{Symbol}
|
||||
\renewcommand{\symbolname}{Unit}
|
||||
|
||||
% Adjusts the column widths for the symbols list
|
||||
\setlength{\tabcolsep}{5pt}
|
||||
\renewcommand{\glslongextraDescAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.7\textwidth - \tabcolsep - \tabcolsep}} % Description
|
||||
\renewcommand{\glslongextraNameAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.12\textwidth - \tabcolsep - \tabcolsep}} % Symbol
|
||||
\renewcommand{\glslongextraSymbolAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.18\textwidth - \tabcolsep - \tabcolsep}} % Unit
|
||||
|
||||
% print list of symbols
|
||||
\renewcommand{\arraystretch}{0.6}
|
||||
\printunsrtglossary[type=symbols, style=long-name-desc-sym, title={List of Symbols}, toctitle={List of Symbols}]
|
||||
\thispagestyle{proposal}
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% CHEMICAL SPECIES
|
||||
|
||||
% Formatting for chemical species
|
||||
\renewcommand{\glsnamefont}[1]{\normalfont{#1}}
|
||||
|
||||
% change column headers:
|
||||
\renewcommand{\entryname}{Name}
|
||||
\renewcommand{\symbolname}{Formula}
|
||||
\renewcommand{\descriptionname}{Comment}
|
||||
|
||||
% Adjusts the column widths for the symbols list
|
||||
\setlength{\tabcolsep}{5pt}
|
||||
\renewcommand{\glslongextraDescAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.5\textwidth - \tabcolsep - \tabcolsep}} % Description
|
||||
\renewcommand{\glslongextraNameAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.25\textwidth - \tabcolsep - \tabcolsep}} % Name
|
||||
\renewcommand{\glslongextraSymbolAlign}{>{\raggedright\arraybackslash}p{\dimexpr 0.25\textwidth - \tabcolsep - \tabcolsep}} % Fomula
|
||||
|
||||
% print list of speces
|
||||
\renewcommand{\arraystretch}{1.1}
|
||||
\printunsrtglossary[type=species, style=long-name-desc-sym, title={List of Species}, toctitle={List of Species}]
|
||||
\thispagestyle{proposal}
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% GLOSSARY
|
||||
|
||||
% Formatting for symbols
|
||||
\renewcommand{\glsnamefont}[1]{\normalfont\bfseries{#1}}
|
||||
|
||||
\printglossary[type=main, toctitle=Glossary, style=index]
|
||||
\thispagestyle{proposal}
|
||||
|
||||
|
||||
|
||||
|
||||
%% ------------------------------------------------------------------%
|
||||
% INDEX
|
||||
|
||||
% Formatting for index
|
||||
\renewcommand{\glsnamefont}[1]{\normalfont\bfseries{#1}}
|
||||
|
||||
\printindex
|
||||
\thispagestyle{mainbody}
|
||||
|
||||
\end{document}
|
||||
Reference in new issue
Block a user