% Thomas Kuster
% 24. November 2005
% Seminar Atmosphäre

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\title[Influence of NO$_{\textnormal{x}}$ on O$_3$ Content]{The Influence of Nitrogen Oxides on the Atmospheric Ozone Content}
\subtitle{P.~J.~Crutzen 1970}
\author{%
  Thomas Kuster%\inst{1}
  }
\institute[ETH Zürich]{
 %\inst{1}%
 Department of Environmental Sciences\\
 ETH Zürich}
\date[ETH 2006]{Stratospheric Chemistry, 7.12.2006}

\subject{Crutzen, 1970}
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%   1. Semester, MSc Enviromentale Science and Atmosphere and Climate Science, ETH Zürich\\
%   \hyperref{http://fam-kuster.ch/index.php?navigation=ETH&main=http://n.ethz.ch/student/kusterth/eth/html/}{}{}{http://fam-kuster.ch}

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  \frametitle{Outline}
  \tableofcontents
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\section[Crutzen]{Prof. Paul Jozef Crutzen}
\subsection{Personal, Academic Studies}

\begin{frame}<1>[label=foil:crutzen]
 \frametitle{Paul Jozef Crutzen}
 \begin{columns}
  \column{0.45\linewidth}
  \includegraphics[width=\linewidth]{./images/crutzen}
  \tiny{
  \\\vspace{1em}
  \hyperref{http://nobelprize.org/nobel_prizes/chemistry/laureates/1995}{}{}{http://nobelprize.org\dots}
  }
  \column{0.55\linewidth}
%\vspace*{\fill}
%\vfill
  \begin{block}{Personal}%\footnote{Translation from Spanish}
   \begin{itemize}
    \item Born December, 3, 1933 in Amsterdam Holland
    \item Married, two childern
   \end{itemize}
  \end{block}
  \begin{block}{Academic Studies}
   \begin{itemize} 
    \item Civil Engineering, 1951--1954, Amsterdam, Holland.
    \item Academic Studies and Research Activities 1959--1973 at the University of Stockholm, Sweden.
%      \begin{itemize}
%       \item M.Sc. (Filosofie Kandidat), 1963.
%       \item Ph.D. (Filosofie Licentiat), Meteorology, 1968,
%         
%        Title: "Determination of parameters appearing in the 'dry' and the 'wet' photochemical theories for ozone in the stratosphere", Examiner: Prof. Dr. Bert Bolin, Stockholm, Sweden. D.Sc. (Filosofie Doctor), 1973, Stockholm,Sweden,
% 
%        Title: "On the photochemistry of ozone in the stratosphere and troposphere and pollution of the stratosphere by high-flying aircraft", Promoters: Prof. Dr. John Houghton, FRS, Oxford, and Dr. R.P. Wayne, Oxford.
% (Ph.D. and D.Sc. degrees were given with the highest possible distinctions).
%      \end{itemize}
    \end{itemize}
  \end{block}
 \end{columns} 
\end{frame}

\subsection{Noble Prize}
\begin{frame}<1>[label=foil:nobelprize]
 \frametitle{The Nobel Prize in Chemistry 1995}
 \framesubtitle{"for their work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone"}
 \begin{columns}
  \column{0.33\linewidth}
  \includegraphics[width=\linewidth]{./images/crutzen}
  Paul Jozef Crutzen % Josef
  
  *1933
  
  the Netherlands
%   \tiny{the Netherlands
%   Max-Planck-Institut für Chemie Mainz, Federal Republic of Germany
%   Born 1933}
  \column{0.33\linewidth}
  \includegraphics[width=\linewidth]{./images/molina}
  Mario José Molina % José
  
  *1943 (Mexico City)
  
  USA
%   \tiny{USA
%   Massachusetts Institute of Technology (MIT) Cambridge, MA, USA
%   Born 1943 (Mexico City)}
  \column{0.33\linewidth}
  \includegraphics[width=\linewidth]{./images/rowland}
  F. S. Rowland %Frank Sherwood Rowland
  
  *1927
  
  USA
%   \tiny{USA
%   University of California Irvine, CA, USA
%   Born 1927}
 \end{columns} 
\end{frame}

\section{Chemistry}
\subsection{Balance of O$_3$}
\begin{frame}
 \frametitle{Balance of O$_3$}
 \begin{block}{Odd Oxygen}
  \begin{itemize}
   \item balance between atomic oxygen and ozone
   \item reaction is to slow to balance the O$_3$
   \item Equation: (5), (7), (8)
  \end{itemize}
 \end{block}
 \begin{block}{OH and HO$_2$}
  \begin{itemize}
   \item destruction of ozone by OH or HO$_2$
   \item this hypothesis does not explain the ozone observation
   \item Equation: (14), HO$_2$ + O$_3$ not used (very speculative)
  \end{itemize}
 \end{block}
 \begin{block}{Odd Nitrogen (NO and NO$_2$)}
  \begin{itemize}
   \item direct controlling effect on the ozone $\Rightarrow$ controlling the ozone production rates
   \item Equation: (1), (2), (3)
  \end{itemize}
 \end{block}
%  \begin{eqnarray}
%   NO + O_3 \overset{k_1}{\rightarrow} NO_2 + O_2\\
%   NO + O_3 \overset{k_1}{\rightarrow} NO_2 + O_2\\
%   NO + O_3 \overset{k_1}{\rightarrow} NO_2 + O_2\\
%   NO + O_3 \overset{k_1}{\rightarrow} NO_2 + O_2\\
%  \end{eqnarray}
\end{frame}

%\subsection{Odd Oxygen}
\begin{frame}
\frametitle{Odd Oxygen}
 \begin{block}{Reactions}
  \vspace{-1em}
  \begin{align}
   \textnormal{O} + \textnormal{O}_2 + \textnormal{M} & \overset{k_5}{\rightarrow} \textnormal{O}_3 + \textnormal{M} & {} \setcounter{equation}{4}\\
   \textnormal{O}_3 + h\nu & \overset{j_7}{\rightarrow} \textnormal{O} + \textnormal{O}_2 & \quad 308\,nm < \lambda < 1140\,nm \setcounter{equation}{6}\\
   \textnormal{O}_3 + h\nu & \overset{j_8}{\rightarrow} \textnormal{O}(^1\textnormal{D}) + \textnormal{O}_2 & \lambda < 308\,nm \setcounter{equation}{7}
 \end{align}
 \end{block}
 \begin{block}{Rate Constants}
  \begin{columns}
  \column{0.35\linewidth}
   \vspace{-1em}
   \begin{align*}
    k_5 = {} & 8 \cdot 10^{-35} e^{(445/T)}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\\
    j_7 = {} & ?\\
    j_8 = {} & ?
   \end{align*}
  \column{0.35\linewidth}
    \vspace{-1em}
    \begin{align*}
    k_5 : {} & k_0^{300} = 6.0\cdot 10^{-34}, n = 2.4\\
    j_7 = {} & ?\\
    j_{8_\infty} = {} & 7.8\cdot10^{-3}\small{\,\frac{1}{\textnormal{s}}}
   \end{align*}
  \end{columns}
  \vspace{0.5em}
  \tiny{left: \cite{crutzen1970}, right: \cite{sander2006} \& \cite{brasseur2005}}
 \end{block}
\end{frame}

%\subsection[OH and HO$_2$]{OH and HO$_2$}
\begin{frame}
\frametitle{OH and HO$_2$}
 \begin{block}{Reactions}
  \vspace{-1em}
  \begin{align}
   \textnormal{OH} + \textnormal{O}_3 & \overset{k_{14}}{\rightarrow} \textnormal{HO}_2 + \textnormal{O}_2 \setcounter{equation}{13}\\
   \textnormal{HO}_2 + \textnormal{O}_3 & \overset{k_{31}}{\rightarrow} \textnormal{OH} + 2\textnormal{O}_2 \setcounter{equation}{30}
  \end{align}
 \end{block}
 \begin{block}{Rate Constants}
  \begin{columns}
  \column{0.35\linewidth}
   \vspace{-1em}
   \begin{align*}
    k_{14} & = 10^{-13}{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\\
    k_{31} & : \textnormal{not used}
   \end{align*}
  \column{0.35\linewidth}
    \vspace{-1em}
    \begin{align*}
    k_{14} & = 1.7\cdot10^{-12}\exp{(-940/T)}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\\
    k_{31} & = 1.0\cdot10^{-14}\exp{(-490/T)}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}
   \end{align*}
  \end{columns}
  \vspace{0.5em}
  \tiny{left: \cite{crutzen1970}, right: \cite{sander2006}}
 \end{block}
\end{frame}

%\subsection[Odd Nitrogen]{Odd Nitrogen (NO and NO$_2$)}
\begin{frame}
\frametitle{Odd Nitrogen (NO and NO$_2$)}
 \begin{block}{Reactions}
  \vspace{-1em}
  \begin{align}
   \textnormal{NO} + \textnormal{O}_3 & \overset{k_{1}}{\rightarrow} \textnormal{NO}_2 + \textnormal{O}_2 \setcounter{equation}{0}\\
   \textnormal{NO}_2 + h\nu & \overset{j_{2}}{\rightarrow} \textnormal{NO} + \textnormal{O} \setcounter{equation}{1}\\
   \textnormal{NO}_2 + \textnormal{O} & \overset{k_{3}}{\rightarrow} \textnormal{NO} + \textnormal{O}_2 \setcounter{equation}{2}
  \end{align}
 \end{block}
 \begin{block}{Rate Constants}
  \begin{columns}
  \column{0.30\linewidth}
   \vspace{-1em}
   \begin{align*}
    k_{1} & = 1.7 \cdot 10^{-12}\cdot e^{-1310/T}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\hspace{-1.5em}\\
    j_{2} & = 5 \cdot 10^{-3}\small{\,\frac{1}{\textnormal{s}}}\\
    k_{3} & = 3.2 \cdot 10^{-11}\cdot e^{-530/T}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\hspace{-1.5em}
   \end{align*}
  \column{0.30\linewidth}
    \vspace{-1em}
    \begin{align*}
    k_{1} & = 3.0 \cdot 10^{-12}\cdot e^{-1500/T}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}\\
    j_{2} & = 1 \cdot 10^{-2}\small{\,\frac{1}{\textnormal{s}}}\\
    k_{3} & = 5.1 \cdot 10^{-12}\cdot e^{210/T}\small{\,\frac{\textnormal{cm$^3$}}{\textnormal{\#\,s}}}
   \end{align*}
  \end{columns}
  \vspace{0.5em}
  \tiny{left: \cite{crutzen1970}, right: \cite{sander2006} \& \cite{brasseur2005}}
 \end{block}
\end{frame}

\subsection{Change of Odd Oxygen}
\begin{frame}
\frametitle{Change of Odd Oxygen (O and O$_3$)}
 \begin{block}{Time Rate}
  \vspace{-1em}
  \begin{align*}
   \frac{d}{dt}[\textnormal{O}_\textnormal{x}] = {} & + \underbrace{2 j_4 [\textnormal{O}_2]}_{P}\\
   & - \underbrace{2 k_3 [\textnormal{O}][\textnormal{NO}_2]}_{D_1}\\
   & - \underbrace{\left\{(k_{11}[\textnormal{O}] + k_{14}[\textnormal{O}_3])[\textnormal{OH}] + k_{13}[\textnormal{O}][\textnormal{HO}_2]\right\}}_{D_2}\\
   & - \underbrace{2 k_6[\textnormal{O}][\textnormal{O}_3] \tag{22}}_{D_3}
  \end{align*}
 \end{block}
\end{frame}

\section{Impact}
\begin{frame}
\frametitle{Impact}
\framesubtitle{Record Count (total 600 times cited)}
\includegraphics[page=1, viewport=70 110 705 510, clip, width=\linewidth]{./recordcount}
\end{frame}

\section{Discussion}
\begin{frame}
\begin{block}{Discussion}
 \begin{itemize}
  \item Nitrogen oxides are of great importance in ozone photochemistry
  \item Observations of the nitrogen oxides in the stratosphere
  \item Sources of N$_2$O
  \item Photodissociation products of N$_2$O
  \item Most of the NO and NO$_2$ is produced at very high levels, influence by solar cycle?
  \item What products are formed in the photolysis of ozone below 234\,nm?
  
  O$_3$ + $h\nu$ $\rightarrow$ O($^1$S) + O$_2$($^3\Sigma_g^-$)
 \end{itemize}
\end{block}
\end{frame}

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\subsection{List of figures}
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  \begin{thebibliography}{10}
  \beamertemplatearticlebibitems
  \bibitem[Portraits]{portraits}
   Portraits of P. J. Crutzen, M. J. Molina and F. S. Rowland
   \newblock \url{http://nobelprize.org/nobel_prizes/chemistry/laureates/1995/}
   
  \end{thebibliography}
\end{frame}

\subsection{Bibliography}
\begin{frame}[allowframebreaks]
 \frametitle{Bibliography}
 \begin{thebibliography} %{Wiki: Cultura maya}
  \beamertemplatearticlebibitems  
  % Followed by interesting articles. Keep the list short.  
  \bibitem[Crutzen, 1970]{crutzen1970}
    P.~J.~Crutzen
    \newblock The Influence of Nitrogen Oxides on the Atmospheric Ozone Content.
    \newblock {\em Quarterly Journal of the Royal Meteorological Society}, 96:320--325, 1970.
  
  \bibitem[Sander, 2006]{sander2006}
    S.~P.~Sander et.\,al.
    \newblock Chemical Kinetics and Photochemical for Use in Atmospheric Studies
    \newblock {\em Jet Propulsion Laboratory Publication 06-2}, Evaluation Number 15, July 10, 2006.
    \newblock \url{http://jpldataeval.jpl.nasa.gov/pdf/JPL_15_AllInOne.pdf}

  \bibitem[Brasseur \& Solomon]{brasseur2005}
    G.~P.~Brasseur and S.~Solomon
    \newblock Aeronomy of the Middle Atmosphere
    \newblock {\em Springer}, 2005.
        
  \bibitem[Crutzen, 1995]{crutzen1995}
    P.~J.~Crutzen
    \newblock Autobiography
    \newblock \url{http://nobelprize.org/nobel_prizes/chemistry/laureates/1995/crutzen-autobio.html}
  
  \bibitem[Crutzen, Homepage]{crutzenhp}
    P.~J.~Crutzen
    \newblock Personal Homepage
    \newblock \url{http://www.mpch-mainz.mpg.de/~air/crutzen/}
        
  \end{thebibliography}
\end{frame}

%\subsection{Additional Slides}

\end{document}
