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\begin{document}
\setcounter{section}{0} \renewcommand{\thefigure}{S.\arabic{figure}}
\section{Supplements}  
\subsection{Detailed model description}
\label{App:RTM_appendix}

The reactions in the reactive transport model describe organic matter degradation coupled to different electron acceptors. Reactions are divided in primary redox reactions and other biogeochemical reactions (Table \ref{Tab:model_reactions}). The succession of oxidants during organic matter degradation \citep{Froelich1979} is described by means of Monod kinetics (Table \ref{Tab:reactions}; \citet{Boudreau1997}). This means that the oxidants with the highest metabolic free energy yield are preferentially used until they become limiting and the oxidant with the next highest energy yield is used \citep{Berg2003,Boudreau1996a,Wang1996}. Respiratory reactions occur where \ce{O2}, \ce{NO3^-}, \ce{Mn(OH)2}, \ce{Fe(OH)3} and \ce{SO4$^{2-}$} serve as electron acceptors and finally organic matter is subject to methanogenesis (\citet{Reed2011b,Reed2011a,Rooze2016}; Table \ref{Tab:reactions}). Organic matter includes carbon (C), nitrogen (N) and P in a C:N:P ratio of 106:16:0.35. In the model, oxidation of \ce{CH4} is possible with \ce{O2}, \ce{Mn(OH)2}, \ce{Fe(OH)3} and \ce{SO4$^{2-}$}. Dissolved inorganic carbon in the model is calculated as the sum of the carbon in \ce{CO2} and \ce{HCO3^{2-}}, which is produced or consumed by modeled reactions (Table \ref{Tab:model_reactions}).

The generic mass conservation equations for solids and solutes are described by Eq. \ref{eq:distr_solid} and \ref{eq:distr_disol};

\begin{equation}
\label{eq:distr_solid}
\mathit{(1-\phi)\frac{\partial C_s}{\partial t} = -(1-\phi)v \frac{\partial C_s	}{\partial z} + \sum R_s}
\end{equation}

\begin{equation}
\label{eq:distr_disol}
\mathit{\phi \frac{\partial C_{aq}}{\partial t} = \phi D' \frac{\partial ^2 C_{aq}}{\partial z^2} - \phi u \frac{\partial C_{aq}}{\partial z} + \sum R_{aq}}
\end{equation}

\begin{equation}
\label{eq:tortuosity}
\mathit{D' = \frac{D_m}{1-ln\phi ^2}}
\end{equation}

where $C_s$ is the concentration of solid species (\unit{mol} \unit{L^{-1}}), $C_{aq}$ is the concentration of dissolved species (\unit{mol} \unit{L^{-1}}), t is time (\unit{yr}), $\phi$ is the sediment porosity, $v$ and $u$ are the advective velocities of solid and dissolved species (\unit{cm} \unit{yr^{-1}}), respectively. Variables $v$ and $u$ were described by a depth-dependent function to account for changes in porosity \citep{Meysman2005}. Distance from the sediment-water interface is $z$ (\unit{cm}), $D'$ the diffusion coefficient of dissolved species (\unit{cm^2} \unit{yr^{-1}}), corrected for tortuosity in the porous medium (\citep{Boudreau1996b}, Eq. \ref{eq:tortuosity}). $\sum R_s$ and $\sum R_{aq}$ are the net reaction rates from the chemical reaction (Table \ref{Tab:reactions}) for solid and dissolved species. 

Porosity ($\phi$) is described by Eq. \ref{eq:porosity} to account for sediment compaction \citep{Meysman2005,Reed2011a},

\begin{equation}
\label{eq:porosity}
\mathit{\phi (x) = \phi _{\infty} + ( \phi _0 - \phi _{\infty} ) e ^{-\frac{x}{y}}}
\end{equation}

where $\phi _0$ is the porosity at the sediment-water interface, $\phi _{\infty}$ is the porosity at depth and y is the porosity attenuation factor/e-folding distance (Fig. \ref{Fig:por+tur+irr}A, Table \ref{Tab:Environment}).
The model code was written in R with the use of the marelac geochemical dataset package \citep{Soetaert2010}. To calculate the transport in porous media, the R package Reactran was used \citep{Soetaert2012a}. The set of ordinary differential equations was solved numerically with the Lsode integrator algorithm \citep{Petzold1983}.

Zero gradient boundary conditions were applied to the base of the model domain for all chemical species. To avoid influence of the boundary conditions at the base of the model domain results, the total depth of the model was set to 90 cm (divided into 900 grid cells of 0.1 cm). 

Reaction parameters were mostly taken from literature or obtained within existing parameter ranges (Table \ref{Tab:k-values}). If these were not available, or no fit to the data could be obtained with existing ranges, parameters were constrained by fitting the model to the measured data. 

\noappendix       %% use this to mark the end of the appendix section


\setcounter{figure}{0} \renewcommand{\thefigure}{S.\arabic{figure}}
\begin{figure}[H]
\center
\includegraphics[height=\dimexpr \textheight - 4\baselineskip\relax]{Macrofauna_all_2}
\caption{Wet weight of macrofauna (ww \unit{m^{-2}}; in grams) at sites NB1, N6, N10, N7 and  NB8 in the \"{O}re Estuary from 1995-2015 (www.SMHI.se).}
\label{Fig:Macrofauna_NB8}
\end{figure}

\begin{figure}[H]
    \centering
        \includegraphics[width=\textwidth]{Pb-210_fit}
        \caption{Solid phase depth profiles of \ce{^{210}Pb} at sites NB1, N6, N10, N7 and NB8 and model fits (black lines). Sites NB1, N6, N10 and N7 were sampled in April 2015. Site NB8 was sampled in August 2015.}
        \label{Fig:Pb-210}
\end{figure}

\begin{figure}[H]
\center
\includegraphics[width=1\columnwidth]{irr+tur+por}

\caption{Depth profiles used in the model A: Measured porosity (\unit{vol} \unit{vol^{-1}}) for April 2015 (black circles) and fitted porosity (black line); B: bioturbation coefficient ($D_b$; \unit{cm} \unit{yr^{-1}}); C: bioirrigation coefficient ($\alpha$; \unit{yr^{-1}}); D: Re-adsorption coefficient for 
\ce{HPO4^{2-}}.} 
\label{Fig:por+tur+irr}
\end{figure}

\begin{figure}[H]
\center
\includegraphics[width=1\columnwidth]{Fe-oxides_scenario2}

\caption{Transient scenarios used in the reactive transport model between 1965 and 2015; A: different phases of organic matter; B different phases of Fe oxides; C: different phases of manganese; D: average P:Fe ratio of all Fe oxide fractions combined, E: total P input bound to Fe oxides. The various types of organic matter, Fe oxides and Mn oxides are indicated as $\alpha$ (highly reactive), $\beta$ (less reactive) and $\gamma$ (refractory).}
\label{Fig:Fe-oxdes_transient}
\end{figure}

\begin{figure}[H]
\center
\includegraphics[width=1\columnwidth]{Extractions_NB8}

\caption{Solid phase depth profiles of the easily reducible Fe oxides (\ce{Fe_{ox1}}) and reducible (crystalline) Fe oxides (\ce{Fe_{ox2}}) including vivianite, Fe carbonates (\ce{Fe_{carb}}), magnetite (\ce{Fe_{mag}}), elemental S (\ce{S^0}) and S in pyrite (CRS) for site NB8 in April 2015.}
\label{Fig:Extractions_NB8}
\end{figure}


\begin{figure}[H]
\center
\includegraphics[width=\textwidth,height=\textheight,keepaspectratio]{Reaction_rates}

\caption{Depth profiles of reaction rates calculated for the baseline scenario in 2015. Rates are in \unit{mol} \unit{m^{-3}} \unit{yr^{-1}}. Reactions are described in Table \ref{Tab:model_reactions}.}
\label{Fig:Reaction_rates}
\end{figure}

\begin{figure}[H]
\center
\includegraphics[width=0.6\columnwidth]{Sink_siwtch2}
\caption{Solid phase depth profiles of A: Fe bound to Fe oxides and vivianite; B: P bound to Fe oxides and vivianite.}
\end{figure}

%\begin{figure}[H]
%\center
%\includegraphics[width=\textwidth,height=\textheight,keepaspectratio]%Sens_fractionation}
%\caption{Modeled burial forms of P as a function of changes in A: %sedimentation rates between 0.25 and 2 cm \unit{yr^{-1}}; B: organic %matter inputs ranging between -70\% and +25\% C: inputs of Fe oxides %ranging between -25\% and 25\%. Corresponding P burial rates are shown in %figure 9.}
%\label{Fig:fractionation_Fe_OM}
%\end{figure}

\begin{figure}[H]
\center
\includegraphics[width=1\columnwidth]{river_discharge_sweden}
\caption{Averaged summer river discharge for 86 Swedish rivers from 1900-2015 (www.SMHI.se).}
\label{Fig:River_discharge_Sweden}
\end{figure}

\clearpage

\newpage
\setcounter{table}{0} \renewcommand{\thetable}{S.\arabic{table}}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%Chemical Species
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\begin{table}[H]
\center
\caption{Chemical species included in the model.}
\label{Tab:Chemical_species}
\begin{tabular}{ll}
\hline
\textbf{Species}   	&\textbf{Notation}		        \\ \hline
Solid               &                               \\ \hline
Organic matter$^a$  & OM$^{\alpha,\beta,\gamma}$    \\ 
Iron oxide$^a$   	&\ce{Fe(OH)3}$^{\alpha,\beta}$  \\ 
Elemental sulfur	&\ce{S^0}						\\
Iron monosulfide	&\ce{FeS}						\\
Pyrite				&\ce{FeS2}						\\
Iron-bound Phosphorus&\ce{Fe(OH)_3P}					\\
Vivianite			&\ce{Fe3(PO4)2}					\\
Siderite			&\ce{FeCO3}						\\
Organic phosphorus  &P$_{org}$						\\
Authigenic (Ca) phosphorus & CaP					\\
Detrital phosphorus & DetrP							\\
Manganese oxide$^b$	&\ce{Mn(OH)2}$^{\alpha,\beta}$  \\
Manganese carbonate	&\ce{MnCO3}						\\  \hline
Solute              &                               \\ \hline
Chloride			&\ce{Cl^-}						\\
Oxygen				&\ce{O2}			          	\\ 
Nitrate				&\ce{NO3^-}				        \\ 
Sulfate				&\ce{SO4^2-}			        \\ 
Methane				&\ce{CH4}						\\ 
Iron				&\ce{Fe^2+}						\\
Ammonium$^c$		&$\sum$\ce{NH4^+}				\\
Hydrogen sulfide$^c$&$\sum$\ce{H2S}	      		    \\			
Phosphate$^c$		&$\sum$\ce{HPO4^2-}			    \\
Dissolved Inorganic Carbon&\ce{DIC}					\\
Manganese			&\ce{Mn^2+}						\\
\hline
\end{tabular}

$^a$ chemical species consist of 3 types: reactive ($\alpha$), less reactive ($\beta$) and refractory ($\gamma$). Fe oxide$^{\beta (pulse)}$ and Fe oxide$^{\beta (max)}$ are not specifically named because they have the same characteristics as Fe oxide$^\beta$.  \newline 
$^b$ chemical species consist of two types: reactive ($\alpha$) and less reactive ($\beta$). \newline
$^c$ $\sum$ denotes that all species of an acid are included. 

\end{table}

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Reactions
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

\begin{table}[H]
\centering
\caption{Reaction pathways and stoichiometries implemented in the model.}
\label{Tab:reactions}
\resizebox{\textwidth}{!}{
\begin{tabular}{ll}
\hline
\textbf{Primary redox reactions                                                     } &     \\ \hline

OM$^{\alpha,\beta}$ + a\ce{O2} $\rightarrow$ a\ce{CO2} + b\ce{NH4^+} + c\ce{H_3PO4} + a\ce{H2O}            & R1  \\

OM$^{\alpha,\beta}$ + 0.8a\ce{NO3^-} + 0.8a\ce{H^+} $\rightarrow$ a\ce{CO2} + b\ce{NH4^+} + c\ce{H_3PO4} + 0.4a\ce{N_2} + 1.4a \ce{H2O}   & R2  \\

OM$^{\alpha,\beta}$ +2a\ce{Mn(OH)2}$^{\alpha}$ + 2a\ce{H+} $\rightarrow$ 2 \ce{Mn^2+} +a\ce{CO2} + c\ce{H_3PO4} + 2a\ce{H2O}& R3 \\

OM$^{\alpha,\beta}$ + 4a \ce{Fe(OH)3}$^{\alpha}$ + 4a$\chi^{\alpha}$Fe$_{ox}$P + 12a\ce{H+} $\rightarrow$ a\ce{CO2} + b\ce{NH4^+} + (c+4a$\chi^{\alpha}$)\ce{H_3PO4} + 13a\ce{H2O} + 4a\ce{Fe2+}     & R4  \\

OM$^{\alpha,\beta}$ + 0.5a \ce{SO4^2-} + a\ce{H^+} $\rightarrow$ a\ce{CO2} + b\ce{NH4^+} + c\ce{H_3PO4} + 0.5a\ce{H2S} + a\ce{H_2O}               & R5  \\

OM$^{\alpha,\beta}$ $\rightarrow$ 0.5a\ce{CO2} + b\ce{NH4^+} + c\ce{H_3PO4} + 0.5a\ce{CH4}                                 & R6  \\

\ce{CO2} + 4\ce{H2} $\rightarrow$ \ce{CH4} + 2\ce{H2O} 
& R7  \\

\hline
\textbf{Secondary and other reactions}                                                              
&     \\
\hline
2\ce{O2} + \ce{NH4^+} + 2\ce{HCO3^-} $\rightarrow$ \ce{NO3^-} + 2\ce{CO2} + 3\ce{H2O}                                   & R8  \\

\ce{O2} + 4\ce{Fe^2+} + 8\ce{HCO3^-} + 2\ce{H2O} + 4$\chi^{\alpha}$\ce{H_2PO4^-} $\rightarrow$  4 \ce{Fe(OH)3}$^{\alpha}$+ 4$\chi^{\alpha}$ \ce{Fe_{ox}P} + 8\ce{CO2}        & R9  \\

2\ce{O2} + \ce{FeS} $\rightarrow$ \ce{SO4^2-} + \ce{Fe^2+}                                                      & R10  \\

7\ce{O2} + 2\ce{FeS2} + 2\ce{H2O}  $\rightarrow$ 4\ce{SO4^2-} + 2\ce{Fe^2+} + 4\ce{H^+}                                & R11  \\

2\ce{O2} + \ce{H2S} + 2\ce{HCO3^-} $\rightarrow$ \ce{SO4^2-} + 2\ce{CO2} + 2\ce{H2O}                                   & R12 \\

2\ce{O2} + \ce{CH4}  $\rightarrow$ \ce{CO2} + 2\ce{H2O}                                                       & R13 \\

2\ce{Fe(OH)3}$^{\alpha}$ + 2$\chi^{\alpha}$\ce{Fe_{ox}P} + \ce{H2S} + 4\ce{CO2} $\rightarrow$ 2\ce{Fe^2+} + 2$\chi^{\alpha}$\ce{H_2PO4^-} + \ce{S^0} + 4\ce{HCO3^-} + 2\ce{H2O} & R14 \\

2\ce{Fe(OH)3}$^{\beta,\beta(max),\beta(pulse)}$ + 2$\chi^{\alpha}$\ce{Fe_{ox}P} + \ce{H2S} + 4\ce{CO2} $\rightarrow$ 2\ce{Fe^2+} + 2$\chi^{\alpha}$\ce{H_2PO4^-} + \ce{S^0} + 4\ce{HCO3^-} + 2\ce{H2O} & R15 \\

\ce{Fe^2+} + \ce{H2S} $\rightarrow$ \ce{FeS} + 2\ce{H+}                                     & R16 \\

\ce{FeS} + \ce{H2S} $\rightarrow$ \ce{FeS2} + \ce{H_2}                                                                & R17 \\

4\ce{S0} + 4\ce{H2O} $\rightarrow$ 3\ce{H2S} + \ce{SO4^2-} + 2\ce{H+}                                            & R18 \\

\ce{FeS} + \ce{S^0} $\rightarrow$ \ce{FeS_2} 
& R19 \\

\ce{SO4^2-} + \ce{CH4} + \ce{CO2} $\rightarrow$  2\ce{HCO3^-} + \ce{H2S}                                              & R20 \\

\ce{CH4} + 8\ce{Fe(OH)3}$^{\alpha,\beta,\beta(max),\beta(pulse)}$ + 8$\chi^{\alpha,\beta}$ \ce{Fe_{ox}P} + 15\ce{H^+} $\rightarrow$  \ce{HCO3^-} + 8\ce{Fe^2+} + 8$\chi^{\alpha,\beta}$\ce{H_2PO4^-} + 21\ce{H2O}
& R21 \\

\ce{Fe(OH)3}$^{\alpha}$ + ($\chi^{\alpha}$ - $\chi^{\beta}$)\ce{Fe_{ox}P} $\rightarrow$ \ce{Fe(OH)3}$^{\beta}$ + ($\chi^{\alpha}$ - $\chi^{\beta}$)\ce{H_2PO4^-} 
& R22 \\

\ce{Fe^2+} + \ce{CO3^2-} $\rightarrow$ \ce{FeCO3}                                                      & R23 \\

\ce{Fe(PO4)_2} + 3\ce{H2S} $\rightarrow$ 2\ce{FeS} + 2\ce{HPO4^{2-}} + 4\ce{H+}
& R24 \\

\ce{Mn^2+} + \ce{HCO3^-} + \ce{OH^-} $\rightarrow$ \ce{MnCO3} + \ce{H2O}
& R25 \\

2\ce{Mn^2+} + 2\ce{O2} + 4\ce{H+} $\rightarrow$ 2\ce{Mn(OH)2}$^{\alpha}$ 
& R26 \\

\ce{Mn(OH)2}$^{\alpha,\beta}$ + 2\ce{H3PO4} + 2\ce{Fe^2+} $\rightarrow$ \ce{Mn^2+} + 2$\chi^{\alpha}$Fe$_{ox}$P 
& R27 \\

\ce{Mn(OH)2}$^{\alpha}$ + \ce{H2S} $\rightarrow$ \ce{Mn^2+} + \ce{S0} + 2\ce{H2O}
 &R28 \\
 
 \ce{Mn(OH)2}$^{\beta}$ + \ce{H2S} $\rightarrow$ \ce{Mn^2+} + \ce{S0} + 2\ce{H2O}
 &R29 \\

\ce{Mn(OH)2}$^{\alpha}$ $\rightarrow$ \ce{Mn(OH)2}$^{\beta}$ 
& R30 \\

4 \ce{Mn(OH)2}$^{\alpha,\beta}$ + \ce{CH4} + 7\ce{H+} $\rightarrow$ 4\ce{Mn^2+} + \ce{HCO3^-} + 5\ce{H2O}
& R31 \\

\ce{Fe(OH)3}$^{\beta,\beta(pulse)}$ + ($\chi^{\beta (max)}$ - $\chi^{\beta,\beta(pulse)}$)\ce{HPO4^{2-}} $\rightarrow$ \ce{Fe(OH)3}$^{\beta (max)}$
& R32 \\


\hline
\end{tabular}}
Organic matter is of the form (\ce{(CH2O)_a(NH4^+)_b(H3PO4)_c}, where a=1, b= 1/16 and c = 300/1. $\alpha$, $\beta$, \& $\gamma$ describe different fractions (i.e. highly reactive, less reactive and refractory). $\chi^{\alpha,\beta,\gamma}$ describes the different P:Fe ratios of \ce{Fe(OH)$_3^{\alpha,\beta,\gamma}$. Reactions$~$ for$~$ different$~$ \ce{Fe(OH)3}$^\beta$ $~$fractions$~$ ($\beta$ $,~$ $\beta (max)$ $~$and$~$ $\beta (pulse)$} are the same and are therefore combined as \ce{Fe(OH)3}$^\beta$).
\end{table}



%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Environment
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\begin{table}[H]
\centering
\caption{Environmental parameters used in the model.}
\begin{tabular}{lllll}
\hline
\textbf{Description}          & \textbf{Symbol} & \textbf{Value or expression} & \textbf{unit} 	&\textbf{source} \\
\hline
Porosity at the Surface               &$\phi_0$ 		& 0.935 				&vol vol$^{-1}$ 		& a \\
Porosity at depth                     &$\phi _\infty$ 	& 0.87					& vol vol$^{-1}$		& a \\
Porosity e-folding distance           &$\gamma$    		& 35 					&cm    			& b \\
Sediment density                      &$\rho$      		& 2.65					&g \unit{cm^{-3}} 		& c \\
Temperature                           &$T$         		& 2.77 					&\unit{^{\circ}C} 	  	& a \\
Salinity                              &$S$         		& 5.05      			&	& a \\
Advective velocity 					  &$v_\infty$  		& $\frac{F_{sed}}{\rho (1-\phi_\infty)}$ && $-$\\ 
of solids at depth                	  &					       					& \\
Bioturbation coefficient at       &$D_{b}$  		& 1.76 						&\unit{cm^2} \unit{yr^{-1}}		& b \\
sediment-water interface  & 		&      			&  \\
Bioirrigation coefficient at     &$\alpha$   		& 45*10$^4$ 				&\unit{yr^{-1}}		 	& b \\
sediment-water interface  & 		&      			&  \\
Mixed layer depth                     &$\varsigma$ 		& 11					&cm  				& b \\
C:N ratio of organic matter			  & 		C/N		&6.625					& mol mol$^{-1}$    & d \\
C:P ratio of organic matter			  & 		C/P		& 300 					&mol mol$^{-1}$     & b \\
P:\ce{Fe(OH)3}$^\alpha$  			  & 	$\chi ^\alpha$& 0.28 				&mol mol$^{-1}$		& b \\
P:\ce{Fe(OH)3}$^\beta$  			  & 	$\chi ^\beta$& 0.23					&mol mol$^{-1}$		& b \\
P:\ce{Fe(OH)3}$^\gamma$  			  & 	$\chi ^\gamma$& 0.11 				&mol mol$^{-1}$		& b \\
P:\ce{Fe(OH)3}$^{\beta(max)}$  		  & 	$\chi^{\beta(max)}$& 0.28 			&mol mol$^{-1}$		& b \\
P:\ce{Fe(OH)3}$^{\beta(pulse)}$  	  & 	$\chi^{\beta(pulse)}$& 0 			&mol mol$^{-1}$		& b \\
\hline      
\end{tabular}

Sources: (a) Measured; (b) Model constrained; (c) \citet{Reed2011a}; (d) \citet{Redfield1958}.
\label{Tab:Environment}
\end{table}

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Start concentrations
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

\begin{table}[H]
\centering
\caption{Boundary conditions of solids and solutes at the sediment-water interface in the model. Time dependent fluxes of OM$^{\alpha ,\beta ,\gamma}$, \ce{Fe(OH)3}$^{\alpha ,\beta ,\gamma}$, \ce{Mn(OH)2}$^{\alpha ,\beta}$, Mn carbonates and sedimentation rate at the sediment-water interface are shown in figure 3. For all chemical species a zero-gradient boundary condition was specified at the bottom of the model domain.}
\label{Tab:Boundary}
\begin{tabular}{lrl}
\hline
\textbf{Solids}  & \textbf{Flux at sediment}                &\textbf{Unit}   \\
 & \textbf{water interface}                &  \\
\hline
F FeS       & 0                      & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F \ce{FeS2} & 0                      & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F S0        & 0                      & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F \ce{FeCO3}& 0.27                   & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F Vivianite & 0 				     & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F Detr. P   & 0.034				     & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
F Auth. P   & 0.03				     & \unit{mol} \unit{m^{-2}} \unit{yr^{-1}} \\
\hline
\textbf{Solutes} & \textbf{BW concentration} & \textbf{Unit}  \\
\hline
C \ce{O2}          & 0.091           & \unit{mol} \unit{m^{-3}}     \\
C \ce{NO3^-}       & 0               & \unit{mol} \unit{m^{-3}}     \\
C \ce{SO4$^{2-}$}  & 4.05            & \unit{mol} \unit{m^{-3}}     \\
C \ce{Fe^{2+}}     & 0               & \unit{mol} \unit{m^{-3}}     \\
C \ce{Mn^{2+}}     & 0               & \unit{mol} \unit{m^{-3}}     \\
C \ce{H2S}         & 0               & \unit{mol} \unit{m^{-3}}     \\
C \ce{NH4^+}       & 0               & \unit{mol} \unit{m^{-3}}     \\
C \ce{HPO4^{2-}}  & 0.21            & \unit{mol} \unit{m^{-3}}     \\
C \ce{DIC}         & 1.5             & \unit{mol} \unit{m^{-3}}     \\
\hline
\end{tabular}
\end{table}




\begin{table}[H]
\centering
\caption{Analyses of vivianite crystals from below the SMTZ at site NB8 with electron microprobe-EDS. Vivianite crystals were collected from 3 different depths. The average value and standard deviation for each element was caulculated from 7 EDS point analyses.}
\label{Tab:EDS}
\begin{tabular}{ll}
\hline
\textbf{Element}     & \textbf{mol \%}               \\
\hline
O            & 37.8 $\pm$ 3.4 \\
Na           & 0.4  $\pm$ 0.2 \\
Mg           & 0.8  $\pm$ 0.6 \\
Al           & 6.3  $\pm$ 6.2  \\
Si           & 2.6  $\pm$ 1.5 \\
P            & 13.5 $\pm$ 5.4 \\
Ca           & 0.3  $\pm$ 0.2 \\
Mn           & 6.9  $\pm$ 2.3 \\
Fe           & 31.4 $\pm$ 6.3 \\
\hline
             & \textbf{mol mol$^{-1}$}  \\
\hline
Fe/P         & 3.3  $\pm$ 2.0 \\
Fe/Mn        & 4.7  $\pm$ 0.8 \\
(Fe+Mn)/P    & 4.1  $\pm$ 2.5 \\
Mn/P         & 0.8  $\pm$ 0.5 \\
(Fe+Mn+Mg)/P & 4.3  $\pm$ 2.5 \\
\hline
\end{tabular}
\end{table}



%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Reactions in de model
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\begin{table}[H]
\centering
\caption{Reaction equations implemented in the model.}
\label{Tab:model_reactions}
\resizebox{\textwidth}{!}{\begin{tabular}{lr}
\hline
\textbf{Primary redox reaction equations}\\
\hline
$R1=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{[\ce{O2}]}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$ \\
& E1\\
$R2=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{[\ce{NO3^-}]}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right) \left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E2\\
$R3=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{[\ce{Mn(OH)2}]}{K_{m,\ce{Mn(OH)2}}+[\ce{Mn(OH)2}]} \right)
\left(\frac{K_{m,\ce{NO3^-}}}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right) \left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E3\\
$R4=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{[\ce{Fe(OH)3}]}{K_{m,\ce{Fe(OH)3}}+[\ce{Fe(OH)3}]} \right)
\left(\frac{K_{m,\ce{Mn(OH)2}}}{K_{m,\ce{Mn(OH)2}}+[\ce{Mn(OH)2}]} \right)
\left(\frac{K_{m,\ce{NO3^-}}}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right) \left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E4\\
$R5=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{[\ce{SO4^{2-}}]}{K_{m,\ce{SO4^{2-}}}+[\ce{SO4^{2-}}]} \right)
\left(\frac{K_{m,\ce{Fe(OH)3}}}{K_{m,\ce{Fe(OH)3}}+[\ce{Fe(OH)3}]} \right)
\left(\frac{K_{m,\ce{Mn(OH)2}}}{K_{m,\ce{Mn(OH)2}}+[\ce{Mn(OH)2}]} \right)
\left(\frac{K_{m,\ce{NO3^-}}}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right)\left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E5\\
$R6=k_{\alpha,\beta}OM^{\alpha,\beta}
\left(\frac{K_{m,\ce{SO4^{2-}}}}{K_{m,\ce{SO4^{2-}}}+[\ce{SO4^{2-}}]} \right)
\left(\frac{K_{m,\ce{Fe(OH)3}}}{K_{m,\ce{Fe(OH)3}}+[\ce{Fe(OH)3}]} \right)
\left(\frac{K_{m,\ce{Mn(OH)2}}}{K_{m,\ce{Mn(OH)2}}+[\ce{Mn(OH)2}]} \right)
\left(\frac{K_{m,\ce{NO3^-}}}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right)\left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E6\\
$R7=k_1 DIC
\left(\frac{K_{m,\ce{SO4^{2-}}}}{K_{m,\ce{SO4^{2-}}}+[\ce{SO4^{2-}}]} \right)
\left(\frac{K_{m,\ce{Fe(OH)3}}}{K_{m,\ce{Fe(OH)3}}+[\ce{Fe(OH)3}]} \right)
\left(\frac{K_{m,\ce{Mn(OH)2}}}{K_{m,\ce{Mn(OH)2}}+[\ce{Mn(OH)2}]} \right)
\left(\frac{K_{m,\ce{NO3^-}}}{K_{m,\ce{NO3^-}}+[\ce{NO3^-}]} \right)\left(\frac{K_{m,\ce{O2}}}{K_{m,\ce{O2}}+[\ce{O2}]} \right)$\\
& E7\\
\hline
\textbf{Secondary redox and other reaction equations} & \\
\hline
$R8 = k_2[\ce{O2}][\ce{NH_4^{+}}]$
& E8\\
$R9 = k_3[\ce{O2}][\ce{Fe^{2+}}]$
& E9\\
$R10 = k_4[\ce{O2}][\ce{FeS}]$
& E10\\
$R11 = k_5[\ce{O2}][\ce{FeS_2}]$
& E11\\
$R12 = k_6[\ce{O2}][\sum\ce{H2S}]$
& E12\\
$R13 = k_7[\ce{O2}][\ce{CH4}]$
& E13\\
R14 = $k_8$[\ce{Fe(OH)3$^\alpha$}][$\sum$\ce{H2S}]
& E14\\
R15 = $k_9$[\ce{Fe(OH)3$^{\beta ,\beta(max) ,\beta (pulse)}$}][$\sum$\ce{H2S}]
& E15\\
$R16 = k_{10}[\ce{Fe^{2+}}][\sum\ce{H2S}]$
& E16\\
$R17 = k_{11}[\ce{FeS}][\sum\ce{H2S}]$
& E17\\
$R18 = k_{12}[\ce{S^0}]$
& E18\\
$R19 = k_{13}[\ce{Fe^{2+}}][\ce{S^0}]$
& E19\\
$R20 = k_{14}[\ce{SO_4^{2-}}][\ce{CH_4}]$
& E20\\
R21 = $k_{15}$[\ce{Fe(OH)3$^{\alpha,\beta,\beta(max),\beta(pulse)}$}][\ce{$CH_4$}]
& E21\\
R22 = $k_{16}$[\ce{Fe(OH)3$^\alpha$}]
& E22\\
$R23 = k_{17}[\ce{Fe^{2+}}][\ce{HCO_3^{-}}]$
& E23\\
$R24 = k_{18}[\ce{Fe_3(HPO_4^{2-})_2}][\sum\ce{H2S}]$
& E24\\
$R25 = k_{19}[\ce{Mn^{2+}}][\ce{HCO_3^-}]$
& E25\\
$R26 = k_{20}[\ce{Mn^{2+}}][\ce{O_2}]$
& E26\\
R27 = $k_{21}$[\ce{Mn(OH)2$^{\alpha,\beta}$}][\ce{HPO$_4^{2-}$}][\ce{Fe$^{2+}$}]
& E27\\
$R28 = k_{22}[\ce{Mn(OH)2^\alpha}][\sum\ce{H2S}]$
& E28\\
R29 = $k_{23}$[\ce{Mn(OH)2$^\beta$}][$\sum$\ce{H2S}]
& E29\\
R30 = $k_{24}$[\ce{Mn(OH)2$^\alpha$}]
& E30\\
R31 = $k_{25}$[\ce{Mn(OH)2$^{\alpha,\beta}$}][\ce{$CH_4$}]
& E31\\
R32 = $k_{26}$[\ce{Fe(OH)3$^{\beta,\beta(max),\beta(pulse)}$}][\ce{HPO$_4^{2-}$}]
& E32\\
\hline

\end{tabular}}
\small
\end{table}





%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% k-values
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

\begin{table}[H]
\centering
\caption{Reaction parameters used in the model.}
\label{Tab:k-values}
{\begin{tabular}{lllll}
\hline
\textbf{Parameter}  & \textbf{Value}  & \textbf{Unit} & \textbf{Source} & \textbf{Values in literature}               \\
\hline
k$_\alpha$                   & 0.3      & \unit{yr^{-1}}    & a,b    & 0.05-1.62                          \\
k$_\beta$                    & 0.0086   & \unit{yr^{-1}}    & b,h    & 0.0025-0.0086                      \\
K$_{O_2}$                       & 20       & \unit{\mu m} \unit{L^{-1}} & c      & 1-30                             \\
K$_{NO_3^-}$                     & 4        &\unit{\mu m} \unit{L^{-1}}& c      & 4-80                             \\
K$_{Mn(OH)_2}$                 & 4        &\unit{\mu m} \unit{g^{-1}}& c      & 4-32                             \\
K$_{Fe(OH)_3}$                 & 65       &\unit{\mu m} \unit{g^{-1}}& c      & 65-100                             \\
K$_{\ce{SO_4^{2-}}}$          & 1.6      &\unit{\mu m} \unit{L^{-1}}& c      & 1.6                                \\
k1 (E7)                      & 0.044    & \unit{yr^{-1}}    & i       & 0.0011                  \\
k2 (E8)                      & 10000    &mmol \unit{yr^{-1}} & c,d    & 5000-39000                         \\
k3 (E9)                      & 1.4*10$^5$&mmol \unit{yr^{-1}}& c      & 1.4*10$^5$           \\
k4 (E10)                     & 300      &mmol \unit{yr^{-1}}& c      & 300                                \\
k5 (E11)                     & 1        &mmol \unit{yr^{-1}}& c      & 1                                  \\
k6 (E12)                     & 160      &mmol \unit{yr^{-1}}& c      & 160                                \\
k7 (E13)                     & 10$^7$   &mmol \unit{yr^{-1}} & c      & 10$^7$               \\
k8 (E14)                     & 55       &mmol \unit{yr^{-1}}& c,g,i  & 8-100                     \\
k9 (E15)                     & 44       &mmol \unit{yr^{-1}}& c,j    & 0.004-100                     \\
k10 (E16)                    & 9000     &mmol \unit{yr^{-1}}& b,d    & 100-14800                          \\
k11 (E17)                    &10$^{-15}$&mmol \unit{yr^{-1}}& e,i    & 0.0003-3.15                        \\
k12 (E18)                    & 3        &\unit{yr^{-1}}& f      & 3                                  \\
k13 (E19)                    & 0.0025   &mmol \unit{yr^{-1}} & f,g    & 0.001-7                            \\
k14 (E20)                    & 17       &mmol \unit{yr^{-1}}& c,g    & 10(c)-120(g)                       \\
k15 (E21)                    & 0.0021  &mmol \unit{yr^{-1}}& g,i    & 1.6*10$^{-7}$ - 0.0074 \\
k17 (E23)                    & 0        &mmol \unit{yr^{-1}}& i      & 0.0027                             \\
k18 (E24)                    &8*10$^{-4}$&mmol \unit{yr^{-1}}& i      & 8*10$^{-4}$ \\
k19 (E25)                    & 0.265     &mmol \unit{yr^{-1}}&        & Model constrained                  \\
k20 (E26)                    & 1200      &mmol \unit{yr^{-1}}& c      & 800-20.000                         \\
k21 (E27)                    & 0.002     &mmol \unit{yr^{-1}}& f      & 2                                  \\
k22 (E28)                    & 0.5     &mmol \unit{yr^{-1}}& c      & $<$100.000 (20)             \\
k23 (E29)                    & 0.4    &mmol \unit{yr^{-1}}& c      & $<$100.000 (20)             \\
k24 (E30)                    & 1.8      &\unit{yr^{-1}}& f      & 1.8                                \\
k25 (E31)                    & 0.0017 &mmol \unit{yr^{-1}} &        & Model constrained                  \\
k26 (E32)                    & 3      & mmol \unit{yr^{-1}}&        & Model constrained                  \\
Vmax                         & 10$^{-6}$ & \unit{yr^{-1}}&        & Model constrained                  \\
half saturation conc. \ce{Fe^{2+}}& 1000     & \unit{\mu mol} \unit{yr^{-1}}  &        & Model constrained                  \\
half saturation conc. \ce{HPO_4^{2-}} & 1000     & \unit{\mu mol} \unit{yr^{-1}}&        & Model constrained \\
\hline
\end{tabular}}
\newline
Sources:$^a$\citep{Moodley2005}; $^b$\citep{Reed2011a}; $^c$\citep{Wang1996}; $^d$\citep{Reed2011b}; $^e$\citep{Rickard1997}; $^f$\citep{Berg2003}; $^g$\citep{Rooze2016}; $^h$\citep{Reed2016}; $^i$\citep{Egger2016a}; $^j$\citep{Egger2016b};
\end{table}


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