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Porewater nitrate profiles in sandy sediments hosting submarine groundwater discharge described by an advection–dispersion-reaction model

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Abstract

In order to separate the effects of reaction from those of transport on vertical porewater concentration profiles of nitrate at an intertidal groundwater seepage site (Ria Formosa, Portugal), a free-boundary solution of an Advection–Dispersion-Reaction (ADR) model was used to describe the shape of NO3 − concentration profiles collected in situ. The model includes three sequential reaction layers, postulated with basis on the local distribution of the benthic organic C:N ratio and major identifiable changes in concentration gradients with depth. The advective nature of the system was used to propose a mass balance simplification to the constitutive equations permitting a free-boundary solution, which in turn allowed prediction of sediment–water fluxes of NO3 −. Sensitivity analysis confirmed that in similarly advective-dominated environments, both the porewater concentration distribution and the interfacial fluxes are strongly dependant on seepage rate and benthic reactivity. The model fitted the measured profiles with high correlation (usually higher than 90%), and model-derived sediment–water NO3 − fluxes were in good agreement to fluxes measured in situ with Lee-type seepage meters (0.9948 slope, R2 = 0.8672, n = 8). Nitrate oxidation and reduction rates extracted from model fits to the data (10−2–100 mmol m−2 h−1) agreed with literature values. Because dispersive effects are not included in direct mass balances based on the porewater concentrations, the model presented here increases the accuracy of apparent reaction rate estimates and geochemical zonation at Submarine Groundwater Discharge (SGD) sites. The results establish the importance of sandy sediments as reactive interfaces, able to modulate mass transfer of continental-derived contaminants into coastal ecosystems. We suggest that tools such as the one described here might be used to advantage in preparing further experimental studies to elucidate how benthic reactivity affects nitrate distribution and fluxes in sediments affected by SGD.

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Abbreviations

z :

Depth (L)

\( \hat{C}(z) \) :

Concentration of solute per sediment volume (M L−3)

C 0 :

Concentration of solute per sed. vol. at the upper interface (M L−3)

C aq :

Concentration of solute per sed. vol. at the lower interface (M L−3)

D molec :

Molecular diffusion in water (L2 T−1)

D if :

Molecular diffusion in sediment (L2 T−1)

D isp :

Mechanical dispersion (L2 T−1)

D ef :

Efective dispersion (L2 T−1)

v :

Advective velocity (L T−1)

K n :

Nitrification rate (M L−3 T−1)

K d :

Nitrate reduction rate (T−1)

L x :

Layer depth limit (L)

P e :

Peclet number

D a1 :

Damköhler number for nitrification

D a2 :

Damköhler number for nitrate reduction

J :

Flux per area of total sediment (M L−2 T−1)

φ :

Porosity

θ :

Tortuosity

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Acknowledgments

The authors gratefully acknowledge M. Simão, S. Pólvora and C. Moita for their help during fieldwork. The “Laboratório de Análises Químicas” kindly offered the room and spectrophotometer time required for nutrient analysis. Financial support was provided by the Portuguese Foundation for Science and Technology (FCT) through grant contracts SFRH/BD/39170/2007 (Fellowship to JSPI) and SFRH/BD/38856/2007 (Fellowship to CL), and project O-DOIS: Oxygen dynamics coupled to carbon mineralization in sandy intertidal sediments, contract ref: POCTI/CTA/47048/2002. The two anonymous reviewers and the editor are acknowledged for their constructive comments which helped to improve the earlier draft of the manuscript.

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  1. School of Natural Sciences, Trinity College, Dublin, Ireland

    J. Severino P. Ibánhez & Carlos Rocha

  2. Department of Marine Chemistry and Geology, Royal Netherlands Institute for Sea Research (Royal NIOZ), Texel, The Netherlands

    Catarina Leote

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  1. J. Severino P. Ibánhez
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  2. Catarina Leote
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  3. Carlos Rocha
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Correspondence to J. Severino P. Ibánhez.

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Ibánhez, J.S.P., Leote, C. & Rocha, C. Porewater nitrate profiles in sandy sediments hosting submarine groundwater discharge described by an advection–dispersion-reaction model. Biogeochemistry 103, 159–180 (2011). https://doi.org/10.1007/s10533-010-9454-1

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