Análisis y Modelado Del Comportamiento de Lixiviación PDF

Universidad de Cantabria
Escuela Técnica Superior de Ingenieros Industriales y de

Telecomunicación
Departamento de Ingeniería Química y Química Inorgánica
ANÁLISIS Y MODELADO DEL COMPORTAMIENTO DE LIXIVIACIÓN

DE METALES DE SEDIMENTOS CONTAMINADOS EN CONTACTO
CON FUGAS DE CO2 PROCEDENTES DE SISTEMAS DE CAPTURA
Y ALMACENAMIENTO DE CARBONO (CAC)
ANALYSIS AND MODELING OF METAL RELEASE FROM CONTAMINATED

SEDIMENT SUBJECT TO CO2 LEAKAGES FROM CARBON CAPTURE AND
STORAGE (CCS) SITES
Memoria de Tesis Doctoral presentada para optar al título de Doctor por la Universidad de
Cantabria
Programa Oficial de Doctorado en Ingeniería Química y de Procesos (BOE núm. 36, de 10 de

febrero de 2010. RUCT: 5311209) con Mención hacia la Excelencia (BOE núm. 253, de 20 de
octubre de 2011. Referencia: MEE2011-0031)
María Cruz Payán Fraile
Directores de Tesis:
Javier R. Viguri Fuente
Alberto Coz Fernández Santander, Abril 2013

Esta tesis doctoral se presenta en la modalidad de compendio de trabajos publicados
previamente o aceptados para publicación en revistas científicas de carácter internacional
incluidas en el Journal of Citation Reports-Science Edition (JCR-SCE), cumpliendo con los
criterios y bases establecidos para ello en la “Normativa de los Estudios de Doctorado de la
Universidad de Cantabria” y en la “Normativa para la elaboración de Tesis Doctorales como
compendio de artículos en el Programa de Doctorado de Ingeniería Química de la Universidad
de Cantabria”, establecida en el Departamento de Ingeniería Química y Química Inorgánica.
Durante el periodo de investigación se ha realizado una estancia predoctoral de tres meses en la
Katholieke Universiteit Leuven (Bélgica).
Los artículos que constituyen el cuerpo de esta tesis se encuentran dentro de la línea y objetivos
de investigación basados en el comportamiento de lixiviación de metales de sedimentos
contaminados en contacto con fugas de CO2 procedentes de sistemas de captura y
almacenamiento de carbono. Dichos artículos se han elaborado de una manera secuencial en el
tiempo e interrelacionada en sus aspectos científicos, de acuerdo a los objetivos planteados en
el trabajo de investigación, mostrándose así en la presente tesis doctoral. A continuación se
indican los artículos ya publicados en el marco de esta tesis:
Payán, M.C., Verbinnen, B., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012. Potential
influence of CO2 release from a carbon capture storage site on release of trace metals from
marine sediment. Environmental Pollution 162, 29-39.
Payán, M.C., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012. Evaluation through
column leaching tests of metal release from contaminated estuarine sediment subject to CO2
leakages from Carbon Capture and Storage sites. Environmental Pollution 171, 174-184.
Payán, M.C., Galan, B., Ruiz, G., Coz, A., Viguri, J.R., 2013. Pb and Zn release from intertidal
marine sediment in contact with acidified CO2 seawater: mathematical model for column leaching
tests. Chemical Engineering Science 95, 85-93.
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AGRADECIMIENTOS / ACKNOWLEDGMENTS
Esta tesis doctoral ha sido realizada en el marco del Subprograma de Formación de Personal
Investigador (F.P.I.), mediante una beca y posterior contrato concedidos por el Ministerio de
Ciencia e Innovación de España a la autora de la tesis, María Cruz Payán Fraile, desde el 1 de
agosto de 2009 (referencia BES-2009-015845), así como de una ayuda para llevar a cabo una
estancia breve de investigación en KU Leuven (Lovaina, Bélgica).
Los trabajos de investigación realizados contaron además con el apoyo económico del proyecto
del Ministerio Ciencia e Innovación español CTM2008-06344-C03-01.
This doctoral thesis has been carried out within the framework of the Subprogram for Training of
Researcher Staff (F.P.I. “Formación de Personal Investigador”), by means of a fellowship and
subsequent contract awarded by the Spanish Ministry of Science and Innovation to the author of
the thesis, María Cruz Payán Fraile, from 1st August 2009 (reference BES-2009-015845), in
addition to financial help to undertake a short research stay at KU Leuven (Leuven, Belgium).
The research work conducted also had the financial support of the Spanish Ministry of Science
and Innovation project CTM2008-06344-C03-01.
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En primer lugar, mi más sincero agradecimiento a mis directores de tesis, Javier Viguri y Alberto
Coz. Por confiar en mí desde el principio, por la ayuda y dedicación que me han ofrecido en todo
momento y por enseñarme a amar la investigación.
A Ana Andrés, por ser una de las primeras personas en animarme a entrar en este mundo y
empezar así un doctorado.
A Berta Galán y Gema Ruiz y al resto del grupo GER por ser tan buenos compañeros de trabajo
y por los buenos momentos pasados juntos en comidas, seminarios y celebraciones. También
me gustaría dar las gracias a toda la gente del Departamento de Ingeniería Química y Química
Inorgánica.
I am very grateful to Carlo Vandecasteele (KU Leuven) for giving me the opportunity to undertake
a research stay under his supervision in Leuven and for his kindness and advice during my time
in Belgium. I would also like to thank all the people I worked with in Leuven. I had very nice time
there!!
My thanks also go to all the people who were with me in Germany and gave me the first idea of
doing a PhD.
A mis padres, por apoyarme siempre y comprender mi forma de ser. A mis hermanas, porque la
distancia no impide mantenernos unidas y por enseñarme a ver el cielo más azul. Os echo
mucho de menos.
Por supuesto, quiero dar las gracias a toda la gente con la que he convivido durante estos años
en la lluviosa Santander, too many to be named y que han querido compartir conmigo su tiempo
y seguro enseñarme algo que ha contribuido en mi forma de ser.
Y finalmente, aquí está la tesis y aquí termina una etapa.
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TABLE OF CONTENTS
AGRADECIMIENTOS/ACKNOWLEDGMENTS ii
TABLE OF CONTENTS v
RESUMEN GENERAL 1
ABSTRACT 9
1. GENERAL INTRODUCTION 17
1.1. Global climate change and possible mitigation options 19
1.2. The Carbon Capture and Storage (CCS) technology 20
1.2.1. The CCS three-step process 21
1.2.2. Legal framework for CCS 22
1.2.3. CCS projects around the world 23
1.3. CO2 sequestration in sub-seabed geological structures 24
1.4. Risk assessment and management of storage of CO2 streams in geological

formations 26
1.4.1. Risk of CO2 leakages in the marine environment 31
1.5. The leaching process 33
1.5.1. Objectives and principles of leaching tests 33
1.5.2. Basic characterization tests 34
1.5.3. Compliance tests 35
1.6. Modeling of the leaching tests results 36
1.7. Objectives and thesis structure 38
1.8. References 40
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2. ARTÍCULOS CIENTÍFICOS/SCIENTIFIC PAPERS 49
2.1. Payán, M.C., Verbinnen, B., Galan, B., Coz, A., Vandecasteele, C., Viguri, 51
J.R., 2012. Potential influence of CO2 release from a carbon capture storage site
on release of trace metals from marine sediment. Environmental Pollution 162, 29-
39.
2.2. Payán, M.C., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012. 64
Evaluation through column leaching tests of metal release from contaminated
estuarine sediment subject to CO2 leakages from Carbon Capture and Storage
sites. Environmental Pollution 171, 174-184.
2.3. Payán, M.C., Galan, B., Ruiz, G., Coz, A., Viguri, J.R., 2013. Pb and Zn 77
release from intertidal marine sediment in contact with acidified CO2 seawater:
mathematical model for column leaching tests. Chemical Engineering Science 95,
85-93.
3. PROCEDURES AND MATERIALS USED. OVERALL SUMMARY OF RESULTS AND

DISCUSSION 91
3.1. Tier approach procedure 93
3.2. Sediment characterization 94
3.2.1. Area of study: Suances estuary 94
3.2.2. Sediment sampling and characterization 96
3.3. Leaching tests 98
3.3.1. Leaching solutions 98
3.3.2. Leaching tests procedure 100
3.3.3. Analyses of the leachates 110
3.4. Modeling of the leaching results 111
3.4.1. Empirical modeling 111
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3.4.2. Mathematical modeling of column leaching results with Aspen Custom
Modeler 112
3.4.3. Geochemical modeling with Visual MINTEQ 113
3.5. Discussion of results 114
3.5.1. Sediment characterization results 114
3.5.2. Equilibrium leaching test results 123
3.5.3. Column leaching test results 126
3.5.4. pH dependence leaching test results 142
3.6. References 149
4. CONCLUSIONS AND FUTURE WORK 159
4.1. Conclusions 161
4.2. Future work 163
APPENDIX. DISSEMINATION OF RESULTS 165
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La facilidad para soñar hace que, aunque se te trunquen algunos planes, siempre tengas
otros con los que continuar soñando.
RESUMEN GENERAL
Resumen general
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Resumen general
RESUMEN GENERAL
La Captura y Almacenamiento de Carbono (CAC) es una tecnología que tiene como objetivo
capturar CO2 gaseoso de su fuente de emisión y depositarlo bajo tierra con una permanencia del
99% en al menos 100 años. La tecnología CAC se considera una de las opciones más
prometedoras para mitigar las emisiones atmosféricas de CO2 procedentes de la utilización a
gran escala de combustibles fósiles y el subsiguiente cambio climático. El secuestro geológico de
CO2 implica su inyección a grandes profundidades oceánicas, bajo la superficie, normalmente en
acuíferos salinos profundos, en reservas agotadas de gas y petróleo, en recuperación mejorada
de petróleo (EOR) y gas (EGR) y en minas de carbón. La Captura, Utilización y Almacenamiento
de Carbono (CCUS) es una tecnología innovadora que conlleva el uso productivo de la captura
de CO2 relacionado con la utilización de CO2 para fines beneficiosos como los sistemas EOR. El
secuestro de CO2 en formaciones geológicas del fondo marino se encuentra entre las técnicas
más estudiadas en la actualidad por la comunidad investigadora internacional debido a su
potencial para reducir los gases de efecto invernadero. El marco legal para las tecnologías CAC
está basado en las enmiendas adoptadas por el Protocolo de Londres y la Convención OSPAR
que permiten y regulan el almacenamiento de CO2 de sistemas CAC en formaciones geológicas
bajo el lecho marino. La Directiva Europea para el almacenamiento geológico de CO2 establece
el marco legal para esta actividad de una forma segura para el medio ambiente y haría viable el
desarrollo y uso sostenible de las tecnologías CAC. La acidificación del medio marino y potencial
contaminación por sustancias peligrosas debido a su movilidad de sedimentos contaminados en
contacto con agua de mar acidificada, es motivo de preocupación en el marco de protección del
medio marino de la UE establecido bajo la Directiva de Estrategia Marina.
Durante el secuestro geológico, el CO2 se almacena por atrapamiento hidrodinámico, mineral o

por solubilidad. Se prevé que la inyección de CO2 mediante tecnologías CAC ocupará grandes
áreas. Aunque el CO2 es inyectado en la parte más baja de la formación del almacén, es poco
probable que la roca sea perfectamente homogénea e impermeable en esas zonas; la presencia
de heterogeneidades y barreras discontinuas, con zonas de fallas y fracturas, hace que el CO2
se mueva hacia arriba entre las barreras, creando un penacho extenso y sinuoso donde el CO2
se desplaza y se disuelve en el agua de poro. En términos de riesgo, se han identificado cuatro
formas de fuga de CO2: difusión a través de la roca, fuga a través de los espacios porosos
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Resumen general
cuando se sobrepasa la presión capilar, fuga a través de fracturas, y fugas en pozos cuando se
degradan o abandonan inapropiadamente. La disolución de CO2 en la fase fluida, directamente
en el acuífero salino del almacén (salmueras acuosas) o durante la fuga de CO2 gaseoso a
cortas o largas distancias (agua de poro, agua de mar, agua subterránea) produce fluidos ácidos
ricos en CO2. Estos fluidos pueden fugar de la misma manera que el CO2 gaseoso (difusión
vertical y horizontal a través de capas confinadas y sedimento, advección a través de fracturas y
fallas). Tales fugas pueden disolver la roca y estarían en contacto con distintas capas de la
formación, incluyendo sedimentos contaminados.
Se hace necesario por tanto, evaluar las consecuencias de las fugas potenciales de CO2 de
zonas de almacenamiento geológico en la superficie del sedimento y en el fondo del mar. Los
contaminantes pueden liberarse de los sedimentos en medios acidificados. La evaluación de la
biodisponibilidad de estos contaminantes en el medio es importante para la salud y es crítico
entender los riesgos ecológicos en los sistemas acuáticos. Así, la evaluación del modelo de
riesgo a aplicar, tiene que tener en cuenta la evaluación de los efectos de las concentraciones de
CO2, incluyendo como factores principales la salud, los receptores potenciales dentro del medio
marino y la liberación de metales del agua de mar y sedimentos en un medio ácido. Para evaluar
la contaminación marina procedente de sedimentos en contacto con fugas de CO2, es necesaria
la determinación cualitativa y cuantitativa de contaminantes, así como las características de
movilidad bajo diferentes escenarios de acidificación.
El principal objetivo de esta tesis es generar nuevo conocimiento sobre los potenciales efectos
de las fugas de CO2 en sedimentos marinos contaminados de sistemas CAC a través del
análisis, modelado y evaluación de la movilidad de metales y carbono orgánico disuelto (COD)
debido a fugas de CO2. El alcance de este objetivo principal se lleva a cabo por medio de una
estrategia estructurada que consiste en cuatro etapas de investigación escalonadas. Las etapas
1 y 2 engloban la caracterización ambiental y físico-química del sedimento de una zona de
potencial almacenamiento de CO2 en el estuario de Suances, al norte de España. La etapa 3 se
centra en el comportamiento de los parámetros globales (pH, conductividad y COD) de los
ensayos de lixiviación. La etapa 4 comprende la evaluación de la liberación de metales en
función del pH y L/S bajo diferentes escenarios de acidificación utilizando distintos ensayos de
lixiviación.
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Resumen general
El grupo Europeo CEN/TC 292 especifica varios ensayos de lixiviación estandarizados para la
caracterización de residuos, suelos y sedimentos. Los ensayos de lixiviación estandarizados y
sus versiones modificadas, han sido ampliamente usados en este tipo de matrices para estudiar
los mecanismos de reacción o para estudiar procesos de carbonatación (acelerada y natural) a
través de procesos de análisis, modelado y optimización, entre otros propósitos.
En esta tesis, la influencia de las fugas de CO2 en la lixiviación de metales y COD de sedimentos
marinos contaminados se lleva a cabo utilizando ensayos de lixiviación. Se realizan ensayos de
lixiviación de equilibrio a ratios L/S de 2, 4, 10, 15, 20, 30 y 40 L/kg basados en la norma EN
12457. Se llevan a cabo ensayos de lixiviación en columna de acuerdo a la norma modificada
CEN/TS 14405. Como agentes de lixiviación se usan agua desionizada, agua de mar (pH 8) y
agua de mar acidificada, mediante burbujeo directo de CO2, a distintos valores de pH (5, 6 y 7).
El ensayo de lixiviación de dependencia de pH CEN/TS 14429 se realiza en el rango completo
de pH (0-14) utilizando agua desionizada y agua de mar como agentes de lixiviación. El empleo
de agua de mar acidificada ayuda a simular diferentes condiciones de acidificación del medio
marino debido a fugas de CO2 de CAC y debido a vertidos ácidos al agua de mar. Basándose en
los resultados de las etapas 1 y 2, los parámetros analizados en los lixiviados fueron pH,
conductividad, COD y la concentración de los contaminantes As, Cd, Cr, Cu, Ni, Pb y Zn.
Se asume una estrategia escalonada de análisis de los resultados; se parte de análisis empíricos
simples, utilizando el menor número de parámetros a ajustar sin significado físico;
posteriormente análisis semi empíricos, utilizando expresiones matemáticas con parámetros con
significado físico y finalmente, el uso de modelos geoquímicos para predecir el comportamiento
de las especies presentes en el sedimento. Las expresiones matemáticas empíricas y semi
empíricas se usan para ajustar la liberación acumulada de metales y COD en función del ratio
L/S y del pH de los ensayos de lixiviación en columna. Los resultados experimentales de los
ensayos de lixiviación de dependencia de pH se modelan con el software geoquímico Visual
MINTEQ. Las fases sólidas mayoritarias presentes en el sedimento y las posibles fases sólidas
de los metales de estudio, complejos químicos con DOC y adsorción en hidróxidos de hierro, se
modelan en agua desionizada y en agua de mar. Adicionalmente, se propone un modelo
matemático de las cinéticas de liberación de Pb y Zn de sedimentos marinos con agua de mar
acidificada con CO2 a valores de pH entre 5 y 8 utilizando ensayos de lixiviación en columna.
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Resumen general
Los ensayos de lixiviación de equilibrio alcanzan un mínimo de pH de 6.8 para los lixiviados de
agua de mar. La fuerte influencia de la acidificación del agua de mar en la lixiviación de los
metales del sedimento se acentúa con el aumento de la concentración para As, Cd, Ni, Pb y Zn.
Se estudian ratios L/S>10 para determinar los mecanismos de lixiviación: sólo Cd, Ni y Zn
muestran mecanismos controlantes de disponibilidad a valores específicos de pH y agentes de
lixiviación. El resto de los casos estudiados no muestran un mecanismo de control predominante.
Los ensayos de lixiviación en columna presentan una liberación acumulada del metal que es
función lineal del ratio L/S hasta el final del test (L/S=10 L/kg). A pesar de la capacidad de
neutralización del sistema agua de mar-sedimento, se esperan acidificación y liberaciones
importantes a escala local a bajos valores de pH. La lixiviación del DOC es importante al pH del
agua de mar natural y en condiciones ligeramente ácidas; en un escenario de fugas de CO2 el
mero burbujeo de CO2 movilizaría grandes cantidades de DOC y, en etapas sucesivas,
complejaría los metales movilizados debido a la acidificación gradual del agua de mar. El modelo
cinético propuesto para la lixiviación en columna de Pb y Zn, considera la transferencia de masa
externa y la difusión en la fase sólida, obteniendo buena concordancia entre los valores de
concentración experimentales y modelados bajo diferentes condiciones ácidas; mediante el
software Aspen Custom Modeler, se obtienen los valores de difusión efectiva del sólido
Def,Zn=1.21 10-12 m2/s y Def,Pb=1.56 10-13 m2/s, así como los valores de difusión superficial en la
fase sólida para cada pH experimental.
El sedimento estudiado muestra una alta capacidad de neutralización ácida tanto en agua
desionizada (ANCpH=4=3.58) como en agua de mar (ANCpH=4=3.97). La capacidad buffer del agua
de mar también tiene influencia en el test debido a que se necesitan cantidades ligeramente
mayores de ácido y base para conseguir el mismo valor de pH y mayor número de réplicas para
alcanzar la condición de equilibrio. La lixiviación de metales con agua desionizada y agua de mar
presenta resultados y tendencias similares, aunque la lixiviación de metales es ligeramente más
alta cuando se emplea agua desionizada; estos resultados de concentración fluctúan más con el
pH al emplear agua de mar. El modelado geoquímico mediante Visual MINTEQ muestra
diferencias muy pequeñas entre los resultados con agua de mar y agua desionizada para As, Cd
y Pb. Los resultados modelados muestran concentraciones de metal con diferencias máximas de
un orden de magnitud respecto a los resultados experimentales para la mayoría de los metales.
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ABSTRACT
Abstract
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Abstract
ABSTRACT
Carbon Capture and Storage (CCS) is a technology which aims to capture CO2 gas from its point
source of emission and deposit it underground with 99% permanence over at least 100 years.
CCS is considered as one of the most promising options to mitigate atmospheric emissions of
CO2 from large-scale use of fossil fuels and subsequent climate change. Geologic sequestration
of CO2 involves the injection of the carbon dioxide into deep oceans, into the subsurface, typically
into deep saline aquifers, in depleted oil and gas reservoirs, in enhanced oil and gas recovery
(EOR and EGR, respectively) and in unminable coal seams. Carbon capture, utilization, and
storage (CCUS) is a rising technology entailing the productive use of the captured carbon dioxide
related to the use of CO2 for beneficial purposes as EOR.
Sequestration of CO2 in sub-seabed geological formations is currently among techniques

intensely studied by the international research community for their potential to reduce greenhouse
gases. The legal framework for CCS technologies is based on the amendments adopted by the
London Protocol and the OSPAR Convention that allows and regulates the storage of CO2 from
CCS systems in geological formations under the seabed. The EU Directive on the geological
storage of CO2 establishes the legal framework to this activity in a safety way to the environment
and would make feasible the sustainable develop and deployed of the CCS technologies. The
marine environment acidification and the potential contamination by hazardous substances due to
their mobilization from contaminated sediment in contact with acidified marine water, is a subject
of concern in the framework of the UE marine environment protection established under the
Marine Strategy Framework Directive.
During geologic sequestration, CO2 is stored via hydrodynamic, solubility or mineral trapping.
Injection of CO2 by CCS technologies will occupy extensive areas. Although CO2 is injected into
the lower part of the storage formation, it is unlikely that cap rock will be perfectly homogeneous
and impermeable in that areas; the presence of heterogeneity and discontinuous barriers, with
faults and fracture zones, make the buoyant CO2 will move upward between the barriers, creating
a sinuous extensive plume where CO2 displace and dissolve in native pore water.
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Abstract
In terms of risk, four ways of CO2 release have been identified: diffusive loss through the cap
rock, leakage through pore spaces when capillary breakthrough pressure has been exceeded,
leakage through faults or fractures, and well leakage when wells are degraded or inappropriately
abandoned. The dissolution of CO2 into a fluid phase, directly in the saline aquifer of storage
(aqueous brines) or during the CO2 gas leakage at short or long distances (native pore water,
seawater, groundwater) generates acidic CO2 rich fluids. These fluids can leak in the same way
that CO2 gas (vertical and horizontal diffusion through confining layers and sediment, advection
through fractures and faults, contact in bulk). Such leakages can dissolve the cap rock and would
be in contact with different formation layers including contaminated sediment cores.
The consequences of potential CO2 leakages from geological storage sites into surface sediment
and into deep sea are then necessary to be evaluated. Trace metals and organic contaminants
would be release from contaminated sediment due to the seawater acidification. The
bioavailability assessment of these contaminants in the environment is important for health and it
is critical to understand the ecological risks in aquatic systems. Thus, the model of risk
assessment to be applied has to take into account the effect assessment of CO2 concentrations
including as the main factors human health, potential receptors within the marine environment
and chemicals released from seawater and sediment in a decreased pH environment. To assess
the marine contamination from sediment in contact with CO2 leakages, it is necessary the
qualitative and quantitative determination of contaminants as well as the characterization of their
mobility characteristics under different acidified scenarios.
The general objective of this thesis is to generate new knowledge about the potential effects of
CO2 leakages on contaminated marine sediment in CCS systems by means of the analysis,
modeling and assessment of the mobility of metals and dissolved organic carbon (DOC) due to
CO2 leakages. The achievement of this general objective is accomplished through a Tier
structured approach consists of four tiers of investigation. Tier 1 and 2 comprise the
environmental and physico-chemical characterization of the sediment from a potential CO2
storage area in Suances estuary, Northern Spain. Tier 3 focuses on the global parameter
behavior (pH, conductivity and DOC) of the leaching tests. Tier 4 comprises the assessment of
metal release as a function of pH and L/S under different scenarios of acidification using different
leaching tests. In addition, the modeling of the behavior of this metal release is carried out.
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Abstract
The European group CEN/TC 292 specifies several standardized leaching tests for waste
materials, soil and sediment characterization. Leaching standard tests and modified versions
have been widely used with these matrices to study the reaction mechanisms or to study
carbonation processes (gas, liquid or supercritical accelerated carbonation and natural ageing) by
the process parameter analysis, modeling and optimization, among other purposes.
In this thesis, the influence of CO2 leakage on metal and DOC leaching from contaminated
marine sediment is addressed using leaching tests. Equilibrium leaching tests at L/S ratios of 2,
4, 10, 15, 20, 30 and 40 L/kg were performed based on EN 12457. Column leaching tests were
carried out according to a modified version of CEN/TS 14405. Deionized water, seawater (pH 8)
and acidified seawater at different pH values (5, 6, and 7) obtained by CO2 bubbling, were
employed as leaching solutions. The modified CEN/TS 14429 pH dependence leaching test was
performed in the whole pH range (0-14) using deionized water and seawater as leaching
solutions. The use of acidified seawater helps to mimic different acidification conditions of the
marine environment due to CO2 leakages from CCS and due to accidental acid spills to seawater.
The parameters in the leachates pH, conductivity, Dissolved Organic Carbon (DOC) and As, Cd,
Cr, Cu, Ni, Pb and Zn were considered based on Tier 1 and 2 results.
A stepwise strategy with different analysis approaches is conducted to fit DOC and metal
concentrations in leachates as a function of L/S ratio and pH; (i) from the simplest empirical
analysis, using the lowest number of adjustable parameters without physical meaning, (ii) to semi
empirical analysis, using mathematical expressions with parameters with physical meaning, and,
(iii) the use of geochemical models to model the dominant speciation of each component of
interest as a result of aqueous reactions and physico-chemical phenomena of the studied metals
in sediment. In this case, Visual MINTEQ geochemical software to predict metal release from
sediment has been used together with the experimental results of the pH dependence tests. The
major solid phases present in the sediment and the possible solid phases of the metals under
study, organic matter complexation and hydrous ferric oxide (HFO) adsorption, are modeled in
both deionized water and seawater. Finally, a mathematical model of the kinetics of Pb and Zn
release from marine sediment with CO2 acidified seawater at pH values of 5, 6, 7 and 8 using
column leaching tests is proposed; the Freundlich equation is used for the description of the
equilibrium process and the parameters are estimated by the model.
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Abstract
According to the leaching results, equilibrium leaching tests reach a lowest pH of 6.8 for seawater
leachates. The strong influence of seawater acidification on metal leaching from sediment due to
CO2 leakage is emphasized with the increase of concentration for As, Cd, Ni, Pb and Zn. Higher
L/S ratios than 10 were studied in order to determine the leaching mechanisms. Only Cd, Ni and
Zn show availability control mechanism at specific pH values and leaching agents. For the rest of
the studied cases, no clear dominant leaching mechanism exists.
A cumulative metal release as a linear function of the L/S ratio until the end of the test (L/S=10
L/kg) is shown for column leaching tests. Despite the neutralization capacity of the seawater-
carbonate rich sediment system, important acidification and releases are expected at local scale
at lower pH. The DOC leaching is high at seawater natural pH and slightly acidic conditions; in a
CO2 leakage scenario the CO2 bubbling at seawater natural pH would mobilize high quantities of
DOC and, in latter steps, would complex metals mobilized by the gradual seawater acidification.
The kinetic model proposed for Pb and Zn column leaching considers external mass transfer and
solid phase diffusion, obtaining a good agreement between experimental and modeled values
under different acidic conditions; using Aspen Custom Modeler software, the effective solid
diffusion values Def,Zn=1.21 10-12 m2/s and Def,Pb=1.56 10-13 m2/s and the solid-phase surface
diffusion values for each pH experiment are obtained.
Regarding the results of the pH dependence tests, the studied sediment shows a high acid
neutralization capacity when using deionized water (ANCpH=4=3.58) and seawater
(ANCpH=4=3.97). The buffering capacity of the seawater also influences the test due to the fact
that a slightly higher amount of acid or base are needed to achieve the same value of pH and
higher number of replicates are necessary to reach the equilibrium condition. Metal leaching for
deionized water and seawater presents similar results and tendencies, although metal leaching is
slightly higher when using deionized water and these concentration results fluctuate more with pH
when using seawater. Experimental results modeled with Visual MINTEQ geochemical model
show minor differences between seawater and deionized water for As, Cd and Pb. The modeling
results show metal concentrations with differences of zero and one orders of magnitude respect
to the experimental results for most studied contaminants.
14
15
16
GENERAL INTRODUCTION
General introduction
18
1. GENERAL INTRODUCTION
1. 1. Global climate change and possible mitigation options
Concern about global climate change, and the challenges and risks it poses, will require
sustained efforts to develop understanding and effective solutions while at the same time meeting
the growing needs of society for energy. Oil, coal and gas are the dominant current sources of
energy. Over the next 30 years, energy use is forecast to grow by more than 50 per cent (EIA
Report, 2011). Climate change presents a long-term risk associated with the build-up of carbon
dioxide (CO2, primarily from fossil fuel use) and other greenhouse gases in the atmosphere.
Figure 1.1 shows the increasing evolution of atmospheric CO2 concentrations since 1959 (CO2
Now, 2013). The oceans are a natural carbon sink and have so far absorbed approximately half of
all anthropogenically produced CO2 (Siegenthaler and Sarmiento, 1993). Since ca. 1760, the pH of the
ocean´s surface (the upper 200 m of the water column) has decreased by approximately 0.1 of a
unit, and further reductions of 0.1 to 0.5 units are expected during the next 100 years (Caldeira and
Wickett, 2003, 2005; Orr et al., 2005).
410
390
Atmospheric CO2 (ppm)
370
350
330
310
290
1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015
Year
Figure 1.1. Evolution of atmospheric CO2 concentrations since 1959 (CO2 Now, 2013)
Pressure to reduce CO2 emissions in response to the threat to global warming has highlighted
various mitigation options. Carbon dioxide Capture and Storage (CCS) is one of a portfolio of CO2
mitigation methods to avoid anthropogenic climate change (Kharaka et al., 2008; Li et al., 2009; Eke et
al., 2011; Hosa et al., 2011). Other mitigation options include increased energy efficiency, renewable
19
energy sources, enhancement of biological sinks, nuclear power, advanced coal, reduction of
non-CO2 greenhouse gas emissions and plug-in hybrid electric vehicles (IPCC, 2007, 2011; Kharaka
et al., 2008). Under certain assumptions CCS can contribute globally up to 20% of necessary
emission reductions by 2050. One of the most promising places to store the resulting large
volumes of CO2 for a long time is in sedimentary rocks below the continental margins.
1.2. The Carbon Capture and Storage (CCS) technology
Carbon dioxide capture and storage (CCS) is a process consisting of the separation of CO2 from
industrial and energy-related sources, transport to a storage location and long-term isolation from
the atmosphere with 99% permanence over at least 100 years (IPPC, 2005, 2007). Among the
various possible repositories for storing CO2, deep geological formations are most promising in
terms of capacity and duration of storage, technical feasibility and minimal environmental impact
(Wang and Jaffle, 2004). However, a full understanding of long-term environmental risks is needed
before large-scale CCS implementation is feasible (Wang and Jaffle, 2004; Little and Jackson, 2010).
One of the risks associated with this technology lies in possible CO2 migration or leakages from
the storage site (Little and Jackson, 2010; Basallote et al., 2012). CCS can be separated into three
elements (Brown et al., 2011) as shown in Figure 1.2.
Figure 1.2. The main steps of CCS processes (SCCS and Scottish Enterprise, 2012)
20
1.2.1. The CCS three-step process
The capture process consists of the separation of CO2 from an effluent stream and its
compression to a liquid or supercritical state. In most cases today, the resulting CO2
concentration is greater than 99%, though lower concentrations may be acceptable (Brown et al.,
2011). Three processes are available for the capture of CO2 from such large point sources: post-
combustion capture, pre-combustion capture and oxyfuel combustion (IPCC, 2007).
CO2 injection streams may contain other substances derived from the source material (RAMF,
2006). At present, European regulation does not set quantitative limits on the composition of a
captured CO2 stream. Impurities in CO2 streams can include nitrogen (N2), oxygen (O2) and water
(H2O), but also air pollutants such as sulphur and nitrogen oxides (SOx and NOx), particulates,
hydrochloric acid (HCl), hydrogen fluoride (HF), mercury, other metals and trace organic and
inorganic contaminants (Mikunda and de Coninck, 2011). The types of impurities that may be present
in a CO2 stream destined for CO2 storage depends on fuel type, the nature of the process and the
application of capture and separation technologies.
For the large-scale CO2 transport from the CO2 capture locations to the location of the geological
storage sites, pipelines, ships and tanker trucks are considered the most likely means of
transport. Apart from cost, the mode of transportation can be linked to the amount of CO2 being
transported and the distance between the production and injection sites. Injection depth is one of
the important characteristics of an injection site. The shallower the reservoir, the more
commercially feasible it is to inject CO2. However, it cannot be too shallow since CO2, the injected
gas, should remain in the dense or supercritical state after the injection (at least 800 m of
overlying rock is recommended). It is observed that most of the projects are between 1000 and
2500 m deep (Hosa et al., 2011).
The liquid or supercritical CO2 is injected into the storage reservoir, which can be either a
geological reservoir or the ocean. Captured CO2 could be deliberately injected into the ocean at
great depth, where most of it would remain isolated from the atmosphere for centuries. There is
great uncertainty regarding the storage capacity. Global potential in geological reservoirs is within
the range of about 476-5880 Gt CO2, with a best estimate of 1660 Gt (Bode and Jung, 2006). The
21
geographical distribution of the possible storage capacity differs for different types of reservoirs.
Saline aquifers seem to be distributed most evenly across the world, but also the distance to
large amounts of point sources of CO2 is of relevance (Bode and Jung, 2006; IPCC, 2007). Table 1.1
presents the geological reservoir types and their estimated global storage capacity (Damen et al.,
2006).
Table 1.1. Geological reservoir types and estimated global storage capacity (Damen et al., 2006)
Reservoir type Global capacity (Gt CO2)
Depleted oil and gas fields 920
Deep saline aquifers 240-10000
Unminable coal seams 40-270
1.2.2. Legal framework for CCS
The current status of CCS regulation varies significantly across the world. Some of the most
significant regulations for the geologic storage of CO2 are the EU CCS and Marine Directives,
London Protocol and OSPAR Convention (Condor et al., 2011). There are existing national and
international legislations which may be applicable to onshore and offshore CCS (Ogunlade, 2011).
Table 1.2 gathers the applicable international, European and national (Spanish) legislations on
CCS.
Table 1.2. Applicable international, European and Spanish legislations on CCS

International Legislation
1996 Protocol to the 1972 Convention on the Prevention of Marine Pollution by Dumping of Wastes and
other Matter (the “London Convention”)
Convention for the Protection of the Marine Environment of the North East Atlantic (the “OSPAR
Convention”)
European Legislation
Directive on the Geological Storage of Carbon Dioxide (CCS Directive) Directive 2009/31/EC
Marine Strategy Framework Directive 2008/56/EC
Spanish Legislation
Law 40/2010 of Geological Storage of Carbon Dioxide
22
1.2.3. CCS projects around the world
The site selection for CCS is a crucial step which has to demonstrate that the site is capable of
meeting required storage performance criteria and to establish a baseline for the management
and monitoring of the CO2 injection and storage (RAMF, 2006). At present, several countries are
interested in the development of carbon capture and storage (CCS) technologies (Fig. 1.3).
Furthermore, the EU is promoting and contributing to progress in CCS technologies by financially
supporting new projects. Thus, since numerous projects on CO2 storage in sub-seabed
geological structures are currently in hand, studies are urgently needed to obtain reliable
research-based information for correct risk assessment and to plan monitoring networks (Keating
et al., 2011; Basallote et al., 2012). North America and Europe are the most active regions for CCS
development, which is evident in the number of projects (Hosa et al., 2011).
Figure 1.3. CCS projects around the world: active CCS projects (large scale, yellow points), pilot
CCS projects (small scale, blue points) and active CO2 storage projects (green points) (Carbon
Capture & Sequestration Technologies, 2013)
In Spain, CCS is one of the mitigation tools included between the different strategies to help to
mitigate climate change as is reflected in the Spanish Climate Change and Clean Energy
Strategy (EECCEL, 2013). In the case of Spain, eleven different areas have been chosen as
potential subterranean structures for CO2 storage. (BOE, 2008). Figure 1.4 shows the location of
23
these stores in the country. Four of these stores are located in the continental shelf of the
Cantabrian Sea (northern Spain). Some of these coastal and estuarine areas are contaminated,
especially because of the urban and industrialized areas, with high concentrations of a wide
variety of metals and organics in sediment (Coz et al., 2007; Viguri et al., 2007; Alvarez-Guerra et al., 2008).
Store 8
Store 11
Store 7
Store 9
Store 3
Store 1
Store 4 Store 2
Store 5
Store 6
Store 10
Figure 1.4. Potential subterranean structures for CO2 storage in Spain
1.3. CO2 sequestration in sub-seabed geological structures
Geologic sequestration of CO2 involves the injection of CO2 into deep oceans, into the
subsurface. Possible geological storage reservoirs are depleted oil and gas reservoirs, enhanced
oil and gas recovery (EOR and EGR, respectively), saline aquifers and unminable coal seams
(Fig. 1.5). Subsurface geological storage is possible both onshore and offshore (IPCC, 2005).
Storage in deep saline aquifers appears to hold the most combined promise in terms of storage
capacity, proximity to emission sources and state of the art technology (Bruant et al., 2002; Brown et
al., 2011). During geologic sequestration, CO2 is stored via hydrodynamic, solubility or mineral
trapping (Damen et al., 2006). Related to the use of CO2 for beneficial purposes as enhanced oil
recovery (EOR), carbon capture, utilization, and storage (CCUS) is a rising technology entailing
the productive use of the captured CO2. Thus, CCUS technologies achieve CO2 mitigation while
24
storing and commercially utilizing the captured CO2, and advanced approaches to natural gas
and oil recovery (Carter, 2012).
Terrestrial
Terrestrialsequestration
sequestration Power
Powerstation
station
with
withCO
CO2 capture
2 capture
Chemical
conversion
Unminable
coal beds
Depleted oil or
gas reserve Deep
Deepsaline
saline
Enhanced recovery formation
formation
Figure 1.5. Carbon sequestration options: terrestrial sequestration and oceanic sequestration
(SCCS, 2011; Montana Environmental Information Center, 2013)
The long-term sequestration of carbon in sub-seabed geological structure is one of the CO2
mitigation strategies considered in numerous conventions and directives such as the London
Protocol (1996), London Convention (2006, 2007), OSPAR Convention 2007, and the EC
Directive, European Parliament on 17 December 2008. Amendments of the London Protocol
were adopted in 2006 with the object of regulating this activity by including the “Risk Assessment
and Management Framework for CO2 Sequestration in Sub-seabed Geological Structures” and
the “Specific Guidelines for Assessment of Carbon Dioxide Streams for Disposal into Sub-seabed
Geological Formations” (Basallote et al., 2012).
Risk assessment is a first step in a strategy to set up management and control measures to
minimize risks of underground CO2 storage. The potential migration or release of CO2 into the
marine environment comprises two aspects: first, potential releases during the operational phase
of CCS; and, second, migration and releases of CO2 from the sub-seabed geological structure
following the injection process. Potential operational releases would most likely result from major
seal failure or disruption of the means of emplacement of the CO2 in the geological structure i.e.
the pipeline or means of insertion from a vessel and the injection well. The physical effects
25
associated with major releases of gaseous CO2 are primarily the disturbance of unconsolidated
bottom sediment caused by the flow and expansion of CO2 as it passes through the upper
sediment column and into the overlying water column. Associated with such events would also be
turbulence and therefore increased vertical mixing in the water column. However, such
disturbance would require a substantial and rapid release of gaseous phase CO2 to cause a
major disturbance. At the extreme, a substantial and rapid gas release at the seafloor could
cause damage to the marine environment, interference with other legitimate uses of the sea,
including fishing and maritime transport, with the potential for associated risks to human health
(RAMF, 2006).
The following aspects should be considered to assist in the management of storage of CO2
streams in geological formations (OSPAR, 2007):
o Assessment of the suitability of a potential injection-site for permanent containment of

CO2 streams and identification of the necessary measures for hazard reduction,
remediation and mitigation
o Characterization of the risks to the marine environment from storage of CO2 streams in
geological formations on a site-specific basis
o Collection of necessary information (monitoring) and development of a strategy to
manage uncertainties and minimize risks
1.4. Risk assessment and management of storage of CO2 streams in geological formations
In the case of CO2 leakage from a sub-seabed reservoir, the released CO2 may change pH and
pCO2 in the sediment pore water and the seawater, which represents a risk to local biota in itself.
CO2 acidification may cause cascade effects in ecosystem if it affects a process that has a key-
function in the complex ecosystem. The actual impacts of acidification, including secondary
mechanisms, may range across a broad spectrum of chemical, ecological and physiological
processes. Therefore not only the primary effects (CO2 increase and pH decrease) but also
secondary effects (change in the mobility, solubility and bioavailability of trace and heavy metals,
nutrients and inorganic-organic toxins) should be studied. Regarding the acidification of the
environment, a decrease of pH associated with increase of CO2 could produce chemical changes
26
in the sediment-seawater interface, leading to biogeochemical alteration in marine ecosystems. In

addition, acidic conditions due to decreased pH will enhance the mobility of trace metals or other
contaminants that could be present in marine sediment, making these substances more available
in the overlaying water column (Ardelan et al., 2009; Riba López et al., 2010; Basallote et al., 2012;
Karamalidis et al., 2013).
The consequences of potential CO2 leakages from geological storage sites into sediment
matrices in contact with water have been studied previously. Those works aim to know different
objectives as the potential metal release from sediment to the marine environment, as well as the
changes in parameters like pH, total organic carbon (TOC), conductivity and alkalinity due to CO2
leakages (Ardelan et al., 2009, 2010; Carey et al., 2009) or to know the changes in the bacterial
community structure (Widdicombe et al., 2009; Ardelan et al., 2012). The potential effects of the CO2
leakages from geological sequestration systems involve many ecosystems interactions at
different temporal and spatial scales leading to direct and in-direct effects on the marine biota and
human health. In this context an appropriate risk management study makes necessary the
integration of the different studied approaches during the risk assessment. Other pieces of work
used aquifer samples (Little and Jackson, 2010; Lu et al., 2010; Keating et al., 2011; Viswanathan et al., 2012)
and lake samples (Tynan and Opdyke, 2011; Frye et al. 2012) to study changes in pH and different
elements under the same situation. All the previous studies employed several sediment-water-
CO2 contact systems; bubbling of CO2 gas through natural seawater before the contact with the
sediment or bubbling both sediment and water with CO2 gas, as way of acidification (Table 1.3).
For the last 10 years, the research group of the University of Cantabria which this thesis is
involved and currently named GER research group (www.geruc.es) has developed different
research projects related to the characterization and determination of the impact of contaminated
sediment in the surrounding environment as well as the assessment of the potential effects of
CO2 leakages on contaminated marine sediment in CCS systems. According to this, the
framework of the present thesis proposes a Tier structured approach for the determination of
metal and DOC release from contaminated sediment under CO2 leakages from CCS sites.
Furthermore, laboratory leaching tests (equilibrium and column) of the potential effects of CO2
leakages from geological storage sites into surface sediment and into deep sea are developed
(Payán et al., 2012a, b, 2013).
27
Table 1.3. Laboratory and small scale studies of the effects of potential CO2 leakages from geological storage sites into surface sediment and into deep sea
Sediment-water-CO2 Sediment Liquid and seawater Release parameters
Reference S-L-G contact variables
contact characteristics characteristics under study
Overlying water. Continuously Fe, Mn, Co, Al, Cr, As,
Ardelan et al., flow-rate of seawater = 1 L/min Operation pressure = 10 bar Pb, Ce and U
A 1400 liter Titanium tank Surface sediment
2012 Pure CO2 was purged through Duration = 30 days Bacterial community
20 cm thick sediment structure
Water
11 columns with CO2 in the Mixtures of quartz Inlet leakage flow rate = 0.05,
Ionic strength = 0.001, 0.01 and
inlet solution and 2 columns and cadmium laden 0.20, 1 mL/min with a solution of
Frye et al., 2012 0.10 M Cd
with no inlet CO2 (control illite (Artificial river 0-43.79 mM CO2
Inlet pH = 3.86, 5.04, 5.09, 5.10,
columns) and lake sediment) Duration = 30, 200 and 250 h
5.11, 7.46, 7.90
Batch laboratory. 3 days to reach a steady state
One reactor exposed to CO2-charged synthetic CO2 introduced into the reactor
Viswanathan et al., Aquifer sediment
hydrated CO2 and one groundwater solutions and samples taken after 1 h of As
2012 samples
reactor kept as steady-state CO2 bubbling for 1 h CO2 bubbling
(CO2-free control) Duration = 26 days
Mineral assemblage
pH, HCO3-, Ca, Mg, Na,
Bateman et al., Ti-column, 100 cm long, 3.6 with quartz, Reactant fluid at a constant flow T = 130ºC P = 300 bar
K, Si, Ba, Sr, Mn, Fe,
2011 cm internal diameter labradorite, K- rate equilibrated with CO2 Duration = 3.5 months
Al, Ni, Zn, Cr, Cl, SO4
feldspar, mica, calcite
28
Sediment-water-CO2 Liquid and seawater Release parameters
Reference Sediment characteristics S-L-G contact variables
contact characteristics under study
Experiments using aquifer Initial equilibration period, then Pure water or a synthetic water,
pH, major and trace
Keating et al., 2011 samples collected at Aquifer samples CO2 was added. Control of pH then CO2 gas was bubbled into
elements: Ca, U
outcrops with HCl the sample
Laboratory experiments Natural carbonate Natural seawater (~9360 mL)
Tynan and T = 23.6 ºC
Fish tank (24 cm x 19.5 cm x sediment samples (1 cm CO2 gas injected in the tank to Alkalinity
Opdyke, 2011 Duration = One week
21 cm) deep) the water
High P/high T Sandy loam soil T = 25 ºC Mg, K, Al, Ti, V, Cr, Mn,
No liquid phase
Wei et al., 2011 Parr reactor Soil placed in reactor and P = 25 bars Fe, Co, Cu, Rb, Sr, Mo,
CO2 injected into the reactor
3 replicates incubations incubated with CO2 Duration = 3 days Cs, Ba, Pb, Th, Zn, Cd
Samples from 4 freshwater 400 g placed into bottles at a
Laboratory incubations of Dry aquifer sediment from 17
Little and Jackson, aquifers water/rock ratio of 3/1: another pH, Li, Co, Mo, Ba, U,
CO2 infiltration under distinct locations
2010 99.8% pure CO2 stream set was exposure to CO2 As, B, Se, Tl
oxidizing conditions
Constant rate = 0.2 L/min T = 20ºC, Patm. t > 300 days
During the first 2 weeks, Ar gas
pH, Ca, Al, Zn, Cl, Mg,
was flushed through the
Fe, Cs, SO4, Na, B, Ni,
Laboratory-batch reaction reactors to approach
Lu et al., 2010 Aquifer rock samples Shallow groundwater Br, K, Co, Rb, F, Si, Cu,
experiments equilibrium. In the second 2-
As, NO3, Mn, Mo, Cr, Sr,
week phase, CO2 gas was
U, Ba, V
flushed through the reactors
29
Sediment-water-CO2 Sediment Liquid and seawater Release parameters
Reference S-L-G contact variables
contact characteristics characteristics under study
Seawater (upper Acidification of seawater Total acid-leachable and

Sediment samples from 1st phase 16 days; 2nd phase 10 days with
section) and sediment at pH 6.5- 7 by CO2 gas dissolved fractions of
the Trondheim Fjord at same sediment but replenished seawater
Ardelan. et al. (lower section) in a from a sprinkler hose Fe, Mn, Co, Al, Cr, Ni,
the depth of 250 m CO2 chamber and control chamber with N2 to
2009, 2010 chamber purged with holes placed as a Pb, Cd, Cu, Zn
Sediment were mimic the sediment suspension.
intermittently with pure spiral below the sediment pH, TIC, total alkalinity,
equilibrated for 3 days L/S = 0.045; P = 1.5 bar; T = 6.5 ºC ± 0.3 ºC
CO2 gas layer (0.045 L/S; 1.5 bar) pCO2
Batch reactions of water Quartz-rich alluvial Continuous CO2 bubbling

pH, TDS, As, Ba, Ca,
and sediment with a deposits sediment (< 2 at P = 1 atm 3 days of equilibration period
Carey, et al., 2009 Cd, Co, Cr, Cs, Cu, Mn,
continuous CO2 mm) pH = 8.1 Duration = 15 days
Ni, Pb, Se, U, V, Zn.
bubbling Synthetic groundwater TDS = 1000 ppm
pH, T, O2 saturation
A mesocosm-based Muddy and sandy Duration = 2 weeks (short term) and 20
Bubbling of CO2 gas levels and alkalinity
Widdicombe, et al. experiment with sediment weeks (long-term)
through natural seawater. Structure and diversity
2009 sediment and acidified Natural seawater Samples were taken at t = 0, 6, 12, 18 and
pH = 5.6, 6.5, 7.3 and 8 of macrofaunal and
seawater 24 h
nematode assemblages
300 kg/day CO2 injected
Small-scale field Collection of 80 shallow groundwater pH, alkalinity, Fe, Mn,
Kharaka et al., at 1.1-2.5 m below
experiment Sandy gravel deposits samples before, during, and after CO2 gas Pb, As, Zn, Ca, K, Cd,
2008 ground surface, 0.5-1 m
Shallow groundwater injection Cu.
below the water table
30
1.4.1. Risk of CO2 leakages in the marine environment
The Earth´s oceans and sediment act as the main sink and buffer of atmospheric CO2, and have
helped keep the system in a dynamic equilibrium for millennia (Tynan and Opdyke, 2011). In the
event of more likely CO2 release episodes, the CO2 enriched stream could potentially contact the
marine sediment and/or the water column. This contact could potentially alter the physiochemical
nature of marine sediment, the surrounding boundary layer of marine waters, and/or the water
column (RAMF, 2006).
Anthropogenic activities and natural sources can discharge different metals to marine water in
both dissolved and suspended solid forms through estuaries (Katsumi, 2011; Demirak et al., 2012; Hill et
al., 2013; Moukhchan et al., 2013). Normally, such metals tend to accumulate in the sediment by
superficial adsorption or precipitation in upper few centimeters of the coastal sediment (Chaudhary
et al., 2012; Demirak et al., 2012). Therefore, sediment constitutes the principal sink for organics and
trace metals in aquatic systems. Any variation of environmental conditions can lead to the release
of the mobile fractions into the sediment water phase (Centioli et al., 2008).
Seawater is chemically a very complicated system because it contains all naturally occurring
elements with different concentration levels along with unidentified organic materials (Katsumi,
2011). When the threshold of the natural buffer capacity of the seawater is exceeded, the potential
CO2 leakages in the marine environment will acidify the surroundings at pH values ranged from
natural seawater at pH 8 until the worst expected acidification local scenario at pH 5 with the
consequent negative effects (Carey et al., 2009; Jacquemet et al., 2009; Wigand et al., 2009; Viguri et al.,
2010). A decrease in pH reflects an increase in hydrogen ion concentrations. Consequently, the
hydrogen ions will protonate the aquatic ligands and replace the trace metals, causing an
increase in the free metals ion activity; this is considered the most bioavailable form of dissolved
metals.
According to the EU Directive (CCS Directive, 2009), the characterization and assessment of the
potential storage shall include effects of exposure to reduced pH in those environments as a
consequence of CO2 leakage and the study of mobilized metals in a decreased pH environment.
The marine environment acidification and the potential contamination by hazardous substances
31
due to their mobilization from contaminated sediment in contact with acidified marine water is a
subject of concern in the framework of the UE marine environment protection established under
the Marine Strategy Framework Directive (Marine Strategy Framework Directive, 2008). The model of
risk assessment to be applied has to take into account the environmental risks that can be
caused in the environment and/or in the human health due to leakages of CO2 during the injection
or during its short and long-term storage (FRAM, 2007).
In order to know the effects on the marine environment is of special interest to achieve an
assessment of the possible risks. The main issues to assess the associated risks include the
types of receptors which can be exposed, the bio accessibility (depth of water and sediment), the
mobilization of substances, their availability to be transported, their bioavailability and their
effects. The information concerning the effects on species and/or ecosystems is scarce and
focused mainly on systems of great depth. It is therefore advisable to study the response of
representative species to different CO2 concentrations and to the substances mobilized by the
CO2 flux; this will make it possible to establish a quantitative relation between the concentrations
of exposition and the associated effects by means of the use of, e.g., toxicity bioassays,
bioaccumulation and biomarkers of response to the changes in the concentrations of metals due
to CO2 leakages (FRAM, 2007).
The behavior of aquatic sediment as a source of pollutants cannot be fully assessed by the
determination of total metal concentrations (Fytianos and Lourantou, 2004). The main factors
influencing potential risks of heavy metals are their solubility, environmental bioavailability, and
their toxicological bioavailability (Kogbara et al., 2010). In order to evaluate the release of
constituents from a material, a wide variety of leaching tests has been developed under different
conditions. Therefore, leaching tests are considered a very useful tool to estimate the release of
constituents from granular materials. However, the leaching process is very complex and one
single test cannot provide a complete understanding of the heavy metal mobility. In order to have
a better vision of the leaching process, a diversity of tests is used to determine metal release
under changing environmental conditions.
32
1.5. The leaching process
1.5.1. Objectives and principles of leaching tests
The main objective of the leaching tests is to quantify the mobility of chemical species (pollutants
or not) present in solid matrices in a given leaching solution (Cappuyns and Swennen, 2008; INSA Lyon,
2013). Leaching is the process by which inorganic and organic contaminants are released from
the solid phase into the water phase under the influence of mineral dissolution, desorption,
complexation processes as affected by pH, redox, dissolved organic matter and (micro)biological
activity (Cappuyns and Swennen, 2008; Quina et al., 2009; Leaching, 2013). Tests that allow
characterization of waste behavior can generally be classified in three categories according to the
European group CEN/TC 292 (Van der Sloot et al., 2004; Coz et al., 2011; INSA Lyon, 2013):
o Tests of basic characterization aim at obtaining information on characteristic properties of

the waste and on their short and long-term behaviors in the conditions specified by the
considered scenario. Liquid/solid (L/S) ratios, leaching solution composition, factors that
control the leaching as pH, redox potential, complexation capacity and physical
parameters are taken into account in these tests.
o The compliance tests are used to determine if the waste is in compliance with specific
reference thresholds. These tests focus on key parameters and on leaching behavior
identified by the basic characterization tests.
o The tests of check in situ are used to quickly verify that the waste is the same that the
one that underwent the compliance tests. These tests of check in situ are generally the
same as compliance tests or very short leaching tests (10 minutes), but also controls of
temperature or radioactivity, etc.
In CEN/TC 292 test methods are in development for characterization of the leaching behavior of
granular and monolithic materials, which prove to be applicable for a broad range of materials
outside the field of waste (Van der Sloot et al., 2006; Arce et al., 2010). The most used standardized
leaching tests are presented in Table 1.4 (Leaching, 2013).
33
Table 1.4. Standardization of the leaching tests (Leaching, 2013)

European standardization
International standardization
Basic characterization Compliance tests
CEN/TS 14429 – pH CEN/TS 14405 –
dependence leaching test Percolation test
(initial acid/base addition) (L/S=0.1)
ISO/TC 190/SC7/WG6: Batch tests (ISO/AWI
21268 1 and 2) and percolation test (ISO/AWI
CEN/TS 14997 – pH EN 12457 1-4 Granular
21268-3) for soil materials (based on CEN TC
dependence leaching test waste compliance
292 procedure) – F – DIS in 2007. pH
(continuous pH control) leaching test
dependence leaching test (ISO/AWI 21268-4)
for F – DIS in 2007
CEN/TS 14405 – Percolation CEN/TC 292/WG2
test Monolith compliance
leaching test (3 days)
1.5.2. Basic characterization tests
The main objectives of the basic characterization leaching tests are to identify the main
mobilization mechanisms, to characterize the release dynamics of pollutants, and to determine
the influence of some scenario factors on this release dynamics. These basic characterization
tests can also be classified in two categories (INSA Lyon, 2013):
o The static tests aiming at reaching the equilibrium for some parameters (such as pH).
o The dynamic tests are used in order to determine the release dynamics of the material in
standard conditions.
The static leaching tests CEN/TS 14429:2006 and CEN/TS 14997:2006 aim at determining the
influence of the pH and of the acid-basic capacity on the leaching behavior of a material (INSA
Lyon, 2013). These two tests differ in the means implemented to reach the pH balance:
o In the case of the CEN/TS 14429 test, the equilibrium such as defined in the standard is
obtained by adding predefined quantities of acid or base to reach the required values of
pH. The required pH is then obtained by the initial addition of the base or acid quantity
determined by a preliminary titration. A grain size reduction is made to reach more
quickly the equilibrium.
34
o In the case of the CEN/TS 14997 test (called pHstat), the equilibrium condition is insured
by the continuous pH adjustment thanks to the controlled addition of acid or base
throughout the test to maintain the required value of pH.
On the other hand, the dynamic test on granular material particularly adapted to characterize the
behavior of materials subjected to standard conditions of percolation is the column or percolation
test such as defined in the European standard CEN/TS 14405: 2005.
In case of monolithic materials, the CEN/TC 292/WG6 (also named Dynamic leaching test for
monolithic waste) is under development. This leaching test is a test method for determining the
leaching behavior of a porous monolithic material under dynamic conditions and to characterize
the mechanisms of inorganic pollutants transfer in solution (INSA Lyon, 2013).
When different types of tests are compared, it is usually clear that the pHstat test gives the most
important information, but it is costly. In fact, batch test involves in general low cost and simpler
design, and it can be carried out in short periods of time. Column test affords a better
approximation to leaching processes under field conditions, and thus it is more suitable for
prediction purposes. However, in general, column experiments entail moderate cost and are more
time consuming tests. In addition to be aware of the advantages/disadvantages, it is very
important to know the conditions under which the results obtained in column tests can be
extrapolated to batch results (Grathwohl and Susset, 2009; Quina et al., 2011).
1.5.3. Compliance tests
The compliance leaching tests usually are the same as the basic characterization leaching tests
with specific conditions such as reagents, liquid to solid ratios, leaching time and/or stirring. They
are used to compare concentrations or fluxes of emitted pollutants to the criteria of acceptance in
landfill or criteria of valorization – recycling as raw material or substitution material. The most
common compliance tests are the equilibrium and dynamic leaching tests. The equilibrium and
dynamic set of assays can determine the leaching control mechanisms, which can be described
in terms of availability, chemical equilibrium or mass transference rate, obtaining an integral
35
model that makes possible the estimation of the contaminants mobility in a large range of
potential scenarios (Kosson et al., 1996; van der Sloot et al., 2006).
In case of granular materials, it is allowed to use the column test, CEN/TS 14405, for compliance
testing at L/S=0.1 L/kg (first fraction of percolation test), to direct comparison with the acceptance
criteria in the European Landfill Directive (Arce et al., 2010; INSA Lyon, 2013). Regarding the
monolithic materials, CEN/TC 292/WG2 will be able to be used as compliance leaching test for
monolithic waste during 3 days of leaching (van der Sloot et al., 2006; INSA Lyon, 2013).
The most common equilibrium leaching test used for compliance characterization is the EN
12457:2002 on granular materials (Coz et al., 2011). The EN 12457 standard is composed of 4
parts. Each of them treats of specifications of a compliance test for the leaching of granular waste
and/or sludge in specified conditions. The 4 operating modes are (INSA Lyon, 2013):
o Part 1: One stage batch test at a liquid to solid ratio of 2 L/kg for materials with high solid
content and with particle size below 4 mm (without or with size reduction)
o Part 2: One stage batch test at a liquid to solid ratio of 10 L/kg for materials with particle
size below 4 mm (without or with size reduction)
o Part 3: Two stage batch tests at a liquid to solid ratio of 2 L/kg and 8 L/kg for materials
with high solid content and with particle size below 4 mm (without or with size reduction)
o Part 4: One stage batch test at a liquid to solid ratio of 10 L/kg for materials with particle
size below 10 mm (without or with size reduction)
In the European Landfill Directive, only the first two parts at liquid/solid ratios of 2 and 10 L/kg are
used as compliance tests and the regulated limits are divided into three different scenarios (Coz et
al., 2011).
1.6. Modeling of the leaching tests results
The utilization of leaching tests, in combination with their modeling, in the study of the key
parameters controlling the mobility of the contaminants and their application in specific conditions,
make possible the simulation of different scenarios and the prediction of the long-term behavior in
36
solid matrices. In this way, many leaching tests have been developed on several materials
(granular, compacted or monolithic), and different scenarios for their utilization or management
(construction materials, secondary products, treatment or disposal) (van der Sloot et al., 1997).
On the one hand, the measured concentrations in the effluent of a column as a function of time
are dependent on the terms of dispersion, advection and retardation by sorption (Kalbe et al., 2007).
In this way, some authors model the column leaching process by the advection-dispersion model,
which is independent of duration and physical dimensions of the leaching tests. This model also
fits reasonably well under non-equilibrium conditions with an apparent non-equilibrium distribution
coefficient Kd (Grathwohl and Susset, 2009). In addition, other pieces of work describe the cumulative
leaching obtained in column tests as a function of the L/S ratio through a model with two
parameters (matrix retention and cumulative release at L/S=1) that allow a comparative criteria
between different materials (van der Sloot et al., 1997).
On the other hand, geochemical modeling of metal release is very useful in the study of the
chemical leaching in waste, soil and sediment (Coz et al., 2004; van der Sloot et al., 2007; Dijkstra et al.,
2008). Models as Visual Minteq software based on thermodynamic data for soil components and
phases, have been extensively used (Meeussen, 2003; Cappuyns et al., 2004; Cappuyns and Swennen,
2008; Ho et al., 2013) to identify the long term solubility control by specific mineral phases, to
determine theoretically the distribution of metals between various mineral solid phases and to
predict the long term metal release pattern. Visual Minteq is used for aqueous equilibrium
solubility and can be used to compare the experimental mobility results with respect to the
solubility-controlling phases as a function of pH. It has an extended database with hydrolysis,
complex and solubility reactions, isotherm adsorption and surface complexation. The model is
easily accessible, simple and “user-friendly” (Gustafsson, 2004). The software also predicts, which
minerals are likely to precipitate or dissolve, based on ion speciation and the thermodynamic
properties of minerals involved in the various dissolution and precipitation reactions. The
tendency for a mineral to precipitate or dissolve is represented by its saturation index (Nguyen et
al., 2008). Chemical modeling is based on both the speciation and saturation index calculations
(Cornelis, 2008). Chemical speciation is the dominant speciation of each component of interest in
aqueous medium as a result of aqueous reactions and physico-chemical phenomena. Saturation
index calculations are the main phases that control the solubility of the components of interests.
37
The main chemical reactions in seawater that can be used in the geochemical modeling are:
solubility, complex and hydrolysis reactions, ionic association, ionic exchange and redox.
Furthermore, a geochemical modeling takes into account the temperature dependence, ionic
strength and activity coefficients. On the other hand, gasses formation, adsorption phenomena,
kinetic modeling for irreversible reactions and transport can complete the geochemical model in
case of trace elements.
This doctoral thesis takes into account different mathematical models of the leaching test results:
empirical, semi empirical and geochemical modeling; the application of these different tools
constitutes the sequence of the data analysis of this thesis and shows the relationship between
the different obtained results in the context of weight-of-evidence in environmental assessment
(Payán et al., 2012a, b, 2013).
1.7. Objectives and thesis structure
The present work is carried out in GER research group and specifically in the topic work
“Minimization of waste and environmental control of sediment” that develops activities in the
frame of the Project PN I+D+I of MEC, CTM2008-06344-C03-01 in which the author of the thesis
is employed as a FPI research fellow. The objectives proposed in this coordinated project are
included the Strategic Action of Energy and Climate Change, Line 1 of CO2 Storage and Capture,
which has the mitigation of climate change among its areas of action.
The working hypothesis is that the use of standardized leaching tests for waste can be useful as
first step to study and predict, under controllable and reproducible conditions, the consequences
of Carbon Capture and Storage (CCS) problems, making possible to obtain a preliminary risks
assessment of the behavior of contaminated marine sediment under CO2 leakages. In order to
achieve this, the performance of batteries of dynamic, equilibrium and pH dependence leaching
tests on sediment samples in contact with CO2 is proposed.
The general objective of this thesis is to generate new knowledge about the potential effects of
CO2 leakages on contaminated marine sediment in CCS systems by means of the analysis,
modeling and assessment of the mobility of metals and dissolved organic carbon (DOC) due to
38
CO2 leakages. The achievement of this general objective is accomplished by a Tier structure
through the following standardized basic and compliance characterization tests:
1. Characterization of sediment matrices

2. Column leaching tests
3. Equilibrium leaching tests
4. pH dependence leaching tests
5. Modeling of leaching test results
The release of the main contaminants As, Cd, Cr, Cu, Ni, Pb, Zn and DOC from the marine
surface sediment collected in the estuary of Suances (Northern Spain), an area reserved as
potential CO2 store, is studied; different types of leaching solutions such as deionized water,
natural seawater (pH 8) and acidified seawater at different pH values (pH 5, 6 and 7) are used.
The final results can provide a way forward for site-specific risk assessment in the short, medium
and long term and for developing appropriate and cost-effective, prevention, mitigation and
remediation strategies.
According to the hypothesis of the specific objectives, and taking into consideration the
requirements of the University of Cantabria to the preparation of doctoral thesis as compendium
of scientific papers, the present thesis is organized into the following chapters:
Chapter 1 includes a general introduction of the research work and the objective of the thesis
Chapter 2 includes the scientific papers which form the thesis
Chapter 3 includes a detailed description of the Tier structure and the procedures and materials
used. Furthermore, an overall summary of results and discussion section is presented
Chapter 4 includes the conclusions of the thesis and the future work planned for the successive
research
39
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Guthrie, G.D., Pawar, R., 2012. Developing a robust geochemical and reactive transport model to
evaluate possible sources of arsenic at the CO2 sequestration natural analog site in Chimayo,
New Mexico. International Journal of Greenhouse Gas Control 10, 199-214.
Wang, S. and Jaffe, P.R., 2004. Dissolution of a mineral phase in potable aquifers due to CO2
releases from deep formations; effect of dissolution kinetics. Energy Conversion and
Wei, Y., Maroto-Valer, M., Steven, M.D., 2011. Environmental consequences of potential leaks of
CO2 in soil. Energy Procedia 4, 3224-3230.
Widdicombe, S., Dashfield, S.L., McNeill, C.L., Needham, H.R., Beesley, A., McEvoy, A.,
Øxnevad, S., Clarke, K.R., Berge, J.A., 2009. Effects of CO2 induced seawater acidification on
infaunal diversity and sediment nutrient fluxes. Marine Ecology Progress Series 379, 59-75.
Wigand, M., Kaszuba, J.P., Carey, J.W., Hollis, W.K., 2009. Geochemical effects of CO2
sequestration on fractured wellbore cement at the cement/caprock interface. Chemical Geology
265, 122-133.
46
47
48
ARTÍCULOS CIENTÍFICOS /
SCIENTIFIC PAPERS
Artículos científicos/Scientific papers
50
2. ARTÍCULOS CIENTÍFICOS/SCIENTIFIC PAPERS
2.1. Payán, M.C., Verbinnen, B., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R.,
2012. Potential influence of CO2 release from a carbon capture storage site on release of
trace metals from marine sediment. Environmental Pollution 162, 29-39.
Resumen:
Uno de los principales riesgos en la Captura y Almacenamiento de CO2 (CAC) son las fugas de
CO2 del lugar de almacenamiento. En este trabajo se estudia la influencia de estas fugas en la
lixiviación de metales traza de sedimentos marinos contaminados en una zona potencial de
almacenamiento (norte de España) usando ensayos de lixiviación estandarizados. La influencia
del pH del agente lixiviante en los lixiviados se evalúa utilizando agua desionizada, agua de mar
natural y agua de mar acidificada a pH 5, 6 y 7, obtenida por burbujeo de CO2. Los ensayos de
lixiviación utilizados han sido el ensayo de equilibrio (EN 12457) a diferentes relaciones líquido-
sólido y el ensayo de lixiviación de neutralización ácida y básica, ANC/BNC (CEN/TS 15364).
Los resultados han sido modelados mediante el programa de equilibrio geoquímico Visual
Minteq. Los ensayos de equilibrio dieron valores de pH final para todos los lixiviados de agua de
mar entre 7 y 8 debido a la alta capacidad de neutralización ácida del sedimento. La combinación
de los resultados de los ensayos de lixiviación y el modelado geoquímico concluye con los
mecanismos y predicción de la lixiviación de metales traza en situaciones donde el agua de mar
está acidificada por burbujeo de CO2.
51
Conclusiones:
Para proporcionar mejor información de los parámetros clave que controlan la movilidad de
contaminantes de sedimentos marinos en contacto con fugas de CO2, se llevan a cabo varios
ensayos de lixiviación estandarizados. Los ensayos de lixiviación se realizan usando agua
desionizada, agua de mar natural y agua de mar acidificada por burbujeo de CO2 como agentes
lixiviantes. El valor de pH más bajo alcanzado por los ensayos de lixiviación de equilibrio para los
lixiviados de agua de mar fue de 6,8. Hay que destacar que la lixiviación de los elementos es
más baja cuando se usa agua desionizada que con agua de mar como agente de lixiviación. La
fuerte influencia de la acidificación del agua de mar en la lixiviación de los metales del sedimento
debido a las fugas de CO2 se acentúa por el aumento en la concentración del contaminante para
As, Cd, Ni, Pb y Zn. Se estimó que comparando pH 8 (pH normal del agua de mar natural) con
pH 7.3, las concentraciones de As, Cd, y Zn podrían aumentar un 45% y con pH 6.8 entre 66-
82%. El modelado geoquímico de los datos experimentales con Visual MINTEQ permite predecir
las especies químicas en los lixiviados de los sedimentos a diferentes valores de pH sin mostrar
grandes diferencias en el modelo con agua de mar respecto al modelo con agua desionizada.
Además, el estudio de la movilidad de metales y carbono orgánico disuelto de los ensayos de
columna trabajando en un amplio rango de ratios L/S se propone como trabajo futuro para
determinar el comportamiento experimental de los sedimentos contaminados en contacto con
agua de mar acidificada; el modelado dinámico de estos datos permitiría predecir el
comportamiento del metales a largo plazo y completar el procedimiento de lixiviación propuesto
en este artículo para la evaluación de la movilidad de metales de sedimentos contaminados bajo
condiciones de fugas de CO2 de CAC.
52
Environmental Pollution 162 (2012) 29e39
Contents lists available at SciVerse ScienceDirect
Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol
Potential influence of CO2 release from a carbon capture storage site on release of
trace metals from marine sediment
M. Cruz Payán a, b, Bram Verbinnen b, Berta Galan a, Alberto Coz a, Carlo Vandecasteele b, Javier R. Viguri a, *
a
Department of Chemical Engineering and Inorganic Chemistry, ETSIIT, University of Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain
b
Department of Chemical Engineering, University of Leuven, Willem de Croylaan 46, B-3001 Heverlee, Belgium
a r t i c l e i n f o a b s t r a c t
Article history: One of the main risks of CCS (Carbon Capture and Storage) is CO2 leakage from a storage site. The
Received 1 July 2011 influence of CO2 leakage on trace metals leaching from contaminated marine sediment in a potential
Received in revised form storage area (Northern Spain) is addressed using standardized leaching tests. The influence of the pH of
4 October 2011
the leaching solution on the leachates is evaluated using deionized water, natural seawater and acidified
Accepted 12 October 2011
seawater at pH ¼ 5, 6 and 7, obtained by CO2 bubbling. Equilibrium leaching tests (EN 12457) were
performed at different liquidesolid ratios and the results of ANC/BNC leaching test (CEN/TS 15364) were
Keywords:
modeled using Visual Minteq. Equilibrium tests gave values of the final pH for all seawater leachates
Sediment
CO2 leakage
between 7 and 8 due to the high acid neutralization capacity of the sediment. Combining leaching test
Metal mobility results and geochemical modeling provided insight in the mechanisms and prediction of trace metals
Equilibrium leaching tests leaching in acidified seawater environment.
Geochemical modeling Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction CO2 leakages on the surrounding environment will have to include

the mobilization of substances from sediment by the resulting
Carbon dioxide (CO2) is responsible for the largest part of the acidification. OSPAR and London Protocol have developed a frame-
greenhouse effect and interacts strongly with oceans because of its work and binding guidelines for the evaluation and management of
high solubility. The average reduction in the seawater pH since CCS risks, which comprises six main stages, including the study of
1800 has been estimated at 0.1 units and it is predicted a decrease metal mobilization in a decreased pH environment (RAMF, 2006).
in average surface ocean pH of 0.3e0.5 units by 2100 (Caldeira and The problem of possible CO2 leakages from geological storage
Wickett, 2005; Orr et al., 2005; Dashfield et al., 2008). sites has been tackled in different articles by means of studying the
In Carbon Capture and Storage (CCS) climate change mitigation solubility and mobility of metals from sediment to seawater, the
technologies, CO2 from some industrial processes is captured, changes of pH, Dissolved Organic Carbon (DOC), conductivity and
transported to a storage site and kept in geological formations for alkalinity in the seawater in contact with sediment (Ardelan et al.,
a very long time (Metz et al., 2005; IMO, 2006; Ukaegbu et al., 2009; Ardelan and Steinnes, 2010; Carey et al., 2009) and metal
2009). Different countries have proposed areas as potential accumulation in biota (Riba López et al., 2010) and marine species
subterranean structures for CO2 storage. In Spain, eleven different (Miller at al., 2009; Wood et al., 2008; Widdicombe et al., 2009).
areas have been chosen (BOE, 2008a,b). Four of these stores, are Several particular sedimentewatereCO2 contact systems have
located in the continental shelf of the Cantabrian Sea (Northern been used, working with natural seawater (pH: 7.9e8), acidified
Spain). In some of these coastal and estuarine areas, sediment are seawater mimicking ocean acidification due to the uptake of CO2
contaminated with high concentrations of a wide variety of metals (pH: 7.2e7.5) and acidified seawater mimicking leakage from a CO2
and organics (Viguri et al., 2007; Álvarez-Guerra et al., 2008; storage site (pH: 5e7.3), with pH ¼ 5 as the worst expected local
Irabien et al., 2008). scenario (Carey et al., 2009; Jacquemet, 2009). In the present paper,
One of the main risks of CCS is CO2 leakage to the marine and the behavior of contaminated sediment under CO2 leakage is
estuarine environment (Blackford et al., 2009). Risk assessment of studied using standardized leaching tests.
Leaching of trace metals as a function of pH depends not only on
the equilibrium in which the element participates, but also on the
* Corresponding author. sediment phases that become soluble. Geochemical modeling was
E-mail address: vigurij@unican.es (J.R. Viguri). widely applied to analyze and model leaching from waste and
0269-7491/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2011.10.015
30 M.C. Payán et al. / Environmental Pollution 162 (2012) 29e39
contaminated soil (Apul et al., 2010). Models as Visual MINTEQ and

PhreeqC software based on thermodynamic data for soil compo-
nents and phases, have been extensively used (Cappuyns and
Swennen, 2008; Cornelis et al., 2008), but less attention was
given to sediment (Cappuyns and Swennen, 2008; Shtiza et al.,
2009; Moberly et al., 2010).
The objective of this research is to study the effect of CO2 leak-
ages on the release of metals from contaminated marine sediment
under different scenarios of acidification using equilibrium stan-
dardized leaching tests for waste. The release of the main
contaminants As, Cd, Cr, Cu, Ni, Pb and Zn from the sediment and
the pH, conductivity and DOC behavior were studied by comparing
data obtained with different types of leachants such as deionized
water, natural seawater and acidified seawater at different pH
(pH ¼ 5, 6 and 7). The geochemical model Visual MINTEQ was
applied to the metal release under specific leaching conditions.
In the present work a Tier structured approach for the assess-
ment of the release of metals from sediment is proposed consisting
of four tiers of investigation showed in Fig. 1. The present paper
reports Tier 1 to Tier 4a of the proposed methodology. Tier 4b
methodology and the corresponding results will be reported in
a subsequent paper.
2. Experimental method
2.1. Materials
The studied sediment is marine surface sediment from the estuary of Suances
(Northern Spain), an area reserved as potential CO2 store (BOE, 2008a). This sedi-
ment contains significant concentrations of metals and organic pollutants from the
intensive industrial, mining, agricultural and urban activities upstream of the
estuary (González-Piñuela et al., 2006; Viguri et al., 2007). The estuary of Suances
should be classified as highest priority site with regard to pollution with very high
levels of Pb and Zn and high toxicity in whole estuary and the specific site selected in
this work, nearest to the sea, is representative of the whole estuary (Álvarez-Guerra
et al., 2008). Fig. 2 shows the sediment sampling site, the Suances estuary and the
area reserved for potential CO2 storage.
About 30 kg of surface sediment (0e5 cm layer) with their initial water content, Fig. 2. Sediment sampling site in the Suances estuary located into the area reserved for
were collected using a plastic paddle, sieved through 2 mm plastic mesh to remove potential CO2 storage. +: Sampling location.
the gravel fraction, homogenized and stored frozen in 3 kg plastic bags until use.
2.2. Physico-chemical characterization diffractometer), using Cu Ka radiation and operating at 30 mA and 50 kV. Sample
porosity, p (%), was measured following UNE 7045 standard method.
Sediment for metal analysis was dried at 60 C
and ground to a powder with an
agate mortar and pestle. After digestion with aqua regia for 2 h at 95 C, element
concentrations were determined using ICP-OES by an external laboratory (Activa- 2.3. Leaching tests
tion Laboratories, Canada). Organic matter was measured by loss on ignition (LOI)
according to the DIN 38414-3 method. Total organic carbon (TOC) was analyzed in Equilibrium leaching tests at L/S ¼ 2, 4, 10, 15, 20, 30 and 40 L/kg following EN
Euroglass TOC 1200 equipment (Viguri et al., 2002). The major crystalline 12457 were performed. The leachates obtained from batch tests EN 12457 at L/S
sediment phases were determined by X-ray diffraction analysis (Siemens D5000 ratios of 2 and 10 L/kg are used as compliance test to determine chemical
TIER 1. Environmental TIER 2. Physico-chemical

characterization characterization
(Total sediment concentrations and basic Mineralogy, major and minor elements,
characterization and compliance organic matter content, ANC/BNC,
leaching tests) hydrodynamic properties
- Comparison with SQG, AL, landfill
limits. Assessment of metal release
from contaminated sediment
under CO2 leakages from
CCS
TIER 4. Metal release in
TIER 3. Global parameters leaching tests
behavior Metals vs L/S and pH under different
(pH, conductivity, DOC) scenarios
- Behavior in relation to acidification
and L/S.
TIER 4a. Equilibrium test TIER 4b. Dynamic test
Leaching control mechanism and Modeling to predict
modeling behavior with pH dynamic metal behavior
Fig. 1. Tier procedure for assessment of metal release from contaminated sediment under CO2 leakages from CCS; [SQG: Sediment Quality Guidelines; AL: Action Levels; DOC:
Dissolved Organic Carbon; L/S: Liquid to solid ratio; ANC/BNC: Acid/Base neutralization capacity; CCS: Carbon Capture and Storage].
M.C. Payán et al. / Environmental Pollution 162 (2012) 29e39 31
The chemical equilibrium model Visual MINTEQ (ver. 2.61) was used to assess
metal leaching by comparing model predictions to experimental data from ANC/BNC
leaching tests and to model the dominant speciation of each component of interest
as a result of aqueous reactions and physico-chemical phenomena of the studied
metals in sediment.
Based on the major crystalline phases of the sediment under study, the input
data consisted of the total concentration of the following major components Ca2þ,
Mg2þ, Al3þ and Ba2þ and the following inorganic metal binding ligands PO3 2
4 , CO3 ,

H4SiO4, SO24 and Cl . Furthermore, model input files were composed of the total
concentrations of the elements of interest (As, Cd, Cr, Cu, Ni, Pb, Zn) and the pH, in
the 0e14 range. Possible solid phases were selected to calculate the leachate
composition in equilibrium. On the other hand, following previous works (Meima
and Comans, 1998; Dijkstra et al., 2006, 2008), the leaching of Cd, Cu, Ni and Zn
were modeled by surface adsorption to Fe- and Al-(hydr)oxides using the diffuse
layer surface complexation model (Dijkstra et al., 2004); the specific surface area
Fig. 3. X-ray diffraction pattern of the sediment [(Q): quartz; (,): dolomite; (D): used was 600 m2/g (Dzombak and Morel, 1990; Dijkstra et al., 2004) and the total
calcite]. amount of amorphous hydrous ferric oxide was calculated from Fe concentration
(Apul et al., 2010). The output database includes the saturation index (SI), which
allows to predict the main phases that control the solubility of the components of
concentrations of contaminants in the EU landfill of waste legal framework (EU,
interest (Cornelis et al., 2008). When seawater is considered as the leaching solution
2003); the leachate obtained from L/S ¼ 4 L/kg test is used in bioassays to study
used, the ionic strength of the seawater and Naþ and Cl ions are taken into account
the effect of the release of chemicals on biota (Shuba et al., 1976; Casado-Martínez
in the modeling.
et al., 2006). Higher L/S ratios than 10 were studied in order to determine the
leaching mechanisms. Leaching tests used deionized water, natural seawater at pH
8 and acidified seawater at pH 7, 6 and 5 as leaching agents. Before the leaching 3. Results and discussion
experiments all laboratory material was acid washed. All leaching tests were per-
formed in triplicate.
The metal content potentially available for leaching from the sediment was 3.1. Physico-chemical and environmental characteristics of the
determined according to the standardized availability test NEN 7341 involving two sediment
consecutive extractions at 10 rpm with deionized water acidified by HNO3 at
L/S ¼ 50 L/kg at pH ¼ 7 and at pH ¼ 4, respectively, each for 3 h. Fig. 3 shows the X-ray diffraction (XRD) pattern of the sediment.
The acid and base neutralization capacity (ANC/BNC) test CEN/TS 15364 was
applied to determine the overall buffering capacity of the sediment. For this,
It appears that quartz is the main crystalline phase; Ca-containing
deionized water solutions with predetermined amounts of acid (HNO3) or base phases such as calcite (CaCO3) and dolomite (CaMg(CO3)2) are also
(NaOH) for obtaining pH values in the range 4e12 (maximum difference between detected.
values of 1.5 pH units) are added to eight dried subsamples at L/S ¼ 10 L/kg and The crystalline phases identified by XRD are in agreement with
10 rpm in three stages. The pH of the leachate is measured after each stage, the
the concentrations of the major elements that are given, expressed
equilibrium verified, and the acid/base neutralization curves obtained.
The filtered natural seawater (0.45 mm) used in these tests is supplied by the as oxide in Fig. 4a. The major elements expressed as oxides repre-
Maritime Museum of Cantabria. The natural seawater at pH 8 was acidified with CO2 sent 99.8% of the total sediment mass in dry weight. Quartz
to obtain the required pH values for the leaching tests. Pure CO2 gas was brought in represents 57% of the total mass, aluminum oxide 8% and calcium
contact with natural seawater in a reactor as very fine bubbles. A pH controller (AT oxide, which is usually present as calcite and dolomite, 7%; the
Control System) monitored the pH and controlled the CO2 bubbling from a CO2 gas
supply. Once the required pH in the reactor is reached, the CO2 supply was stopped
organic matter content as TOC is 1.74%. The concentrations of the
via an automated feedback relay system and the acidified seawater is employed metals considered are given in Fig. 4b. The sediment has high
immediately. Using this method it was possible to supply large quantities of CO2- concentrations of Zn (4030 mg/kg) and Pb (407 mg/kg), whereas As,
acidified seawater of a constant pH (precision of 0.1 pH units). Cd, Cr, Cu and Ni concentrations range from 10 to 60 mg/kg. The
Each sample leachate was filtered through a 0.45 mm pore size nitrocellulose
porosity value of the sediment is 65%.
filtration membrane and divided in subsamples for measuring pH, conductivity, DOC
and As, Cd, Cr, Cu, Ni, Pb and Zn concentrations. A Crison pHmeter GLP 22 with elec- A variety of tools may be used to assess the environmental
trode, accurate to 0.01 pH units was used for pH measurement of all leachates. Elec- significance of pollution in sediment (Álvarez-Guerra et al., 2007).
trical conductivity of the leachates was measured using a Crison Conductimeter Basic Table 1 summarizes the sediment legal framework used in this
30. DOC analysis was performed following DIN EN 1484 with a total organic carbon work. In Spain, the recommendations for the management of
Schimadzu TOC-V Analyzer, where the difference method TOC ¼ TC-TIC was applied.
Cation analyses were carried out using an Agilent 7500 ce ICP-MS. Elements
dredged materials in Spanish Ports proposed by CEDEX (1994) are
were quantified via the method of external calibration, performed using standards based on the Action Levels (AL) approach. The sediment quality
prepared daily from 100 ppm Multi-Element Calibration Standard-2A in 5% HNO3 guidelines (SQGs) use quantitative environmental quality stan-
(Hewlett Packard, Palo Alto, CA). An indium (In) internal standard was applied to dards (Long et al., 1995), being one of the most common approaches
both samples and standards (Vanhaecke et al., 1992). The spectroscopic interference
the effects rangeelow (ERL) and effects rangeemedian (ERM).
of ArCl on As was corrected according to the recommendations of US EPA 200.8
method (US EPA, 1994). Each ICP-MS measurement was carried out with three Another approach uses leaching tests to assess compliance with
repetitions and relative standard deviations were below 7%. Accuracy was checked landfill waste acceptance criteria or guidelines for secondary
by measuring standard solutions as unknown samples. material recycling. In the EU legal framework, limiting values of the
a 100 b 10000000 Total concentration Availability

1000000
10
100000
10000
µg/kg
%
1
1000
0,1 100
10
0,01
1
T)
C
O
2
aO
I
3
5
O
gO
nO
LO
O
O
TO
O
a2
K2
3(
As Cd Cr Cu Ni Pb Zn
Ti
C
2
P2
M
Si
2O
N
Al
Fe
Fig. 4. Sediment concentrations of a) major elements (expressed as oxides) and organic matter (expressed as LOI and TOC); b) metals. For the metals also the availability (NEN 7341)
is given.
Table 1
Concentration of metals in sediment (mg/kg) with reference values for comparison (CEDEX, 1994; Long et al., 1995; Viguri et al., 2007) and [C/Climit] ratio between the
experimental concentration (C in mg/kg) and legal threshold acceptance value (Climit in mg/kg) in inert landfill obtained in different compliance leaching tests (EU, 2003).
Sediment concentration 50 11 58 40 25 407 4030
Regional Background (Viguri et al., 2007) 23 5 e 101 26 14 2 16 2 26 4 92 26
Action Levels for dredged material management (CEDEX, 1994)
Action Level I 80 1.0 200 100 100 120 500
Action Level II 200 5.0 1000 400 400 600 3000
SQGs (Long et al., 1995)
ERL 8.2 1.2 81 34 20.9 46.7 150
ERM 70 9.6 370 270 51.6 218 410
Relative leaching concentration [C/Climit] from the compliance leaching tests according to the waste acceptance in Inert landfill criteria (EU, 2003).
L/S: 2 (Equilibrium test) 0.123 0.009 0.032 0.153 0.055 0.006 0.023
L/S: 10 (Equilibrium test) 0.224 0.04 0.025 0.031 0.067 0.006 0.022
L/S: 0.1 (First eluate of column test)a 0.096 0.014 0.034 0.216 0.261 0.028 0.153
a
For this paper, metal concentration results at L/S ¼ 0.1 L/kg from column leaching test according to CEN/TS 14405 are only considered for compliance purposes.
total content and chemical concentrations in the batch tests EN only about one order of magnitude difference are the most mobile
12457-1,2 and percolation test CEN/TS 14405 at L/S ¼ 0.1 are elements in this test.
considered as the acceptance criteria for different classes of land- The pH titration curve of the ANC/BNC test (Fig. 5) shows that
fills (EU, 2003). 0.8 eq/kg of NaOH were added to reach pH ¼ 12, 0.1 eq/kg of HNO3
In Table 1, Pb and Zn are about fifteen- and forty-threefold to reach pH ¼ 7 and 2.4 eq/kg of HNO3 to reach pH ¼ 4. The ANCpH4
higher respectively than the regional background values for estu- value was within the range of values reported in literature (Lager
arine sediment proposed by Viguri et al. (2007). According to the et al., 2005; Rigol et al., 2009). The sediment has a lower BNC
CEDEX (1994) recommendations, the sediment exceeds the action (0.8 eq/kg of NaOH increased pH by 4.6 units) than ANC (1 eq/kg of
level I for Pb and the action level II for Zn and Cd (Table 1), so it can HNO3 decreased pH by 2 units); this pattern can be explained by
be described as heavily polluted (category III). In relation to the the high carbonate content.
SQGs values, the sediment exceeds the ERM values for Zn, Pb and
Cd (Table 1), and is in the range where adverse biological effects
3.2. Behavior of pH, conductivity and DOC in equilibrium leaching
frequently occur. In addition, levels of As, Cd, Cr, Cu and Ni exceed
tests
the ERLs values corresponding to the 10th percentile of chemical
concentrations associated with adverse biological effects. On the
The initial pH of the leaching solution and its evolution during
other hand, Table 1 shows [C/Climit], which is the ratio between the
the equilibrium leaching tests at different L/S ratios is the most
experimental concentration of the metals in different
important variable in metal leaching processes; in addition, the
compliance leaching tests and the limit concentration for accep-
DOC and the conductivity of the solution may influence metal
tance of waste in inert landfills. All the concentrations are actually
leaching. Average values of pH (Standard Deviation, SD < 0.40 pH
below the EU limit value for disposal in inert landfills or
units), conductivity (Relative Standard Deviation, RSD < 10%) and
[C/Climit] < 1. The contradictions of the characterization results in
DOC (RSD < 25%) from triplicate leaching tests are shown in Fig. 6.
function of the used criteria, point out the importance of sediment
The final leachate pH of the equilibrium tests (Fig. 6a) using
characterization in the conditions of seawater acidification close to
deionized water shows a pH close to 8 for the three tested L/S
the real situation that would be reached in potential leakages of CO2
ratios; with seawater, the final pH is more acid for the lower initial
from CCS. In this sense the use of compliance leaching tests at
pH for the three L/S ratios. However, the final pH ranges with
different conditions of L/S contact and the use of acidified seawater
seawater from 6.8 to 8, because of the high acid neutralization
as leaching agent instead of deionized water, would be useful in the
capacity of the sediment. Fig. 6b shows that conductivity remains
risk assessment task.
rather constant at about 55 mS/cm in the leaching tests with
Fig. 4b shows that the highest difference between total
seawater, close to the natural seawater conductivity as expected. On
concentration in sediment and availability is found for Cd, with
the contrary, for deionized water, conductivity decreases as L/S
three orders of magnitude difference, whereas As, Ni and Zn with
increases, i.e. when less solid is available. It is shown that DOC
(mg/L) decreases in general with increasing L/S ratio (Fig. 6c). It is
expected that at high L/S ratios, less sample is available for leaching.
Furthermore, the highest DOC values are obtained with seawater at
14
pH ¼ 8 and the lowest DOC values (up to two orders of magnitude
12 lower) with deionized water. However, when DOC is presented as
10 release per sample mass (mg/kg) as a function of L/S ratio (Fig. 6d),
DOC increases with L/S for all leachants used due to more DOC is
8
dissolved per unit sample mass when less sediment sample is
pH
6 available.
4
2 3.3. Behavior of As, Cd, Cr, Cu, Ni, Pb and Zn in equilibrium leaching
tests
0
-1 -0,5 0 0,5 1 1,5 2 2,5 3
3.3.1. L/S dependent metal release
Acid added (eq/kg)
Although the pH of the leaching solution is generally the most
Fig. 5. Equivalents of acid/base per kilogram of sediment in the ANC/BNC leaching test. important variable in leaching processes, the L/S may also be
a 8,5 b 70
60
Conductivity (mS/cm)
8 50
40
pH
7,5
30
7 20
10
6,5 0
2 4 10 2 4 10
L/S (L/kg)
L/S (L/kg)
c 250 d 1400
1200
200
1000
DOC (m g/L)
DOC (m g/kg)
150
800
100 600
400
50
200
0
0
2 4 10
2 4 10
L/S (L/kg) L/S (L/kg)
Deionized water Seawater pH 5 Seawater pH 6 Seawater pH 7 Seawater pH 8
Fig. 6. a) pH, b) conductivity, c) DOC (mg/L) and d) DOC (mg/kg) results for equilibrium leaching tests using deionized water and seawater at different pH as leachants. Qualitative
evolution of parameters with pH at each L/S is indicated by arrows.
important in specific scenarios as emphasized in several studies the linear fittings (not shown) is used to describe the increase,
(Mizutani et al., 2000; Kosson et al., 2002). constant or decrease metal behavior in leaching and release
Release of the different inorganic species when represented as representation (figure and matrix of mechanisms), being only the
a function of L/S ratio may be availability or solubility controlled metals with linear fitting values of R2 > 0.7 used to describe the
(Al-Abed et al., 2008). The effect of the change of L/S ratio gives an
indication of whether solubility-controlled or diffusion-controlled EQUILIBRIUM LEACHING TESTS
leaching prevails. Solubility-control results in the concentrations L/S: 2, 4, 10, 15, 20, 30, 40
in the leachate (mg/l) being relatively independent of L/S ratio, but Deionized water, natural seawater at pH 8, acidified
the release (mg/kg) increases with L/S. This occurs when avail-
seawater at pH 7, 6 and 5
ability is high and no depletion of the solid phase can be noticed
during the test. On the other hand, diffusion-control or availability
control gives a release (mg/kg) independent of the L/S ratio and the
concentrations in the leachate (mg/l) are inversely proportional to
L/S. This occurs when the leaching constituent has limited avail- Leaching Release
ability, and solubility is high. However, often a mixture of control
processes dominates (Van der Sloot, 2000; Kosson et al., 2002;
Metal (mg/l)
Metal (mg/kg)
Cornelis et al., 2008). Fig. 7 shows the algorithm used to deter-

mine the dominant control mechanism in the metal mobility using
equilibrium leaching tests.
In the present work equilibrium leaching tests at L/S ¼ 2, 4, 10,
15, 20, 30 and 40 L/kg were used. L/S ratios higher than 10 have
been used to simulate different scenarios of sediment in contact
with acidified seawater in a potential CO2 leakage (Townsend et al., L/S ratio L/S ratio
2006; Ndiba and Axe, 2010). The obtained results for As, Cd, Cr, Cu,
Ni, Pb and Zn show for nearly all studied pHs the decrease in
leachate metal concentration (mg/l) with increased L/S may have
been largely caused by a stronger dilution of the leachate with the Matrix of Leaching Mechanisms
increased L/S after depletion of the exchangeable fraction (Ndiba
and Axe, 2010). After application of the proposed mechanism Release (mg/kg)
Leaching (mg/l) Constant
algorithm, only Cd, Ni and Zn show dominant control mechanisms
Mix Availability Mix
at specific pH values and leaching agents; for the rest of the studied
Constant Solubility Mix Mix
cases, no clear dominant leaching mechanism exists. Fig. 8aed
Mix Mix Mix
show the average metal concentration in mg/L and metal release in
mg/kg behavior with L/S ratio at different pHs for Cd (RSD < 25%) Fig. 7. Algorithm used to determine the dominant control mechanism of metal
and Ni (RSD < 20%), respectively. In these figures, the R2 value from mobility using equilibrium leaching tests.
Fig. 8. Leaching metal results of equilibrium tests as a function of L/S: a) Leached concentration (mg/L) of Cd; b) Release (mg/kg) amount of Cd; c) Leached concentration (mg/L) of Ni;
d) Release (mg/kg) amount of Ni.
behavior with L/S and included in the matrix. The results obtained decreases with decreasing pH (Cappuyns and Swennen, 2008), so
(Table 2) are similar to the behavior previously observed in the that the leaching concentration increases. When pH increases the
leaching of metals from treated sediment using leaching tests at L/S leaching concentration reaches a minimum, and at still higher pH,
between 5 and 100 (Ndiba and Axe, 2010) and from waste working for amphoteric elements, again increases. Under alkaline condi-
with leaching tests at L/S ranging from 2 to 20 (Townsend et al., tions, precipitation of oxides, hydroxides, carbonates and phos-
2006). phates determines the leaching behavior (McBride, 1994; Cappuyns
and Swennen, 2008). The solubility of DOC increases with
3.3.2. Metal leaching as function of pH increasing pH although a slight increase in the DOC release is
Fig. 9 shows the metal and DOC leaching results obtained during observed at pH between 4 and 5. The presence of high proportions
the ANC/BNC test. In soils and sediment, the leaching of metals is of fulvic acids in sediment causes an important solubility of organic
directly and indirectly affected by pH. Leaching concentrations drop matter allow pH values (Cappuyns and Swennen, 2008; Centioli
over two orders of magnitude between pH 4 and 6e7 and generally et al., 2008). A possible explanation of the release of Cu at alka-
increase again from pH 6e7 toward strongly alkaline pH, resulting line pH values is the dissolution of organic matter and the
in a V-shaped leaching curve. At low pH metals usually dissolve complexation of dissolved Cu by DOC.
and, additionally, adsorption sites in soils and sediment are pH-
dependent; the number of negative sites for cation sorption
1000000
100000
Table 2
10000
Metal mobility mechanism from Suances sediment after application of the algo-
rithm from Fig. 7.
( µ g /L )
1000
Leaching Release (mg/kg) 100

(mg/l)
Increase Constant Decrease
10
Increase AVAILABILITY
Zn: Deionized water, Cd: Seawater pH:6,7,8 1
natural seawater
0,1
As: Seawater pH:6 Zn: Seawater pH:6 e 0 2 4 6 8 10 12 14
Ni: Deionized water, pH
seawater pH:6
Constant SOLUBILITY As Cd Cr Cu Ni Pb Zn DOC
Cd: Deionized water Ni: Natural seawater As: Seawater pH:5
Ni: Natural seawater Cu: Seawater pH:5
Fig. 9. pH curves of the studied trace elements and dissolved organic matter in the
Decrease e e e
ANC/BNC leaching test.
Fig. 10 shows the leaching concentrations (mg/L) of the studied The ANC/BNC test experimental results were modeled by the
metals in the ANC/BNC leaching test together with the availability geochemical model Visual MINTEQ with deionized water (solid
concentration obtained in the NEN 7341 leaching tests. In the same curves in Fig. 10) and considering seawater as leaching (dashed
figures the results obtained from the equilibrium leaching tests at curves in Fig. 10).
different L/S ratios using different leachants (deionized water, The equilibrium leaching test values are concentrated in the pH
natural seawater and acidified seawater at pH 7, 6 and 5) are shown. range 6.7e8.5. When deionized water is used as a leachant in these
10000 10000
1000 1000
As (µg/L)
As (µg/L)
100 100
10 10
1 1
0,1 0,1
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
10000 10000
1000 1000
Cd (µg/L)
Cd (µg/L)
100 100
10 10
1 1
0,1 0,1
0,01 0,01
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
100000 100000
10000 10000
Cr (µg/L)
Cr (µg/L)
1000 1000
100 100
10 10
1 1
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
10000 10000
1000 1000
Cu (µg/L)
Cu (µg/L)
100 100
10 10
1 1
0,1 0,1
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
Fig. 10. Concentrations and model predictions of metal and DOC leaching as a function of pH. The concentrations estimated by the NEN 7341 availability leaching test are shown as
horizontal dashed lines. For clarity, pH region of 6e9 is enlarged to shown elements and DOC concentration results using equilibrium tests at different L/S ratios and deionized
water, natural seawater and acidified seawater as leachants. Results for deionized water as a leaching solution for the equilibrium tests are presented with a larger size than
seawater data and surrounded by an ellipse.
10000 10000
1000 1000
Ni (µg/L)
Ni (µg/L)
100 100
10 10
1 1
0,1 0,1
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
100000 100000
10000 10000
1000 1000
Pb (µg/L)
Pb (µg/L)
100 100
10 10
1 1
0,1 0,1
0,01 0,01
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
1000000 1000000
100000 100000
10000 10000
Zn (µg/L)
Zn (µg/L)
1000 1000
100 100
10 10
1 1
0,1 0,1
0 2 4 6 8 10 12 14 16 6 6,5 7 7,5 8 8,5 9
pH pH
1000000
1000000
100000
100000
DOC (µg/L)
10000
DOC (µg/L)
10000
1000
1000
100
100
10
10
1
1
0 2 4 6 8 10 12 14
6 6,5 7 7,5 8 8,5 9
pH pH
ANC-BNC L/S 2 L/S 4 L/S 10
L/S 15 L/S 20 L/S 30 L/S 40
Availability Modeling deionised water Modeling seawater
Fig. 10. (continued).
equilibrium tests, the leaching values are generally lower than the Close examination of the data in Fig. 10 showed that equilibrium
corresponding ones for ANC/BNC test located in the pH range leaching tests present lower concentration values with deionized
8.00e8.50. When seawater is used as a leachant in these equilib- water than with seawater. For seawater as a leaching solution,
rium tests, As, Cd, Cr, Pb and DOC concentrations are similar than element concentration in general decreases with L/S, except for Cr.
ANC/BNC ones; for Ni and Zn, concentration values are lower than The highest concentration values are found for the lowest L/S ratios
ANC/BNC values and, for Cu, concentration values are higher than (2, 4 and 10 L/kg) in the center of the pH range for all elements,
ANC/BNC values in the same pH range. except for Cr, which presents the lowest concentration values for
the lowest L/S ratios. When L/S increases from 2 to 40 L/kg, Pb2(OH)3Cl, Pb3O2SO4, Pb4(OH)6SO4 and Pb4O3SO4 at pH 11e12.
concentrations decrease by about one order of magnitude. Within Dissolved concentrations of Pb were lowest around pH 6. As the pH
a given L/S ratio, metal concentrations increase as pH decreases for increased, Pb leaching also increased. The match between the
As, Cd, Ni, Pb and Zn; the opposite happens for Cr and Cu. These modeled and experimental data was very good in the whole pH
results point out the strong influence of pH on metal leaching from range, but below pH 6 the model underestimated leaching by about
sediment. These metal concentration increases due to the decrease one order of magnitude.
of pH have been estimated at different pH values. At pH 7.3 (the The modeling study (Fig. 10) showed that at pH 5e9 the
acidified seawater pH reached when mimicking leakage from a CO2 controlling phase for Zn is smithsonite (ZnCO3) (Cappuyns and
storage site), As, Cd and Zn present an increase of metal leaching Swennen, 2007), at pH 9e13, hydrozincite (Zn5(CO3)2(OH)6) and,
around 45% and 18% for Pb compared to at pH 8 (normal seawater at pH 10e13, zincite (ZnO) and Zn(OH)2. According to the modeling
pH). At pH 6.8 (the lowest pH value obtained in these equilibrium results, Zn may precipitate as ZnCO3 at pH 5e13. The release
leaching tests), As, Cd and Zn present an increase between 66 and pattern of Zn as a function of pH displayed a minimum around pH 7
82% and 31% for Pb compared to at pH 8 (normal seawater pH). and then increased slightly until pH 12. The agreement between
According to the modeling results (Fig. 10), As may precipitate as modeled and experimental data was good from pH 9 to 12. For the
BaHAsO4:H2O at pH 4e13. Dissolved concentrations of As were first part of the pH range, both curves matched well with less than
lowest around pH 7 and increased as pH increased. This may be one order of magnitude difference. The lower leaching of Cd and Zn
explained by AsO3 4 binding to iron oxides (Hartley et al., 2004; in relation to the modeled curves could be due to the high CaCO3
Apul et al., 2010); the surface charge of the iron oxides changes concentrations in the sediment as the two elements are likely
with pH from positive at lower pH, which attracts the anions to bound to this phase for which they have a high affinity (Van
negative charge at higher pH values, which repels the anions. The Herreweghe et al., 2002).
match between the modeled and experimental data was very good The modeling results with deionized water and seawater show
from pH 4 to 6 and from pH 9 to 14; from pH 6 to 9, the model metal concentrations with maximum differences of one order of
underestimated the dissolved concentration by less than one order magnitude. For As, Cd, Cu and Pb, this difference is mainly found at
of magnitude. the alkaline pH values. In general, the modeling considering
For Cd the experimental leaching curve had a similar shape as seawater as leaching solution presents good agreement with the
the modeled curve (Fig. 10), but the experimental curve displayed seawater equilibrium leaching tests results and slightly better than
a minimum at pH 6, compared to pH 8 for the model. Moreover, modeling considering deionized water. The ANC/BNC test using
experimental leaching at the minimum is lower than predicted. seawater as leaching solution and the consequent geochemical
According to the modeling results (Fig. 10), Cr may precipitate as modeling of the data obtained is proposed as a future work.
Cr2O3 at pH 5e14. A minimum solubility is predicted between pH
7e11. Experimental data for Cr showed a similar dissolution pattern
4. Conclusions
as a function of pH, but the minimum extended from pH 5 to 10. The
model overestimated the experimental data from pH 4 to 8, with
In order to provide a better knowledge of key parameters
two orders of magnitude difference for the lowest pH and less than
controlling the mobility of contaminants from marine sediment in
one order of magnitude difference at around pH 6e8. Above pH 8
contact with CO2 leakages, a variety of standardized leaching tests
modeled and experimental data matched well.
is performed to determine metal release under changing environ-
For Cu, the modeling study (Fig. 10) showed that the controlling
mental conditions. Leaching tests are carried out using deionized
phases are Cu(OH)2 at pH 11e14, tenorite (CuO) at pH 9e13 and
water, natural seawater and acidified seawater by CO2 bubbling as
malachite (Cu2CO3(OH)2) at pH 10e14. The experimental release
leaching solutions. Equilibrium leaching tests reached a lowest pH
pattern showed a strong increase from the minimum at pH 6 until
of 6.8 for seawater leachates. It is noticeable that element leaching
a maximum at pH 10. Cu shows high affinity for organic matter in
is lower when using deionized water than when seawater is the
soils and sediment, particularly humic acids and formation of
leaching solution used. The strong influence of seawater acidifica-
carbonate and hydroxyl soluble complexes (Dijkstra et al., 2004;
tion on metal leaching from sediment due to CO2 leakage is
Nordmyr et al., 2008). The experimental and modeled release
emphasized with the increase in metal concentration for As, Cd, Ni,
pattern presented a similar shape, but the model underestimated
Pb and Zn. It was estimated that compared to pH 8 (normal
the experimental data by less than one order of magnitude in the
seawater pH) at pH 7.3, As, Cd, and Zn concentrations could
pH range 6e10. Our results are in agreement with the ones of
increase by about 45% and at pH 6.8 by 66e82%. The geochemical
Dijkstra et al. (2008), that showed that the leaching of Cu is well
modeling of the experimental data using Visual MINTEQ allows to
predicted by surface complexation to Fe- and Al-(hydr)oxides, and
predict the chemical species in leachates from sediments at
Cu(OH)2(s) precipitates as it becomes oversaturated at pH 10e12.
different pH values showing not big differences in the model with
Ni leaching results (Fig. 10) were modeled based on surface
seawater respect to the model with deionized water. In addition,
complexation to Fe- and Al-(hydr)oxides (Dijkstra et al., 2006).
the study of the metal and DOC release from column tests (Tier 4b)
From the modeling, it appears that Ni(OH)2 is the controlling phase
working with a wide range of L/S ratios is proposed as future work
for Ni at pH 10e14 (Dijkstra et al., 2006; Buj et al., 2010). The
in order to determine experimental behavior of contaminated
modeled and experimental dissolution pattern for Ni as a function
sediment in contact with acidified seawater; the dynamic modeling
of pH agreed acceptably in the last part of the pH range (pH 7e12),
of these data would allow to predict long time metal behavior and
the model underestimated the experimental data for the first part
complete the proposed leaching Tier procedure in this paper for
of the pH range (pH 4e6) by less than one order of magnitude. The
assessment of metal release from contaminated sediment under
experimental release of Ni displayed a minimum in the range of pH
CO2 leakages from CCS.
6e8; this minimum occurs at pH 8e10 for the model.
According to the modeling results (Fig. 10), Pb may precipitate as
chloropyromorphite (Pb5(PO4)3Cl) at pH 4e11. Furthermore, Pb Acknowledgments
seems to be controlled by plumbgummite (PbAl(PO4)2(OH)5:H2O)
at pH 4e9, hinsdalite ((Pb,Sr)Al3PO4SO4(OH)6) at pH 6e7, hydro- This work was supported by the financial help of the Spanish
cerrusite (Pb2(OH)2CO3) at pH 9e12, Pb(OH)2 at pH 9e14 and Ministry of Science and Innovation, Project CTM2008-06344-C03-
01. M.C. Payán was funded by the Spanish Ministry of Science and DIN EN 1484, 1997. Water Analysis. Guidelines for the Determination of Total
Organic Carbon (TOC) and Dissolved Organic Carbon (DOC).
Innovation by means of an F.P.I. fellowship.
Dzombak, D.A., Morel, F., 1990. Surface Complexation Modeling: Hydrous Ferric
Oxide. Wiley, New York.
EN 12457 1-4, 2002. Characterisation of Waste-leaching-compliance Test for
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US EPA, 1994. Determination of Trace Elements in Waters and Wastes by Viguri, J.R., Irabien, M.J., Yusta, I., Soto, J., Gómez, J., Rodríguez, P., Martinez-
Inductively Coupled Plasma-Mass Spectrometry. Method 200.8. EPA/600/R- Madrid, M., Irabien, J.A., Coz, A., 2007. Physico-chemical and toxicological
94-111. characterisation of the historic estuarine sediments: a multidisciplinary
Van der Sloot, H.A., 2000. Comparison of the characteristic leaching behavior of approach. Environment International 33, 436e444.
cements using standard (EN 196-1) cement mortar and an assessment of their Widdicombe, S., Dashfield, S.L., McNeill, C.L., Needham, H.R., Beesley, A., McEvoy, A.,
long-term environmental behavior in construction products during service life Oxnevad, S., Clarke, K.R., Berge, J.A., 2009. Effects of CO2 induced seawater
and recycling. Cement and Concrete Research 30, 1079e1096. acidification on infaunal diversity and sediment nutrient fluxes. Marine Ecology
Van Herreweghe, S., Swennen, R., Cappuyns, V., Vandecasteele, C., 2002. Chemical Progress Series 379, 59e75.
associations of heavy metals and metalloids in contaminated soils near former Wood, H.L., Spicer, J.I., Widdicombe, S., 2008. Ocean acidification may increase
ore treatment plants: a differentiated approach with emphasis on pHstat- calcification rates, but at a cost. Proceedings of the Royal Society B: Biological
leaching. Journal of Geochemical Exploration 76, 113e138. Sciences 275, 1767e1773.
64
2.2. Payán, M.C., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012.
Evaluation through column leaching tests of metal release from contaminated estuarine
sediment subject to CO2 leakages from Carbon Capture and Storage sites. Environmental
Pollution 171, 174-184.
Resumen:
Mediante ensayos de lixiviación en columna, se muestran tanto el cambio de pH como la

liberación de materia orgánica y metales de sedimentos, debido a las potenciales fugas de CO2
por agua de mar acidificada de una zona CAC (Captura y Almacenamiento de CO2). El ensayo
de lixiviación en columna se usa para simular un escenario donde el flujo de agua de mar
acidificada está en contacto con sedimento contaminado. Se analiza el comportamiento del pH,
carbono orgánico disuelto (COD) y metales As, Cd, Cr, Cu, Ni, Pb y Zn, en función de la relación
líquido-sólido (L/S) y el pH. Se plantea una estrategia gradual de análisis y modelado de
resultados usando expresiones empíricas y un modelo geoquímico para ajustar las
concentraciones de movilidad experimentales. A pesar de la capacidad de neutralización del
sistema agua de mar-sedimento rico en carbonatos, se observa una importante acidificación y
movilidad a escala local a bajos valores de pH. Los resultados obtenidos servirán como una línea
de evidencia para la evaluación del riesgo de CAC, en un contexto internacional donde se
aplicarían este tipo de estrategias para mitigar el cambio climático.
65
Conclusiones:
El ensayo de lixiviación en columna se usa para simular un escenario donde agua de mar natural
y acidificada con CO2, a pH 5, 6 y 7, está en contacto con sedimento contaminado de una
potencial zona CAC. El valor de pH inicial del agente de lixiviación empleado se neutraliza
ligeramente por el sistema agua de mar-sedimento rico en carbonatos, aunque bajo condiciones
de acidificación a pH 5, se esperan importantes efectos negativos a escala local debido a la alta
variación de pH encontrada (∆pH = -0.9). La lixiviación de COD es importante al pH del agua de
mar natural y condiciones ácidas ligeras; en un escenario de fugas de CO2(g) el burbujeo de CO2
al pH del agua de mar natural movilizaría grandes cantidades de COD y, en pasos sucesivos,
complejaría los metales movilizados por la acidificación gradual del agua de mar. Se muestra
una liberación del metal acumulada como una función lineal del ratio L/S hasta el final del ensayo
(L/S = 10 L/kg a 56 h). Se han estudiado expresiones matemáticas empíricas y semi-empíricas
para ajustar la liberación acumulada de metales en función de la relación L/S y del pH,
obteniendo buenos coeficientes de correlación y factores de retención del metal a cada pH
estudiado. Con el objeto de modelar el comportamiento geoquímico de los contaminantes en los
ensayos de columna, se ha utilizado el programa de simulación geoquímico Visual MINTEQ,
dando resultados razonables con respecto a los elementos As, Cd, Cr, Ni, Pb y Zn.
Se proponen los ensayos de lixiviación trabajando a pH constante y la determinación

experimental de las concentraciones de hidróxidos de Fe y Al y de ácidos húmicos y fúlvicos
para mejorar la evaluación de la movilidad de metales dada su importancia en el proceso de
lixiviación de metales.
Los resultados obtenidos pueden ser utilizados como una línea de evidencia para la evaluación
del riesgo de CAC en un contexto donde estrategias a corto plazo para mitigar el cambio
climático requieren decisión política, investigación y desarrollo focalizados, así como cooperación
internacional.
66
Environmental Pollution 171 (2012) 174e184
Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol
Evaluation through column leaching tests of metal release from contaminated

estuarine sediment subject to CO2 leakages from Carbon Capture and Storage sites
M. Cruz Payán a, Berta Galan a, Alberto Coz a, Carlo Vandecasteele b, Javier R. Viguri a, *
a
Department of Chemical Engineering and Inorganic Chemistry, ETSIIT, University of Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain
b
Department of Chemical Engineering, University of Leuven, Willem de Croylaan 46, B-3001 Heverlee, Belgium
a r t i c l e i n f o a b s t r a c t
Article history: The pH change and the release of organic matter and metals from sediment, due to the potential CO2
Received 17 February 2012 acidified seawater leakages from a CCS (Carbon Capture and Storage) site are presented. Column leaching
Received in revised form test is used to simulate a scenario where a flow of acidified seawater is in contact with recent
17 July 2012
contaminated sediment. The behavior of pH, dissolved organic carbon (DOC) and metals As, Cd, Cr, Cu, Ni,
Accepted 21 July 2012
Pb, Zn, with liquid to solid (L/S) ratio and pH is analyzed. A stepwise strategy using empirical expressions
and a geochemical model was conducted to fit experimental release concentrations. Despite the
Keywords:
neutralization capacity of the seawater-carbonate rich sediment system, important acidification and
Sediment
CO2 leakage
releases are expected at local scale at lower pH. The obtained results would be relevant as a line of
CO2-acidified seawater evidence input of CCS risk assessment, in an International context where strategies to mitigate the
Metal release climate change would be applied.
Column leaching tests Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction phase, directly in the saline aquifer of storage (aqueous brines) or

during the CO2 gas leakage at short or long distances (native pore
Carbon Capture and Storage (CCS) in geological formations is water, groundwater or seawater) generates acidic CO2 rich fluids
one of the global warming mitigation strategies proposed at plan- that can leak in the same way that CO2 gas and would be in contact
etary level. CCS processes consist of capturing flue gas CO2, trans- with different formation layers including recent contaminated
porting and injecting it into geological formations. Sub-seabed sediment (Chadwick et al., 2004; Pacala and Socolow, 2004; Gaus
geological formations and specially storage in deep saline aquifers et al., 2005; Wilkin and Digiulio, 2010; Zhang et al., 2011, Zheng
appears to hold the most promise sequestration method (Bruant et al., 2012).
et al., 2002; Brown et al., 2011). The effects of CO2 gas and CO2 acidified fluids leakages from CCS
CCS technology needs to be scaled up to fully integrate systems have been widely studied because affect at several envi-
commercial scale to assess their sustainability (Rubin, 2010; CCS ronmental compartments (from the caprock to the human health),
Network, 2011). In this context, local demonstration is important that would be located at high distances from the injection well.
in order to maximize public and political support. As a result of the Effects can be classified as: i) Direct effects of elevated CO2
increasing number of ongoing projects, the International conven- concentrations in the near-surface environment; ii) Effects of dis-
tions (RAMF, 2006; London Protocol, 2007; OSPAR, 2007) and the solved CO2 on water chemistry; and iii) Effects that arise from the
European Directive on the geological storage of CO2, regulate its displacement of fluids by the injected CO2 (Metz et al., 2005). In
injection to guarantee that CCS is an available mitigation option particular, acidic CO2 rich fluids can alter pH with undesirable
(DOL, 2009; Reguera et al., 2009). changes in geochemistry, water quality and ecosystem health.
Although CO2 is injected into the lower part of the storage Examples include mobilization of toxic metals, leaching of biolog-
formation, there are several potential mechanism of CO2 leakage to ical nutrients and modification of proton gradients across biological
the near-surface environment. The dissolution of CO2 into a fluid membranes. CO2 acidified fluid can enhance the release of trace
metals from contaminated sediment so that concentrations may
reach undesirable levels at local scale and affecting the environ-
ment and human health due to its characteristics of persistence,
* Corresponding author. bioaccumulation and toxicity (Widdicombe et al., 2009; Little and
E-mail address: vigurij@unican.es (J.R. Viguri). Jackson, 2010; Lu et al., 2010; Riba et al., 2010).
0269-7491/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.envpol.2012.07.029
However, the impact of metals on the environment depends on 2. Experimental method

their speciation, mobility and bio-availability, and these factors are
2.1. Materials
determined by a group of properties of the solid matrix, leaching
conditions and physico-chemical processes (Van der Sloot et al., The studied area, denominated “Cuchía”, has been classified as a potential
1997; Kosson et al., 2002; Schuwirth and Hofmann, 2006; Kalbe receiving site of CCS techniques (BOE, 2008) (Fig. 1). In this area, the oldest
et al., 2008; Navarro et al., 2011). The potential mobilization of outcropping deposits correspond to the Keuper evaporitic mudstones and dolo-
stones, and are overlain by marine carbonates. The shallow platform is carbonate
substances from sediment, that is the principal sink for trace metals
sedimentation recovered, and the sedimentary facies change gradually to
in aquatic systems (Apitz et al., 2005), motivates the development orbitolinid-rich sands and coral-rudist limestones (Najarro et al., 2011). The specific
of risk assessment models to take into account the chemicals sediment sampling site selected in this work, nearest to the sea, is representative of
released from sediment in a decreased pH environment, among the whole narrow and shallow mesotidal estuary of Suances (Álvarez-Guerra et al.,
other effects. 2008; Bárcena et al., in press). The sediment contains significant concentrations of
metals and organic pollutants derived from the intensive anthropic activities
The problem of possible CO2 leakages from geological storage upstream of the estuary. Detailed description of the studied area and sediment
sites into marine sediment has been studied previously at labora- characterization is presented in the Supplementary Information.
tory scale using batch reactor/chamber. Those works aim to know Total metal content and total organic carbon (TOC) of the sediment were
the potential metal release, as well as changes in pH, TOC and other previously determined as described by Payán et al. (2012). The studied sediment has
high concentrations of Zn (4030 mg/kg) and Pb (407 mg/kg), whereas As, Cd, Cr, Cu
parameters, through experiments bubbling both marine sediment
and Ni concentrations range from 10 to 60 mg/kg with a relatively high acid
and seawater with CO2 gas (Ardelan et al., 2009, 2010). neutralization capacity due to the high carbonate content.
Widdicombe et al. (2009) have developed measurements in order
to find the consequences of CO2 leakages on the macrofauna, 2.2. Column leaching tests
employing marine sediment in contact with CO2 acidified seawater.
Column leaching tests were carried out according to CEN/TS 14405, with
The changes in pH and the impact of CO2 on the mobilization of
modification of the column dimensions. Deionized water, natural seawater and
some metals due to CO2 leakage in an aquifer scenario is studied by acidified seawater at pH 7, 6 and 5 were used as leaching agents. Prior to the leaching
Carey et al. (2009), with CO2 gas, synthetic water and sediment experiments all laboratory material was acid washed and bottles, columns and pipes
contact. In a previous work of the research group (Payán et al., were conditioned with seawater. All leaching tests were performed in triplicate.
2012), standard equilibrium leaching tests for the assessment of
the release of metals from sediment under CO2-acidified seawater
environment was proposed.
Column contact of solid material and CO2 acidified fluids has
been previously used to simulate different CO2 leakages scenarios
(Bateman et al., 2005; Ellis et al., 2011; Frye et al., 2012). Bateman
et al. (2005) work provided a well-constrained long-term column
laboratory experiment with synthetic minerals in contact with CO2-
rich synthetic fluids. Ellis et al. (2011) studied the deterioration of
a fractured carbonate caprock, working with a seven day flow-
through experiment with a core sediment and CO2-acidified 1 M
synthetic brine. Frye et al. (2012) studied the Cd desorption from
artificial sediment with leakages of pure CO2-acidified synthetic
solutions with 0.001e0.1 M ionic strength, in small
chromatography columns. Column tests would be also useful to
assess Carbonated Water Injection strategy where core sediment
would be exposed to acidified water due to the potential CO2
leakages (Bateman et al., 2011; Sohrabie et al., 2011).
In this paper, standard column leaching tests are used to
simulate a “worst-case” scenario where acidified fluid (seawater)
at different concentrations of CO2 is in contact with recent sedi-
ment from a potential CCS site, under advective flow. Liquid to
solid (L/S) ratios from 0.1 to 10 L/kg are considered, involving
average contact times of 1e56 h, respectively. Therefore the
results of the present work are representative of what could
happen if several plausible events co-occurred as rapid fracture
deterioration in carbonate rich caprock, high flow rate of CO2
acidified seawater and contact with carbonate rich contaminated
recent sediment. The use of standardized column leaching tests in
terms of fluid velocity, facilitate the comparability between
experiments.
The main objective of this paper is to evaluate the pH, conduc-
tivity and DOC behavior, and the release of As, Cd, Cr, Cu, Ni, Pb and
Zn from a column leaching test. A stepwise strategy with different
approaches for the experimental data analysis was conducted to fit
DOC and metal concentrations in leachates: the simplest empirical
and semiempirical analysis, using mathematical expressions with
the lowest number of parameters and physical meaning parame-
ters, respectively; and the use of a geochemical model through
Visual MINTEQ to study the speciation of each component of Fig. 1. Cuchía area with indication of the reserved zone for potential CO2 storage and
interest. location of the sediment sampling site in the Suances estuary.
Methacrylate columns with 15 cm diameter and 4 cm filling height were used;

HCO 2 þ
3 ðaqÞ þH2 O ðlÞ4CO3 ðaqÞ þ H3 O ðaqÞ K2 ¼ 1:112$10
9
1000 g of sediment was placed into the columns. The up-flow rate through the
columns, in experiments of 1e56 h, was set at 110 mL/h by a multichannel peristaltic (3)
pump, which corresponds with a linear velocity of 15 2 cm/day as recommended
by CEN/TS 14405. In our experiments advective flow dominant over diffusion, with The experiments (Fig. 2a) using natural seawater and acidified
experimental conditions (flow rate, fluid velocity, contact time, solid and fluid
seawater at pH 6 and 7 contribute to the seawater buffer system,
characteristics) commonly used in previous literature, but with standardized contact
columns in order to allow a clearer comparison between experiments. The filtered obtaining initially (t < 61 min; L/S < 0.1) small pH changes due to
(0.45 mm) natural seawater used (0.61 M) with negligible element concentration is the mix of leaching solution with sediment pore seawater at pH 8.
supplied from the Suances estuary by the Maritime Museum of Cantabria. The CO2 Acidified seawater at pH ¼ 5 leads to strong drop pH during the first
acidified seawater was obtained by CO2 bubbling as described previously in Payán
6 h (L/S < 1) due to the feeding of a leaching solution without buffer
et al. (2012). Details about the column experiments and the preparation are
included in the Supplementary Information.
capacity, that displaces pore water, and aggressive enough to
Column leachates were filtered through a 0.45 mm pore size nitrocellulose exceed the neutralization capacity of the sediment at short contact
filtration membrane and each sample was divided into two subsamples, one for times due to a kinetic matter.
measuring pH, conductivity and DOC and the other one acidified for determining As, The evolution of the final pH column leachate as a function of
Cd, Cr, Cu, Ni, Pb and Zn concentrations. A Crison pH meter GLP 22 with electrode,
time (or L/S) (Fig. 2a) depends mainly on the continuous feed of the
accurate to 0.01 pH units was used for pH measurement of all leachates. Electrical
conductivity of the leachates was measured using a Crison Conductimeter Basic 30. acidified seawater H3Oþ ions, because the OH ions contribution is
DOC analysis was performed following DIN EN 1484 with a total organic carbon much lower due to the sediment solubilization. Using seawater at
Shimadzu TOC-V Analyzer. Cation analyses were carried out using an Agilent 7500ce pH 6, 7 and 8, the final leaching solution pH after 56 h (L/S ¼ 10) is
ICP-MS by external calibration, using internal standard and applying ArCl interfer-
7.6 0.07 in all cases due to the buffer capacity of the seawater. At
ence correction, as is described in Payán et al. (2012).
pH ¼ 5 the continuous feeding of H3Oþ ions and the not buffering
2.3. Modeling of column metal leaching data using Visual MINTEQ software
capacity of the liquid system, triggers the dissolution of carbonate
which stabilizes the pH at 6.8 after approximately 11 h (L/S ¼ 2).
The software Visual MINTEQ (ver. 2.61) was used to assess metal leaching by The non-clay minerals dissolution as consequence of the low pH is
comparing chemical model predictions to column experimental data; and to model confirmed in laboratory experiments with different type of sedi-
the dominant speciation of each component of interest as a result of aqueous
ment (Gaus et al., 2005).
reactions, solid phases and physico-chemical phenomena.
Based on bibliography and on the major phases of the sediment under study, the Using CO2 acidified seawater at pH 6, a low acidity change of 0.1
input data consisted of the total concentration of the following major components (DpH ¼ 0.1) is found, similar to the pre-industrial variations in
Ca2þ, Mg2þ, Al3þ and Ba2þ and the following inorganic metal binding ligands PO3 4 , ocean global acidity (Caldeira and Wickett, 2003), meanwhile using

CO32, H4SiO4, SO2
4 and Cl . Furthermore, model input files were composed of the CO2 acidified seawater at pH 5, a high DpH ¼ 0.9 is found.
total concentrations of the elements of interest (As, Cd, Cr, Cu, Ni, Pb, Zn) and the pH,
in the 0e14 range. Possible solid phases were selected to calculate the leachate
Important negative effects are expected at local scale in scenarios
composition in equilibrium. The metal leaching was modeled by surface adsorption with advective flow of CO2 acidified seawater at pH 5, in contact
to Fe- and Al-(hydr)oxides using the diffuse layer surface complexation model; the with carbonate rich contaminated core sediment.
specific surface area used was 600 m2/g (Dzombak and Morel, 1990; Dijkstra et al., Conductivity values obtained (Fig. 2b) are almost constant at the
2004) and the total amount of amorphous hydrous ferric oxide was calculated as an
natural seawater value of 55 mS/cm, for all acidified seawater
approximation from Fe concentration (Cornelis et al., 2008). NICA-Donnan model,
Gaussian model and SHM model, available in Visual MINTEQ, were used for the leaching solutions used and for all fractions collected at different L/
assessment of metal-organic complexation for this work. The output database S ratios; in the case of deionized water, as expected, conductivity
includes the saturation index (SI), which allows the prediction of the main phases decreases as L/S increases.
that control the solubility of the components of interest (Cornelis et al., 2008). The DOC decreases steeply until L/S ¼ 1 L/kg (Fig. 2c) and then more
ionic strength of the seawater and Naþ and Cl ions were taken into account in the
slowly, showing two different behaviors; a fast release of DOC at
modeling.
low L/S ratios (0.1e1 L/kg), which approaches typical pore water
solutions, due to the organic matter solubilization, and a reduced
3. Results and discussion
release at high L/S ratios that can be attributed to the reduced
availability of the DOC after their initial dissolution (Van der Sloot
3.1. Behavior of pH, conductivity and DOC in column leaching tests
et al., 2001); this different behavior with L/S ratio is more notice-
able at pH ¼ 8, that solubilizes higher amounts of DOC as is
Average values of pH (Standard Deviation, SD < 0.15 pH units),
confirmed by Cappuyns and Swennen (2008).
conductivity (Relative Standard Deviation, RSD < 10%) and DOC
The DOC experimental leaching data can be fitted with L/S by
(RSD < 25%) of the leaching solution from triplicate leaching tests
the simple decreasing exponential expression of Eq. (4), obtaining
are shown in Fig. 2.
the correlation coefficients (R2) showed in Table 1.
Chemical equilibria (Eqs. (1)e(3)) among the species of inor-
ganic carbon CO2/H2CO3/HCO 2
3 /CO3 in seawater is described by
DOC ðmg=LÞ ¼ a$ðL=SÞb (4)
the equilibrium constants. Several correlations of these constants
as a function of temperature and salinity have been published When DOC (mg/L) is plotted as a function of the pH (Fig. 2d), it
(Mehrbach et al., 1973; Weiss, 1974; Dickson and Millero, 1987). The appears that DOC remains almost constant (32.8 4.3 mg/L) up to
acidebase plot including concentrations of the species of the pH around 7.5; from then, DOC increases steeply with pH up to
acidebase pairs of carbonate, borate and water in seawater as 550 mg/L. The results are however scattered. For deionized water,
a function of pH determines which species are most involved in the low DOC mobility is obtained, probably due to the lower ionic
exchange of protons in seawater. At 6 < pH < 9 interval, the strength and lower complexation degree. Similar DOC trends have
amphoteric bicarbonate ion HCO 3 is the dominant specie mean- been obtained in sediment leaching tests with values ranging from
while at pH < 6 the dominant species is the carbonic acid H2CO3. 1 to 1000 mg/L DOC at pH 2e12 (Gardner et al., 2007; Cappuyns
and Swennen, 2008).
CO2 ðgÞ þ H2 O ðlÞ4H2 CO3 ðaqÞ K0 ¼ 3:013$102 (1) These results show the importance of DOC leaching at seawater
natural pH and slightly acidic conditions that would be occur
shortly after a large CO2 leakage; in the first steps of this leakage,
H2 CO3 ðaqÞþH2 O ðlÞ4HCO þ
3 ðaqÞþH3 O ðaqÞ K1 ¼ 1:452$10
6
the agitation of sediment by the CO2 bubbling at seawater natural
(2) pH would mobilize high quantities of DOC and, in latter steps,
a 8,5
b
70
8
60
7,5 50
pH
7 40
9 30
6,5
8
7 20
6 6
5
10
5,5 4
0 0,1 0,2
0
5 0 2 4 6 8 10 12
0 2 4 6 8 10 12 L/S (L/kg)
L/S (L/kg)
c 600
80
d 600
70 500
500 60
DOC (mg/L)
50
400
DOC (mg/L)
400 40
30
300 20 300
10
0 200
200 0 2 4 6 8 10 12
Deionised water
100
100
0
0
6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 8,2
0 2 4 6 8 10 12
L/S (L/kg) pH
Fig. 2. a) pH, b) conductivity, c) leachate concentration of DOC (mg/L) as function of L/S; experimental data were fitted with TableCurve 3D 4.0 Systat software; d) leachate
concentration of DOC (mg/L) as function of pH in column leaching tests.
would complex metals mobilized by the gradual seawater obtained at different L/S ratios (Van der Sloot, 2000; Van der Sloot
acidification. and Dijkstra, 2004).
The mass cumulative release of DOC (mg/kg) has been fitted The cumulative metal release for column leaching tests vs. L/S
semi-empirically as a function of L/S ratio by Eq. (5) (Van der Sloot ratio is shown in Fig. 4aeg (in log and linear scales). It appears that
et al., 1997; Cappuyns and Swennen, 2008) and empirically as cumulative element concentrations in the extract increase with L/S
a function of initial pH and L/S ratio (Fig. 3a) by Eq. (6). until the end of the test at L/S ¼ 10 L/kg. This was also observed by
h i other authors who suggested that metals would probably leach in
DOC ðmg=kgÞ ¼ AVB$ 1 eðL=SÞ=k (5) larger amounts, if exposed for longer L/S durations (Delay et al.,
2007; Gardner et al., 2007; Al-Abed et al., 2008). Contrarily, other
column tests pointed out that the effluent would show increasing
DOC ðmg=kgÞ ¼ a$pHb $ðL=SÞc (6) concentration until steady state conditions were reached (Kalbe
et al., 2008; Simon et al., 2008).
The availability (AVB) in Eq. (5) is the maximum available DOC According to the trend of metal release with pH, four groups of
concentration obtained in the equilibrium L/S ¼ 10 L/kg test with metals can be distinguished in Fig. 4aeg. The same type of trend is
seawater at pH ¼ 8 (872.8 mg/kg), and the adjustable parameter k is observed at any studied L/S ratio. Fig. 4h shows the metal behavior
the matrix retention parameter (L/kg). The results of the fittings in with pH at constant L/S ¼ 10 L/kg from the column data: i), As
Table 2 show lower DOC retention parameters at higher pH values. (oxyanionic element), increases with the pH of the leaching solu-
The parameters values of a ¼ 1.3$104, b ¼ 7.00, and c ¼ 0.5 in Eq. tion (Li et al., 2007); ii) Cd, Ni, Pb and Zn (amphoteric and cationic
(6) corroborate the larger influence of pH than L/S, and leads to elements) constitute a group of metals, in which the highest release
a reasonable fitting with a R2 ¼ 0.96 and a parity plot graph (Fig. 3b) is obtained by the lowest pH value, and with metal releases in
with <10% error. seawater in the pH sequence pH 5 > 6 > 7 > 8; iii) for Cu (highly
3.2. Metal behavior in column leaching tests

Table 1
Adjustable parameters (a, b) and correlation coefficient (R2) for Eq. (4).
3.2.1. Metal concentration as a function of L/S
L/S ratio dependent contaminant release from sediment is used DOC ¼ a$L/Sb Seawater Seawater Seawater Seawater
(Eq. (4)) pH 5 pH 6 pH 7 pH 8
as a surrogate to express release as a function of time, from 1 h (L/
S ¼ 0.1) to 56 h (L/S ¼ 10) at a fluid linear velocity of 15 cm/day. a 29.3 32.5 82.3 257.9
b 0.30 0.27 0.46 0.43
Cumulatively leached concentrations (mg/kg) are used because R2 0.98 0.98 0.99 0.99
enable comparison between samples and comparison of the data
Fig. 3. a) DOC (mg/kg) cumulative release as a function of L/S ratio and pH of leachant in column leaching tests. b) Parity plot (10% confidence interval regression) of the
experimental results and the simulated DOC (mg/kg) concentrations predicted by Eq. (6).
DOC-dependent element), the highest metal release is also found at matrices (surface wash-off) in the column leaching tests, element
the lowest pH (seawater at pH 5), and it increases at higher pH. concentrations (mg/L) are plotted as a function of the final leachate
Finally, iv), for Cr, the release is almost constant as a function of pH. pH (Fig. 7). A decreasing behavior with pH at neutral and slightly
In Fig. 4, it can be observed that metal release (mg/kg) in column basic pH values is observed for Cd, Cu, Ni, Pb and Zn; this behavior
leaching test increases almost linearly with L/S at any pH studied, has been observed previously and was attributed to the higher
suggesting solubility limited dissolution of metals as the prevailing adsorption affinity of some pollutants to soil at higher pH values
leaching mechanism. Eqs. (7)e(9) have been used to fit empirically (Voegelin et al., 2003). As and Cr have an increasing tendency and
the cumulative release of metals, obtaining good correlation coef- near constant behavior with pH, respectively, as it was expected
ficients of the experimental data (Tables 3e5, respectively). due to its oxyanionic behavior. Small amounts of As and Cr become
mobile and remain constant at pH between 6.4 and 7.1. This relative
Metal Release ðmg=kgÞ ¼ a$L=S (7) stability under specific pH conditions has been reported previously
(Shaw, 2006) and the release appears to be related to the speciation
h i
Metal Release ðmg=kgÞ ¼ AVB$ 1 eðL=SÞ=k (8) of the contaminants with changes in the ambient pH conditions
(Payán et al., 2012).
Solubility and leaching of metals from sediment are determined
Metal Release ðmg=kgÞ ¼ a$ðL=SÞ$pHb þ c$ðL=SÞ (9) by a group of properties of the solid matrix, leaching conditions and
physico-chemical processes. The pH is one of the key parameters
The use of Eq. (8), where availability, AVB (mg/kg), is the
that determine heavy metal mobility in sediment: speciation,
maximum cumulative metal release at L/S ¼ 10 L/kg obtained at any
dissolution and many processes are pH dependent or may correlate
of the studied pH, leads to obtain the matrix retention factors (k) at
with the pH value. Thus, small changes in pH can lead to significant
each pH (Fig. 5) that match the wide range of values previously
differences in pollutants mobility.
reported for metal release from different solid matrices (Van der
The solubility of metals as a function of pH can be explained
Sloot, 1996; Cappuyns and Swennen, 2008).
partly by the variation in surface charge as a function of pH. This
The simultaneous fitting of metal release to the L/S and pH
partly explains why cationic metals are generally more soluble at
variables by the empirical Eq. (9) leads to the parity plot of Fig. 6. It
low pH values (Cappuyns and Swennen, 2008). Furthermore, the
is observed that, although Cd, Cu and Pb present good values of R2,
release of metals from soils and sediment is to a large extent
some simulated values present high errors. This trade-off is
determined by the release of DOC (Dalgren et al., 2011). In fact it is
explained by two facts: i) The R2 value is highly influenced by the
known that Cu has great affinity for organic matter because of the
highest values, where the adjustment is very good; e.g., Cu presents
capacity to form stable complexes with humic material (Lager et al.,
very high release values for pH 5, but much lower release values for
2005; Centioli et al., 2008; Hyks et al., 2009). Since As occurs as
other pHs. ii) Metals show very heterogeneous behaviors with pH
arsenate in oxidized soils and sediment, a higher solubility is
(e.g., Cd and Cu, Fig. 4h); this behavior can not be explained without
generally observed as pH increases (Cappuyns and Swennen, 2008).
error by the same mathematical equation used for all metals.
Geochemical models have been used over the last years as a tool
to simulate the behavior of components in different matrices
3.2.2. Metal concentration as a function of pH
(Halim et al., 2005; Vink and Meeussen, 2007; Moberly et al., 2010;
The effect of pH on the release of constituents is considered
Rocca et al., 2012). Among others, Visual Minteq has been exten-
a great point of attention in the leaching process; due to the
sively used for geochemical models to simulate the leaching
important processes of solid material solubility from powdery
behavior of pollutants from sediment (Cappuyns et al., 2007; Shtiza
et al., 2009; Charriau et al., 2011; Meck et al., 2011; Van de Moortel
et al., 2011).
Table 2
The introduction of the HFO influence on the modeling with
Adjustable parameters and correlation coefficients (R2) for DOC (mg/kg) release
obtained after fitting experimental values to Eq. (5). Visual MINTEQ improved modeling results of Cd, Cu, Ni and Zn as
well as the consideration of the Gaussian model for cation-DOC
DOC ¼ AVB$[1 e(L/S)/k] Seawater Seawater Seawater Seawater
binding, especially for Pb. Fig. 7 shows the final results of the
(Eq. (5)) pH 5 pH 6 pH 7 pH 8
geochemical model in seawater by solid curves. The model
k (L/kg) 46.5 41.7 21.7 3.2
R2 0.99 0.92 0.80 0.97
predictions results in the case of As, Cd, Cr, Ni, Pb and Zn experi-
mental leaching column data show one order of magnitude
a 1000 b 100
10
100
As (µg/kg)
Cd (µg/kg)
1
150
10
10
100 0,1 8
6
1 50 4
0,01 2
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
0,1 0,001
0 2 4 6 8 10 12 0 2 4 6 8 10 12

c d
100 100000
10000
Cr (µg/kg)
Cu (µg/kg)
10 1000
100
80 100
60 60000
50000
1 40 10 40000
30000
20 20000
0 1 10000
0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
0,1 0,1
0 2 4 6 8 10 12 0 2 4 6 8 10 12

e 10000
f 10000
1000 1000
Ni (µg/kg)
Pb (µg/kg)
100
100
10 4000
500
10 400 3000
300 1 2000
200
1000
1 100
0,1 0
0
0 2 4 6 8 10 12
0 2 4 6 8 10 12
0,1 0,01
0 2 4 6 8 10 12 0 2 4 6 8 10 12

g h
100000
1000000
Cumulative metal release (µg/kg)
L/S = 10 L/kg
100000 10000
Zn (µg/kg)
10000 As
1000
1000 Cd
100 Cr
120000
100 100000
80000
10 Cu
10 60000
40000 Ni
20000
1 0 1 Pb
0 2 4 6 8 10 12
0,1 Zn
0,1
0 2 4 6 8 10 12
4 5 6 7 8 9
L/S (L/kg) pH
DW Col Exp SW pH 5 Col Exp SW pH 6 Col Exp SW pH 7 Col Exp SW pH 8 Col Exp
DW Eq SW pH 5 Eq SW pH 6 Eq SW pH 7 Eq SW pH 8 Eq
DW Col Simul SW pH 5 Col Simul SW pH 6 Col Simul SW pH 7 Col Simul SW pH 8 Col Simul
Fig. 4. aeg) Cumulative experimental (Exp) and simulated (Simul) release of As, Cd, Cr, Cu, Ni, Pb and Zn in column (Col) and equilibrium (Eq) leaching tests using deionized water
(DW) and seawater (SW) at pH values of 5, 6, 7 and 8 as leaching solutions vs. L/S ratio. The cumulative experimental (Exp) release of metals in column (Col) leaching tests is
indicated by the smaller linear scale inner figures. The cumulative simulated (Simul) release of metals in column (Col) leaching tests is indicated by the larger logarithmic scale
figures. Concentration results from equilibrium (Eq) leaching tests are presented with larger size symbols; h) Experimental cumulative release of studied metals in column leaching
tests vs. initial pH at L/S ¼ 10 L/kg obtained from Fig. 4aeg.
Table 3 10000
Parameter and correlation coefficients (R2) for the cumulative metal release in
column leaching tests at L/S 10 L/kg with the different leaching solutions used
(Eq. 7). 1000
M (mg/kg) ¼ pH 5 pH 6 pH 7 pH 8
k (L/kg)
a$L/S (Eq. 7)
a R2 a R2 a R2 a R2 100
As 3.3 0.99 6.8 0.99 6.9 0.99 8.4 0.98
Cd 0.9 0.99 0.045 0.99 0.047 0.92 0.026 0.99
Cr 7.2 0.99 4.8 0.99 3.8 0.99 3.9 0.99 10
Cu 4974 0.99 112.8 0.99 103.8 0.99 216.5 0.89
Ni 40.2 0.99 8.3 0.98 6.6 0.99 3.5 0.99
Pb 390.7 0.98 3.4 0.97 1.6 0.98 1.2 0.98 1
Zn 10150 0.99 780.6 0.89 479.9 0.96 295.7 0.98
Seawater pH 5 Seawater pH 6 Seawater pH 7 Seawater pH 8

Table 4
AVB values, adjustable parameters (k), and correlation coefficients (R2) for each Fig. 5. Matrix retention factors (k) obtained as fitting parameter of metal release
metal for the cumulative metal release in column leaching tests at L/S 10 L/kg for behavior (Eq. (8)) for each metal at the studied pH values.
the different leaching solutions used (Eq. (8)).
M (mg/kg) ¼ pH 5 pH 6 pH 7 pH 8
AVB$[1 e(L/S)/k] The comparison between the column leaching test values ob-
(Eq. (8))
tained in the present work and the equilibrium leaching test values
Metal AVB k (L/kg) R2 k (L/kg) R2 k (L/kg) R2 k (L/kg) R2 obtained previously following EN 12457 (Payán et al., 2012) at L/S
(mg/kg)
ratio of 2, 4 and 10 L/kg is shown in large size symbols in log scale
As 130 35.1 0.99 11.7 0.98 9.3 0.98 5.6 0.95 Fig. 4aeg, as metal release (mg/kg) and in Fig. 8 as metal leaching
Cd 9 6.1 0.93 161 0.99 130 0.93 205 0.99
Cr 71.14 5.9 0.94 8.3 0.96 9.1 0.96 7.6 0.96
(mg/L).
Cu 50,028 10.1 0.99 365 0.99 339.9 0.99 139.7 0.90 For As, at any pH and L/S ratio, for Cu at pH 6, 7 and 8 and low L/S
Ni 389.8 5.8 0.94 34.7 0.97 37.8 0.99 65.3 0.99 ratios, and for Ni at pH 5 with L/S ¼ 10 L/kg, equilibrium leaching
Pb 3764 5.8 0.93 908.5 0.98 1671 0.98 2013 0.98 values are 1e10 times higher than the results obtained for column
Zn 96,731 5.6 0.95 98.5 0.90 139.5 0.96 200.1 0.98
tests (Fig. 8). This behavior has been attributed to the rougher
treatment of the sediment during equilibrium leaching tests (Delay
et al., 2007; Dalgren et al., 2011). Cd, Cr and Pb on the contrary show
difference; these differences are of the same order of magnitude column concentrations 1e10 times higher than the equilibrium
than the ones found in previous literature (Apul et al., 2010; Buj concentrations, as also shown by Seaman et al. (2005) and Li et al.
et al., 2010). However, a limitation of modeling Cu leaching from (2007). The highest differences found are for Zn at pH 5 and high L/S
column test by Visual MINTEQ has been found, with lower values ratios, with column concentrations >50 times higher than equi-
than the experimental ones, especially at low pH values, in which librium. A deeper analysis of Fig. 8, focused on column and equi-
modeling results present differences up to three orders of librium concentration ratios trends as a function of L/S and pH
magnitude. (Supplementary data), shows two general trends in the leaching
The differences between the geochemical model and the results comparison: i) the highest differences have been found at
experimental data are higher for column or batch leaching tests higher L/S ratios for all metals and pHs, and ii) Cr, Cu, and Zn show
than the ANC/BNC tests as can be corroborated in previous litera- the highest differences at the lower pH 5, but on the contrary As, Ni
ture (Van Herreweghe et al., 2002; Dijkstra et al., 2004, 2006; Payán and Pb show the highest differences at the higher pH 8.
et al., 2012). The observed discrepancies in our case could be From these results, it can be concluded that column and
explained by the different experimental procedure of column tests equilibrium leaching tests results are not entirely comparable,
(CO2-seawater acidification, dynamic contact), and the ANC/BNC
test (HNO3-deionized acidification, equilibrium contact).
3.2.3. Comparison between column and equilibrium leaching tests 1000000

Significant or slight discrepancies have been reported in release
100000
from equilibrium and column tests depending on the metal under
10000
study (Gardner et al., 2007; Al-Abed et al., 2008); in some cases
C Simul (µg/kg)
(Lopez Meza et al., 2008; Grathwohl and Susset, 2009; Quina et al., 1000
2009) relationships between the results from both tests have been 100
established. 10
Table 5 0,1
Fitting parameters and correlation coefficients (R2) for the cumulative metal release
0,01
in column leaching tests (Eq. (9)).
0,001
M ¼ a$(L/S)$ As Cd Cr Cu Ni Pb Zn 0,001 0,01 0,1 1 10 100 1000 10000 100000 1000000
pHb þ c (L/S)
C Exp (µg/kg)
(Eq. (9))
a 11.2 1.9$109 1.7$106 2.3$1011 1.8 $108 1.1$1015 1.9$1014 Cr Ni Cu Zn As Cd Pb
b 0.6 13.3 8.6 11.2 9.6 17.8 14.7
c 25.8 0.027 5.7 46.1 5.9 2.6 451.9
Fig. 6. Parity plot of experimental (C Exp) and simulated (C Simul) metal releases (mg/
R2 0.96 0.99 0.99 0.96 0.99 0.99 0.98
kg) predicted by Eq. (9).
100 100
10
10
Cd (µg/L)
As (µg/L)
1
0,1
0,1 0,01
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
1000 10000
1000
100
Cu (µg/L)
Cr (µg/L)
100
10
10
1
1 0,1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
1000 1000
100 100
Ni (µg/L)
Pb (µg/L)
10 10
1 1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
100000
10000
Zn (µg/L)
1000
100
10
1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH
Column Experimental Visual MINTEQ Modeling
Fig. 7. Visual MINTEQ model predictions (solid curves) of metal leaching concentrations (mg/L) as a function of final pH in column leaching tests.
possibly due to the difference in the experimental procedure proposed by Payán et al. (2012), as Tier 4a and 4b in a structured
(contact time, L/S ratio, agitation and static/dynamic conditions) approach for the assessment of metal release from sediment
(Bin-Shafique et al., 2006; Simon et al., 2008; Cetin et al., 2012). under CO2 acidified seawater leakages from CCS, are
However, the results obtained from both group of tests, complementary.
10000 improved the paper. This work was supported by the financial help
Zn
of the Spanish Ministry of Science and Innovation, Projects CTM
1000 Zn Cu 2008-06344-CO3-01, and CTM 2011-28437-CO2-01, ERDF included.
M.C. Payán was funded by the Spanish Ministry of Science and
Pb Innovation by means of an F.P.I. fellowship.
100
Ni
Ccolumn (µg/L)
Ni
Cr Appendix A. Supplementary material
10 Pb
50:1 Cr
10:1 Cu Supplementary material associated with this article can be
1 As
Cd 1:1 Cd found, in the online version, at http://dx.doi.org/10.1016/j.envpol.
2012.07.029.
1:10
0,1
1:50
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78
2.3. Payán, M.C., Galan, B., Ruiz, G., Coz, A., Viguri, J.R., 2013. Pb and Zn release
from intertidal marine sediment in contact with acidified CO2 seawater: mathematical
model for column leaching tests. Chemical Engineering Science 95, 85-93.
Resumen:
Variaciones en las condiciones ambientales en entornos marinos y de estuario pueden conducir

a la movilidad de contaminantes desde los sedimentos a la fase de agua de mar. El riesgo de la
movilidad de los potenciales contaminantes desde suelos y sedimentos a la fase acuosa se
puede evaluar través de ensayos de lixiviación. En este trabajo, se propone una descripción
matemática de las cinéticas de movilidad de Pb y Zn de sedimentos marinos del estuario de
Suances (norte de España) con agua de mar acidificada con CO2 a valores de pH de 5, 6, 7 y 8
usando ensayos de lixiviación. El modelo considera la transferencia de masa externa desde la
fase líquida a la superficie de la partícula y la difusión efectiva dentro de la misma partícula.
Usando el software Aspen Custom Modeler, se obtienen los valores de difusión efectiva en el
sólido para Zn y Pb: Def,Zn = 1.2110-12 m2/s y Def,Pb = 1.5610-13 m2/s. Finalmente, también se
calculan los valores de difusión superficial en el sólido para cada valor de pH estudiado. Los
resultados obtenidos pueden ser útiles como una línea de evidencia para la evaluación del riesgo
de una zona de captura y secuestro de CO2 donde un flujo advectivo de agua de mar acidificada
a diferentes concentraciones de CO2 esté en contacto con sedimento contaminado.
79
Conclusiones:
Este trabajo presenta un modelo cinético dinámico de la evolución de las concentraciones de Pb

y Zn con la relación L/S usando agua de mar natural y agua de mar acidificada con CO2 a pH 5,
6, 7 y 8 como agentes lixiviantes en contacto con sedimento contaminado. El modelo considera
la transferencia de masa desde la fase líquida a la superficie de la partícula y la difusión
superficial en la fase sólida dentro de la misma partícula. Se ha usado la ecuación de Freundlich
para describir el proceso de equilibrio y se han estimado los parámetros con el modelo.
Usando el software Aspen Custom Modeler, se obtienen los valores de difusión efectiva en el
sólido para Zn y Pb: Def,Zn = 1.2110-12 m2/s y Def,Pb = 1.5610-13 m2/s y también se calculan los
valores de difusión superficial en el sólido para cada pH del ensayo. La buena concordancia
obtenida entre los valores de concentración experimentales y modelados confirma que el modelo
desarrollado puede ser aplicado para la lixiviación de metales Pb y Zn de sedimentos
contaminados bajo condiciones ácidas.
Los resultados obtenidos pueden ser útiles como una línea de evidencia para la evaluación del
riesgo de captura y almacenamiento de CO2 y predicen razonablemente bien la movilidad de Pb
y Zn en escenarios donde agua de mar acidificada con CO2 esté en contacto con sedimento
contaminado.
80
Chemical Engineering Science 95 (2013) 85–93
Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces
Pb and Zn release from intertidal marine sediment in contact with

acidified CO2 seawater: Mathematical model for column leaching tests
M.C. Payán, B. Galan, G. Ruiz, A. Coz, J.R. Viguri n
Chemical Engineering and Inorganic Chemistry, University of Cantabria, Cantabria 39005, Spain
H I G H L I G H T S
Zn, Pb sediment desorption in a CO2 leakages scenario from a potential CCS site.
Mathematical modeling of Zn and Pb desorption from sediments using column leaching test.
Effective surface diffusion values Def,Zn ¼1.21 10−12 m2/s, Def,Pb ¼ 1.56 10−13 m2/s.
Metal diffusion in the solid is controlled by diffusion on the surface of the solid.
Zn and Pb solid-phase surface diffusion coefficients for seawater at pH 5, 6, 7 and 8.
art ic l e i nf o a b s t r a c t
Article history: Variations in the environmental conditions in marine and estuarine environments can lead to the release
Received 19 December 2012 of metal fractions from the sediment to the seawater phase. The risk of release of potential pollutants
Received in revised form from soils and sediment to the aqueous phase is well-assessed through leaching tests. In this work,
27 February 2013
a mathematical description of the kinetics of Pb and Zn release from marine sediment of the Suances
Accepted 28 February 2013
Available online 15 March 2013
estuary (northern Spain) with CO2 acidified seawater at pH values of 5, 6, 7 and 8 using leaching tests is
proposed. The model considers the external mass transfer from the bulk liquid phase to the particle
Keywords: surface and the effective diffusion within the particle itself. Using Aspen Custom Modeler software,
Metal desorption the effective solid diffusion values for Zn and Pb are obtained: Def,Zn ¼ 1.21 10−12 m2/s and
Leaching
Def,Pb ¼1.56 10−13 m2/s. Finally, the solid surface diffusion values for each pH studied value are also
Sediment
calculated. The obtained results would be useful as a line of evidence input for the risk assessment of
CO2 acidified seawater
Mass transfer potential carbon capture and a sequestration site where an advective flow of acidified fluid seawater at
Single porosity model different concentrations of CO2 is in contact with recent contaminated sediment.
& 2013 Elsevier Ltd. All rights reserved.
1. Introduction contact with different formation layers including recent contaminated

sediment and could lead to the release of metal fractions from the
Carbon capture and storage (CCS) in geological formations is one of sediment (Chadwick et al., 2004; Gaus et al., 2005; Wilkin and
the mitigation strategies proposed to reduce global anthropogenic CO2 Digiulio, 2010; Zhang et al., 2011; Zheng et al., 2012).
emissions (Metz et al., 2005). Although CO2 is injected into the lower Sediment constitutes the principal sink for trace metals in
part of the storage formation, there are several potential mechanisms aquatic systems. Slight changes in the pH of the natural seawater
of CO2 leakage into the near-surface environment. CO2 dissolution into in contact with contaminated sediment in estuarine areas, due to
the fluid phase, directly in the saline aquifer of the storage, or during CO2 gas leakage, could mobilize metals from sediment, with metal
CO2 gas leakage, generates acidic CO2-rich fluids that can leak in the accumulation and possible toxic effects in biota depending on the
same way that as CO2 gas. This potential CO2 leakage would be in organisms and sediment´s particular characteristics (Cappuyns
and Swennen, 2006, 2008; Riba López et al., 2010).
The risk of release of potential pollutants from soils and
n
Corresponding author. Tel.: þ34 942 201589; fax: þ 34 942 201591. sediment to the aqueous phase is well-assessed thanks to leaching
E-mail addresses: payanmc@unican.es (M.C. Payán),
galanb@unican.es (B. Galan), ruizg@unican.es (G. Ruiz),
tests (Dijkstra et al., 2006; Roskam and Comans, 2009). Column
coza@unican.es (A. Coz), leaching tests evaluate the release of constituents as a function of
vigurij@unican.es (J.R. Viguri). the liquid to solid (L/S) ratio and are considered moderate in terms
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.02.059
86 M.C. Payán et al. / Chemical Engineering Science 95 (2013) 85–93
of cost and consuming-time tests (Cappuyns and Swennen, 2008; The specific objective of this paper is to develop a transport
Lopez Meza et al., 2008, 2010; Quina et al., 2009, 2011; Roskam and mathematical model obtaining the corresponding transport para-
Comans, 2009). Kalbe et al. (2007) evaluates the reproducibility of meters that allow simulation of Pb and Zn release from contami-
column percolation tests in several laboratories using three waste nated marine sediment samples using natural and CO2 acidified
reference materials; the results show that the column dimensions do seawater at pH 5, 6, 7 and 8 as leaching agent.
not have any substantial influence on the column results concluding
that column test, applying adequate specifications, can be a valuable
instrument for the source term determination within the framework 2. Experimental method
of a leachate forecast. Authors such as Grathwohl and Susset (2009)
also indicate that leaching behavior is independent of the duration and The mobility and bioavailability of metals bound to sediment
physical dimension of the leaching tests. depend on multiple factors such as sediment characteristics and
In order to assess the possible risks to the surrounding physico-chemical forms of metals (Elik, 2007). Metal speciation
environment, as is the case under study, besides the experimental and mobility in sediment and soils is mainly controlled by pH,
analyses, accurate models and well-defined transport parameters redox potential, dissolved organic carbon (DOC), salinity, specific
of the process are useful. The determination of the mathematical metal and binding sites (Centioli et al., 2008; Fytianos and
model, which describes metal release under changing environ- Charantoni, 1998; Kalbe et al., 2007; Navarro et al., 2011;
mental conditions, can provide a way forward for site-specific risk Schuwirth and Hofmann, 2006).
assessment over the short, medium and long term; and for Under important acidification conditions in the surroundings of
developing appropriate and cost-effective, prevention, mitigation a CO2 leakage, a seawater pH value of 5 due to CO2 bubbling could
and remediation strategies. be reached (Carey et al., 2009; Jacquemet, 2009); in these
The release of contaminants such as PAH (Policyclic Aromatic circumstances, a great contaminant release from sediment is
Hydrocarbons), BTEX (Benzene, Toluene, Ethylbenzene and Xylene), expected. Using different values of pH for the leaching solutions,
or metals from beds such as contaminated soils, demolition waste, the environmental conditions that may be encountered in these
sediment or municipal solid waste incineration bottom ash are marine systems under different leakage scenarios are approximated.
modeled in the literature. The material balance and the corresponding Sediment from Suances estuary (northern Spain) were
mathematical model of the sorption–desorption process are expressed collected and standard column leaching tests with CO2 acidified
in various forms in the bibliography depending on simplicity and rigor, seawater at different pH values are used in this work. The column
on the objective of the analysis, and on the specific application of the leaching tests were carried out in a saturated column according to
study. Beyer et al. (2009) obtain the model of the leaching of a modified test CEN/TS 14405, 2004. The characteristics of the
contaminants (PAH or metals) from secondary materials (demolition column and packing, the sediment and the experimental condi-
waste, municipal solid waste incineration ash and blast furnace slag) tions are shown in Table 1. The design of this thin-layer column for
to groundwater with the objective of predicting the long time the leaching test with estuarine sediment is recommended since
behavior under natural field conditions. Rao et al. (2001) address the the experimental time of the test is reduced without affecting the
issues related to the decontamination of marine beach sand acciden- process controlling contaminant release, without sample dete-
tally contaminated by petroleum products, studying the sorption and rioration and without plugging problems.
desorption of BTEX onto sand in a laboratory batch reactor; the work Deionized water (pH≈6.5), natural seawater at pH 8 and CO2
presents a mathematical model taking into account the sorption in acidified seawater at pH 5, 6, 7 were used as leaching agents.
combination with volatilization and uses the Freundlich isotherms. The pure CO2 gas was brought into contact with natural seawater
Transport models are also used for contaminated marine sediment to in a reactor as fine bubbles (maximum diameter 4 mm). A pH-
analyze the possibility of using in-situ capping as a remedial option for controller monitors the pH in the inlet stream and controls the CO2
managing contaminated sediment (Go et al., 2009; Go and Stegemann, bubbling from a CO2 gas supply to keep the pH within the pH
2012). Analytical and numerical modeling approaches were compared target. Once the required pH in the reactor is reached, the CO2
for predicting contaminant transport of the organic contaminant in supply is stopped via an automated feedback relay system and the
vertical distribution using several diffusion controlled and advection
dominated scenarios. The authors (Go et al., 2009; Go and Stegemann, Table 1
Characteristic of the column, the packing and the
2012) use the models to evaluate different materials that can be used
sediment.
as a remedial option for managing the contaminated sediment that
involves the artificial placement of a layer of material over the Column and packing
contaminated area. Column diameter (cm) 15
Length of the package (cm) 4
In Spain, eleven different areas have been chosen as potential
Total mass (g) 1000
subterranean structures for CO2 storage and some of them are Dry mass (g) 565
planned to be in operation in the forthcoming years, 2015, (BOE, Porosity of the package (ε) 0.60
2008). One of these potential CCS stores is located in the
Sediment
continental shelf of the Cantabrian Sea (northern Spain), which BET total surface area (m²/g) 7.11
includes the Suances estuary. Previous works (Álvarez-Guerra Mean particle diameter (cm) 0.0085
et al., 2007; Coz et al., 2008) have pointed out that Pb and Zn Pore volume (cm3/g) 0.0217
Skeletal density (g/cm3) 2.319
concentrations in this estuary exceed the recommended values for
Bulk density (g/cm3) 0.914
estuarine sediment, it being described as a heavily polluted area. Particle porosity (εp) 5.6 10−5
Empirical mathematical expressions have been used to fit the Zn concentration (mol/kg) 6.162 10−2
results of cumulative release of metals from column leaching tests Zn concentration (mg/kg) 4030
as a function of L/S ratio (as substitute of time) and pH obtain- Pb concentration (mol/kg) 1.964 10−3
Pb concentration (mg/kg) 407
ing metal retention factors (Payán et al., 2012a). The Visual
MINTEQ software has also been applied to model the geochemical Experimental conditions
Flow rate (mL/h) 110
behaviour of pollutants in batch tests focusing on the leaching of
Linear velocity (cm/h) 0.625
inorganic contaminants and obtaining reasonable results with
regard to As, Cd, Cr, Ni, Pb and Zn (Payán et al., 2012a, 2012b).
M.C. Payán et al. / Chemical Engineering Science 95 (2013) 85–93 87
(intraparticle) continuity relationship for the solute taking into

account the radial distance, and the Freundlich isotherm for the
description of the equilibrium relationship between solute con-
centrations in the aqueous and solid phase. Kleineidam et al.
(2004) study the desorption kinetics of phenanthrene in litho-
components from aquifer sediment or from fresh rock fragments
through columns following long-term sorption batch experiments
and model the solute diffusion from the aqueous phase to the
grains by Fick's second law. Beyer et al. (2009) quantified the
contaminant (PAH, heavy metals) transport parameters by a
numerical model that simulates the spherical intraparticle diffu-
Fig. 1. Flowsheet of the experimental set-up: leaching column and sample sion considering linear equilibrium distribution using a constant
collection vessel. value Kd. The slow diffusion kinetics of As in microporous media
and the lack of simple equations is also the main problem face by
Sigrist et al. (2011) for predicting the performance of the adsorp-
acidified seawater is employed immediately in the column leach- tion equipments.
ing test. Metal concentration in the acidified seawater at the inlet
stream of the column is negligible. 3.1. Mass transfer model development
A sample vessel collects the column outlet stream as shown in
Fig. 1. Up-flow to avoid channeling and plugging was carried out Mass transfer of a solute in a packed bed column for a non porous
for 56 h and L/S ratios of 0.1, 0.2, 0.5, 1, 2, 4, 5, and 10 L/kg were solid can be thought of as occurring in several steps as shown in Fig. 2.
considered as specific points of sample collection. Pb and Zn First, the solute diffuses along the solid, next the solute diffuses along
analyses were carried out using an Agilent 7500ce ICP-MS by the liquid film close to the particle and finally from the liquid film to
external calibration, using internal standard and applying ArCl the bulk fluid. In this case, it is considered that the solid–liquid
interference correction, as described in Payán et al. (2012a). equilibrium is located on the solid surface.
In this work, the differential mass balance for the metal in the
packed bed is based on the following hypotheses: (i) there are no
3. Mathematical model radial gradients, (ii) isothermal operation, (iii) constant liquid velocity
through the bed, and (iv) linear combination of mass-transfer resis-
Column leaching is frequently described by the well known tances corresponding to external mass transfer, from the liquid film to
advection–dispersion model; however depending on the specific the particle surface, and solid diffusion within the particle itself.
application and experimental conditions, different equation sys- The model is expressed mathematically by Eqs. (1)–(3); Eq. (1)
tems appear in the bibliography as explained in the following expresses the mass balance for component i. The first term of
outline. Eq. (1) represents the accumulation of the solute in the bulk liquid,
Grathwohl and Susset (2009) compares batch and column the second term represents the accumulation of the metal in the
leaching tests in waste and soil materials and use the advection– solid, the third term is convective (or advective) flow and the term
dispersion model to adequately describe the behavior of the in the right-hand part of the equation is due to axial dispersion
column leaching test using a distribution constant between the and diffusion (dispersive transport).
solid and the liquid for the equilibrium. The good agreement
∂C i ð1−εÞ ∂C s,i ∂C i ∂2 C i
between theory and data indicates that in many cases leaching þ ρp þv ¼ ðE þ Dm,i Þ ð1Þ
∂t ε ∂t ∂z ∂z2
occurs at or reasonably close to the equilibrium. Kalbe et al. (2007)
indicate the advection–dispersion model for leaching column test where Ci is the concentration of the metal in the liquid, Cs,i is the
taking into account the retardation by sorption and the reaction concentration of the metal in the sediment, v is the average
for organic compounds. The objective of Poon and Chen (1999) is velocity of the liquid through the column, ρp is the density of
the prediction of the effective diffusivities of five metals from the sediment, ε the porosity of the packing, E the axial dispersion
cement-based solidified hazardous waste when leaching column coefficient and Dm,i is the diffusivity of the metal in the liquid
tests are used since the effective diffusivity is characteristic of the phase. The value of Dm,i can be calculated using the Nernst–Haskell
long-term leaching process; to do so, the authors consider the equation and the values obtained for Zn and Pb are: Dm,Zn ¼
advection–diffusion model to take into account the net rate of 7.02 10−9 m2/s and Dm,Pb ¼9.44 10−9 m2/s, respectively. When
production of mobile contaminant caused by chemical reactions
and sorption/desorption process for simulating the flow-through
leaching conditions.
Sorption/desorption processes using fixed-bed reactors also use
diffusion–advection equations to simulate the behavior of different
contaminants in natural systems. It is widely accepted that slow
sorption and desorption processes are due to diffusion-limited trans-
port of solutes to sorption sites inside particles or soil aggregates.
Olmstead and Weber (1990) consider the advection–dispersion equa-
tion and the solid phase continuity equation (intraparticle diffu-
sion) in the model for organic contaminant compounds; the
authors determine the mass-transfer parameters for p-dichloro-
benzene sorption process involving microporous solids such as
activated carbon, ion-exchange resins and soil particles putting an
emphasis on the evaluation of statistical confidence. Three equa-
tions are considered in that work: the fluid-phase continuity Fig. 2. General scheme of the mass transport of solute (i) in a particle of
equation written in one-dimensional form, the solid-phase a packed bed.
the value of Reynolds number is lower than 20, E can be Table 2

determined with the relation Eε=vdp ¼ 1:8 (Levenspiel, 1999) Composition (mol/L) of the inlet streams for the studied metals and the dissolved
carbonate species under different pH conditions.
where dp is the mean particle diameter. In this work, the value
of E is calculated as 4.42 10−10 m2/s. Inlet pH Composition (mol/L)
Eq. (2) describes mass transport for component i in the liquid
interphase and Eq. (3) describes mass transport in the solid phase [Zn2+] [Pb2+] [H2CO3] [HCO-3] [HCO2-
3 ]
for component i.
5 0 0 6.886 10−5 9.998 10−6 1.112 10−9
∂C s,i 6 0 0 6.872 10−7 9.978 10−7 1.110 10−9
ρp ð1−εÞ ¼ kF ap ðC i −C i,eq Þ ð2Þ 6.738 10−9 9.782 10−8 1.088 10−9
∂t 7 0 0
8 0 0 5.691 10−11 8.181 10−9 9.097 10−10
∂Csi 5ð1−εp ÞDef ,i
¼ ap ðCsi −Csi,eq Þ ð3Þ
∂t rp
where Ci,eq is the equilibrium concentration of metal in the liquid,
salinity of 35 g/kg; so it is possible to calculate the concentration of
Csi,eq is the equilibrium concentration of metal in the solid, εp is the
the species in equilibrium for each pH. Table 2 shows metal and
porosity of the particle, Def,i is the effective diffusion coefficient in
H2CO3, HCO−3 , CO2−3 concentrations of the inlet stream.
the solid and kF is the mass transport coefficient in the liquid
In Table 2 it can be seen that the HCO−3 concentration is
phase, rp is the radium of the particle and ap is the surface area of
predominant for inlet pHs of 6, 7 and 8, respectively; however
the particle. Mass transport in the liquid phase is negligible since
the experiment carried out at pH 5, has H2CO3 as predominant
the mass transport in the solid phase is much lower than in the
species. The acidic character of H2CO3 increases the desorption of
liquid phase, therefore Eq. (2) can be neglected.
metals from the sediment.
In relation with the porosity of the particle, the BET total
In relation to the solid–liquid equilibrium of the metal (M)
surface area and pore volume values in Table 1, together with the
under study, the Freundlich isotherm (Eq. (8)) is considered as the
slope of the isotherm indicate that the Suances estuarine sediment
equilibrium expression, with the Freundlich adjustment para-
is non-porous solid.
meters: (1/n)i and bi.
L/S ratio is used in this work as a surrogate to express release as
a function of time and therefore time (t) is substituted by L/S using M 2 þ ðsÞ ⇄ M 2 þ ðaqÞ
the expression: L=S ¼ Q =M S t where Q is the liquid flow rate and ð1=nÞi
Csi,eq ¼ bi C i,eq ð8Þ
Ms is the sediment mass in the column. Finally, the model is
expressed by Eqs. (4) and (5) and the initial and boundary where Csi,eq, Ci,eq are the equilibrium concentrations of the metal in
conditions by Eqs. (6) and (7). the solid and in the liquid, respectively. These (1/n)i and bi
∂C i M s 1 ∂Csi M s ∂C i Ms ∂2 C i parameters depends on the pH, and in this model we assume
þ 2 þ 2 ¼ 2 ðE þ Dm,i Þ ð4Þ the simplest case: linear dependence.
∂ðL=SÞ πr p l ε ∂ðL=SÞ πr p ∂z πr v ∂z2
In general, works (Grathwohl and Susset, 2009; Kalbe et al.,
π r 2p
∂C s,i 5 ð1−εp Þ Def ,i 2007) that model the behavior of compounds in leaching test
¼ ap ðCsi −Csi,eq Þ ð5Þ consider a linear constant distribution coefficient between solid
M s ∂ðL=SÞ rp
and liquid phase. In this work, more general equilibrium expres-
with the initial conditions sion, such as the Freundlich equation, has been selected in order to
C i ðz,0Þ ¼ C i,in apply the model to a greater range of metal concentrations.
Csi ðz,0Þ ¼ Csi,in ð6Þ The values of Freundlich parameters have not been calculated
experimentally due to the imposibility of keeping the pH constant
The boundary conditions along the column for different inlet pH values; therefore, the
C i ðl,tÞ ¼ C i,out values are estimated by the Aspen Custom Modeller software as
∂C i ðl,tÞ shown at Section 4.2.
¼0 ð7Þ
∂z
where Ci,in is the concentration of metal at the inlet of the column 4. Results and discussion
which is 0 in this work, Csi,in is the initial concentration of metal in
the solid, Ci,out is the concentration of metal at the outlet of the 4.1. Analysis of the column leaching tests experimental results
column and l is bed length.
The mathematical modeling of the column requires the equili-
3.2. Equilibrium conditions description brium expressions in the liquid–solid (Eq. (5)) which depends on
the pH through the Freundlich adjustment parameters (n and b) in
The description of the equilibrium conditions is included in the
Eq. (8).
mass transport model through Eq. (5).
The pH values in the sample collection vessel (outlet pH of the
In this work the pH of seawater is modified by CO2 addition,
column as shown in Fig. 1) at different L/S values for inlet pH
therefore the carbonic acid equilibrium reactions in water must be
values of 5, 6, 7 and 8 are presented in Table 3. The change of pH
considered. These reactions are expressed as:
from the inlet value (5, 6, 7 or 8) to the final value in the collection
vessel implies a gradient of pH in the column to be considered
H2 CO3 ðaqÞ þ H 2 OðlÞ⇄ HCO−3 ðaqÞ þ H 3 O þ ðaqÞ K a1 ¼ 1:452 10–6
in the development of the mathematical model through Eqs. (5)
and (8).
HCO−3 ðaqÞ þ H 2 OðlÞ ⇄ CO2− þ
3 ðaqÞ þ H 3 O ðaqÞ K a2 ¼ 1:112⋅10–6
In Table 3 it is observed initially, at the lowest L/S value of 0.1,
that similar outlet pHs values are obtained for the four inlet pHs,
The expressions of Ka1 and Ka2 depend on temperature and indicating that inlet pHs (5, 6, 7 and 8) are neutralized by the
salinity and were obtained from the bibliography (Millero et al., sediment, probably due to the natural interstitial water and pore-
2002, 2006; Roy et al., 1993) considering temperature of 25 1C and water; in fact, the initial column mobilization at L/S ¼0.1 L/kg of
Table 3
Variations of the pH values in the sample collection vessel with L/S and for different inlet pH in the column.
L/S pH in the sample collection vessel
Inlet pH¼ 5 Inlet pH¼ 6 Inlet pH¼ 7 Inlet pH¼ 8
0.1 7.13 7.35 7.61 7.51

0.2 7.07 7.30 7.54 7.49
0.5 6.72 7.26 7.51 7.51
1 6.63 7.26 7.49 7.58
2 6.76 7.32 7.48 7.55
4 6.75 7.34 7.49 7.62
5 6.87 7.37 7.51 7.62
10 6.79 7.47 7.57 7.61
Average pH and statistical deviation in the sample collection vessel for L/S≥0.5 ratios 6.75 7 0.05 7.34 7 0.06 7.517 0.02 7.56 7 0.035
Average pH and statistical deviation for L/S≥0.5 ratios at pH 6, 7 and 8 7.477 0.12
metals occurs when surface wash-off process plays a predominant

role (Delay et al., 2007; Tiruta-Barna et al., 2004). For L/S ratios
≥0.5, it is observed, at all of the inlet pHs, that the pH of the
sample collection vessel changes very slightly and an average
value is considered from L/S¼0.5 to L/S ¼10. These average values
(Table 3) are considered in the mathematical model as the pH at
the outlet of the column. For L/S ¼0.2, an intermediate situation is
observed.
It is also observed that for the inlet pH of 6, 7 and 8, the average
outlet pH for L/S ≥0.5 is 7.47 (last line of Table 3). This value is only
a little lower (0.5 unit) than natural seawater (pH 8) and therefore
low metal mobilization is expected in these cases. However, when
inlet pH is 5, the outlet pH for L/S ≥0.5 is 6.75, which is 1.25 units
lower than natural seawater (pH 8) and therefore higher metal
mobilization is expected.
Fig. 3 shows the concentration release (mg/L) of the column
leaching tests for Zn and Pb as a function of L/S ratio. It can be seen
that, for inlet pH 5, element concentrations in the extract increase
with L/S ratio up to L/S ¼5. However, for pH 6, 7 and 8, metal
concentrations in the extract decrease with L/S ratio until L/S ¼5.
For all the inlet pHs, from L/S ¼5 to L/S ¼10, the concentration
keeps relatively constant or decreases slightly. General metal
behavior shows the highest mobilization of the inorganic compo-
nents in the initial stage of the elution when dissolution and
surface wash-off processes play a predominant role, and a second
stage where the progression of leaching time leads to lower
leaching concentrations of these components in the eluates
Fig. 3. Concentration release (mg/L) of Pb and Zn in column leaching tests.
(Al-Abed et al., 2008; Delay et al., 2007; Kosson et al., 2002;
Tiruta-Barna et al., 2004). This common behavior is observed
clearly in Fig. 3 for both metals at inlet pH of 6, 7 and 8. It is also observed in Fig. 3 that the maximum concentration is
However, for inlet pH 5, different behavior is observed, probably around 11.500 mg/L for Zn and the maximum concentration is
due to the fact that this acid pH generates a stronger dissolution around 420 mg/L for Pb. The Pb concentration values, for seawater
over a longer time. at inlet pHs 6, 7 and 8, are closed to the values obtained when
This uncommon behavior of metal release with inlet pH 5, can deionized water is used. However, the concentration of Zn, when
be explained because under experimental conditions (temperature seawater at pH 6, 7 and 8 is used, is higher that the values
25 1C and salinitiy 35 g/kg) the predominant species at that pH is obtained for deionized water.
H2CO3 (Riba López et al., 2010) (Table 2); furthermore, H2CO3 is
dissociated in water as H2CO3↔H þ þHCO3− which favors a lower 4.2. Modelling results
pH. This lower pH also favors a stronger chemical attack on the
sediment and therefore a higher release of metal concentration in The resolution of the proposed dynamic model and the
comparison to higher pHs. When inlet pH is 7 and 8, the situation estimation of the corresponding parameters are done using Aspen
is just the opposite: the predominant species is HCO3− and the Custom Modeler software which enable us to solve rigorous
fractional amount of H2CO3 is low (Table 2). At pH 6, the situation models and to make a parameter estimation simultaneously. The
is the intermediate and both compounds are present in similar adjustment of the model parameters is carried out using an
amounts. The predominant species at inlet pH of 6, 7 and 8 is NL2SOL algorithm for least-square minimization of the deviation
HCO3− which is an amphoteric species in water that generates a between experimental and theoretical data. The dynamic model
buffer solution that is favorable to pH remaining constant at consists of a two unit-model: the packed bed column, represented
around 7. by Eqs. (4)–(8), and, the sample collection vessel, where the
outlet stream of the column is collected as a mix tank, represented Metal diffusion in the solid can be controlled by diffusion in the
by Eq. (9). pores, by diffusion in the surface of the solid or by both of them as
shown by Eq. (10) (Choy et al., 2004; Diban et al., 2007). The first
dðC Ti V Þ Q dðC Ti VÞ term on the right-hand-side of Eq. (10) indicates diffusivity in the
¼ ¼ Q C Ti,in ð9Þ
dt M S dðL=SÞ pores and the second term on the right-hand-side diffusivity in
the solid-phase surface.
where C Ti is the concentration of metal (i) in the collection sample,
V is the liquid volume in the tank, C Ti,in is the concentration of Dm,i dCsi,eq
Def ,i ¼ εp þ ρp Ds,i ð10Þ
metal in the inlet stream of the tank. The column has been τ dC i,eq
simulated using four steps and it has been checked that, using a
where τ is the tortusity factor of the pores, Ds,i is the solid-phase
greater number of steps, the same results are obtained.
surface diffusion coefficient and dCsi,eq/dCi,eq is the slope of the
Table 4 shows the estimated values of the Freudlinch
liquid–solid equilibrium isotherm.
equation (Eq. (8)) parameters, 1/n and b for Zn and Pb for the
For the present case under study, diffusion on the solid-phase
solid–liquid equilibrium. Fig. 4 represents the solid–liquid simu-
surface is the limiting step since the Suances sediment is a non-
lated equilibrium curves of each metal calculated using the
porous solid (εp ¼5.6 10−5) and low effective diffusion coeffi-
parameters shown at Table 4.
cients are obtained. It is widely accepted that slow sorption and
The values of the effective diffusion parameters in the solid for
desorption processes are due to diffusion-limited transport of
both metals have been estimated by the resolution of Eqs. (4)–(9)
solutes to sorption sites inside the particles or soil aggregates
through comparison with the experimental values, obtaining
(Olmstead and Weber, 1990). Other authors have demonstrated
the following values: Def,Zn ¼1.21 10−12 m2/s and Def,Pb ¼ 1.56
that intraparticle solid diffusion is the rate-limiting step in the
10−13 m2/s.
sorption of Cd and Zn to microporous oxides (Diban et al., 2007).
Therefore, we can conclude that the value of effective diffusion
parameter obtained in the solid for Zn and Pb is related to the
Table 4 value of surface diffusion in the solid phase.
Values of the Freudlich parameters for solid–liquid equilibrium (Eq. (8)). Eq. (11) indicates the relation between the effective diffusion
coefficient (Def,i) and the solid-phase surface diffusion coefficient
pH Zn Pb
(Ds,i) considering diffusion in the pores negligible.
1/n b 1/n b
dCsi,eq
5 0.408 1.564 0.500 2.572
Def ,i ¼ ρp Ds,i ð11Þ
dC i,eq
6 0.291 1.550 0.290 0.327
7 0.278 1.466 0.273 0.265 Effective diffusivity in the solid phase is a constant value but
8 0.265 1.383 0.251 0.205
solid-phase surface diffusivity depends on the pH since dCsi,eq/dCi,eq is
different for each pH value as shown in Fig. 4. Table 5 shows the
solid-phase surface diffusivity values for each pH and each
metal being observed; solid-phase surface diffusivity is 4–100
times higher for Zn than for Pb. These solid-phase surface
diffusivity values are similar to the values obtained by Trivedi
and Axe (2001) Axe and Trivedi (2002). These authors study the
mobility of metals (Cd, Zn and Sr) in soils and sediment and
demonstrate that intraparticle diffusion is the rate-limiting step
in the sorption process for three amorphous oxides (Al(HAO),
Fe(HFO) and Mn(HMO)) which are ubiquitous in soils and
sediment. It is observed (Table 5) that the value of solid-phase
surface diffusivity increases when pH decreases; Trivedi and
Axe (2000) observed the same behavior, which indicates that
surface diffusivity is a function of site density which is consis-
tent with the energy activation theory.
Fig. 5 shows the experimental data and simulated results
obtained by the model presented in the paper. The good agree-
ment between experimental and simulated results can also be
observed in the parity plot in Fig. 6. The statistical parameters of
the comparison between experimental and simulated data for all
pHs together are calculated by the software: standard error of
Table 5
Solid-phase surface diffusivity values for each pH and each metal (Eq. (10)).
pH Zn Pb
dCsi,eq/dCi,eq (kg/m3) Ds (m2/s) dCsi,eq/dCi,eq (kg/m3) Ds (m2/s)
5 3.53 105 1.48 10−18 5.22 105 5.09 10−19

6 1.36 106 3.82 10−19 2.12 107 1.25 10−20
7 1.61 106 3.23 10−19 3.49 107 7.62 10−21
8 1.90 106 2.74 10−19 4.68 107 5.67 10−21
Fig. 4. Simulated solid–liquid equilibrium curves for all studied pHs.
2.00E-04 2.50E-06
pH = 5
pH = 5
1.60E-04 2.00E-06
[Pb] (mol/L)
[Zn] (mol/L)
1.20E-04 1.50E-06
8.00E-05 1.00E-06
4.00E-05 5.00E-07
0.00E+00 0.00E+00
0 5 10 15 0 5 10 15
2.50E-05 3.00E-07
pH = 6 pH = 6
2.50E-07
2.00E-05
[Pb] (mol/L)
[Zn] (mol/L)
2.00E-07
1.50E-05
1.50E-07
1.00E-05
1.00E-07
5.00E-06 5.00E-08
0.00E+00 0.00E+00
0 5 10 15 0 5 10 15
1.60E-05 1.00E-07
pH = 7 pH = 7
8.00E-08
1.20E-05
[Pb] (mol/L)
[Zn] (mol/L)
6.00E-08
8.00E-06
4.00E-08
4.00E-06
2.00E-08
0.00E+00 0.00E+00
0 5 10 15 0 5 10 15
3.00E-05 5.00E-08
pH = 8 pH = 8
2.50E-05 4.00E-08
[Pb] (mol/L)
[Zn] (mol/L)
2.00E-05
3.00E-08
1.50E-05
2.00E-08
1.00E-05
1.00E-08
5.00E-06
0.00E+00 0.00E+00
0 5 10 15 0 5 10 15
Fig. 5. Simulated results and experimental data of the metal concentration at the collection vessel with L/S for the different CO2 acidified seawater at pH 5, 6, 7 and 8.
estimate is 2.964 10−6 for Zn and 4.532 10−8 for Pb, and 5. Conclusions
percentage variation is 99.5 for Zn and 99.0 for Pb. For a total
number of 36 samples of each metal, only 4 samples for Zn and Pb This work presents a dynamic kinetic model of the evolution of
have a relative error higher than 15%. The good agreement shown Pb and Zn concentrations with L/S when natural seawater and CO2
in the figures and the good statistical parameter values confirm acidified seawater at pH 5, 6, 7 and 8 are used as leaching solutions
that this model can be applied for Pb and Zn metal leaching from in contact with polluted sediment. The model considers mass
sediment under acidic conditions. transfer from the bulk liquid phase to the particle surface and the
2.00E-04
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residues. Waste Manage. 29, 2483–2493. 4821–4827.
Quina, M.J., Bordado, J.C.M., Quinta-Ferreira, R.M., 2011. Percolation and batch Zhang, Y., Vouzis, P., Sahinidis, N.V., 2011. GPU simulations for risk assessment in
leaching tests to assess release of inorganic pollutants from municipal solid CO2 geologic sequestration. Comput. Chem. Eng. 35, 1631–1644.
waste incinerator residues. Waste Manage. 31, 236–245. Zheng, L., Apps, J.A., Spycher, N., Birkholzer, J.T., Kharaka, Y.K., Thordsen, J., Beers, S.R.,
Rao, B.H., Swaminathan, R., Asolekar, S.R., 2001. Washing of marine coastal sand in Herkelrath, W.N., Kakouros, E., Trautz, R.C., 2012. Geochemical modeling of changes
a batch reactor: sorption and desorption of BTEX. J. Air Waste Manage. Assoc. in shallow groundwater chemistry observed during the MSU-ZERT CO2 injection
51, 1043–1059. experiment. Int. J. Greenhouse Gas Control 7, 202–217.
90
PROCEDURES AND MATERIALS USED.
OVERALL SUMMARY OF RESULTS AND
DISCUSSION
Procedures and materials used. Overall summary of results and discussion
92
3. PROCEDURES AND MATERIALS USED. OVERALL SUMMARY OF

RESULTS AND DISCUSSION
3.1. Tier approach procedure
A Tier structured approach for the assessment of metal and DOC release from contaminated
marine sediment under CO2 leakages from CCS is proposed consisting of four tiers of
investigation shown in Figure 3.1. Tier 1 comprises information related to the sediment area and
the determination of the total concentration and maximum potential release. Tier 2 involves the
physico-chemical characterization of the sediment (mineralogy, major and minor elements,
organic matter content, ANC/BNC and hydrodynamic properties of the solid material). Tier 3
focuses on final pH, conductivity and DOC behavior in relation to initial pH and L/S ratio. Tier 4
comprises the assessment of metal mobility due to acidification as a function of pH and L/S under
different scenarios: (Tier 4a) leaching control mechanisms and modeling of metal leaching as a
function of pH in equilibrium tests, (Tier 4b) dynamic modeling to predict metal behavior in column
tests, and (Tier 4c) metal mobility assessment in pH dependence tests.
TIER 1. Environmental characterization TIER 2. Physico-chemical characterization

(Total sediment concentrations and basic Mineralogy, major and minor elements, organic
characterization and compliance leaching tests) matter content, ANC/BNC, hydrodynamic
- Comparison with SQG, AL, landfill limits properties
Assessment of metal release from

contaminated sediment under CO2
leakages from CCS
TIER 4. Metal release in
leaching tests
TIER 3. Global parameters behavior Metals vs L/S and pH under different scenarios
(pH, conductivity, DOC)
- Behavior in relation to acidification and L/S. TIER 4a. Equilibrium test
Leaching control mechanism and
modeling behavior with pH
TIER 4c. pH dependence test
Metal mobility in the whole pH
TIER 4b. Dynamic test range
Modeling to predict dynamic
metal behavior
Figure 3.1. Tier procedure for assessment of metal and DOC release from contaminated marine
sediment under CO2 leakages from CCS; [SQG: Sediment Quality Guidelines; AL: Action Levels;
DOC: Dissolved Organic Carbon; L/S: Liquid to solid ratio; ANC/BNC: Acid/Base Neutralization
Capacity; CCS: Carbon Capture and Storage]
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3.2. Sediment characterization
3.2.1. Area of study: Suances estuary
The estuary of Suances (Northern Spain) is an area reserved as potential CO2 storage site (BOE,
2008) and has an intensive ship transport to the inlet industrial harbor and to the nearby
Santander third generation harbor (Fig. 3.2). The studied marine surface sediment contains
significant concentrations of metals and organic pollutants from the intensive industrial, mining,
agricultural and urban activities upstream of the estuary (Álvarez-Guerra et al., 2008).
The Suances estuary (-4.0237/43.4007 ED50) is a narrow and shallow mesotidal estuary, with
typical spring-neap cycle tidal ranges varying between about 5.1 m (extreme spring) and 0.7 m
(extreme neap), located in the northern Spanish coast (Fig. 3.3). It is 5.5 km long, with a 150 m
mean width and a surface area of 389 ha, 76% of which is occupied by intertidal flats. The
shallowest depth is 3.2 m (above the mean sea level) corresponding to the tidal flats located
along the Suances estuary and the depth of the main channel varies between 1 m (head) to 8 m
(mouth) (Bárcena et al., 2011; DMA, 2013).
Figure 3.2. Suances estuary area
Land reclamation has reduced the original estuarine area by 30%, while 50% of the estuary is
bordered by dikes (over 13000 m), which dramatically modify its hydrodynamic conditions,
94
especially since 1878 with the construction of a jetty in the mouth of the estuary for transport
facilities (Gobierno de Cantabria, 2005; Romero et al., 2008).
The main freshwater input to the system comes from two similar rivers draining relatively small
basins, the Saja and the Besaya, which occupy a catchment area of 966.67 km2 with a perimeter
of 166.27 km. The freshwater inflow, in natural conditions, varies from about 1 to 600 m3/s, with
typical flows in the range of 7-24 m3/s (García et al., 2008). These river basins converge in the town
of Torrelavega (56000 inhabitants). After the confluence of the Saja river and the Besaya river, a
small river stretch (1890 m) flows up to an industrial weir which limits the end of the tidal influence
into the river basin, i.e., the head of the Suances estuary. This river stretch is called Saja-Besaya
river as the catchment area of both rivers is very similar. The relatively small surface area, short
length and steep, leads to a rapid hydrological response to rainfall between 15.91 and 20.76 h
and, consequently, a high variability in the river flow (Bárcena et al., 2011).
During the last century, this estuarine zone has been affected by major industrial developments.
The industrial zones modify the basin river hydrology extracting water (2.25 m3/s) and discharging
wastewater (1.25 m3/s). Furthermore, it is worth pointing out that the Alsa-Torina reservoir
discharges about 10 millions of cubic meters to balance out the industrial withdrawals during
summer and drought periods (Bárcena et al., 2011). Other modifications in the area are the
construction of the port of Requejada (1876) and the artificial channel to improve access to it
(1894 and 1926-31). There was construction of several dams in the early-mid 20th century,
intense mining and quarrying activity through the 20th century, and important population growth
and urbanization, linked to mining and industrial development (Bruschi et al., 2012). Presently, about
50% of the estuary is affected by some sort of human action that might have or have had and
influence in its dynamics (Irabien et al., 2008).
95
Figure 3.3. Suances area with indication of the reserved zone for potential CO2 storage and
location of the sediment sampling site in the estuary
3.2.2. Sediment sampling and characterization
The surface sediment samples (0-5 cm layer) were collected on 7 July 2009. Prior to sampling
and storage, all beakers were thoroughly cleaned with acid (10% HNO3), and rinsed in deionized
water. The samples were collected with their initial water content and transported to the
laboratory to prepare the sediment for the analyses and tests. These samples were sieved
through 2 mm mesh to remove the gravel fraction and then homogenized with a spoon until no
color or textural differences could be detected. Sediment samples were kept in plastic bags and
stored frozen in the dark until use.
Different tests were carried out to determine the physical parameters of the sediment and get a
properly hydrodynamic characterization for the column leaching test. The water content (θ) was
calculated from the dry mass (md) obtained from the sample dried in an oven temperature of 110
± 5 ºC, following the Equation 3.1 (EPA, 1985). Where V (cm3) is the volume value of a sediment
96
sample in a 100 cm3 container, mr (g) is the sample mass value before drying in an oven and ρw
(g/cm3) is the water density at laboratory temperature.
–

θ (cm3/cm3) = Eq. 3.1
The pH of the sediment matrix was determined according to the EPA 9040C method for solid
waste, sludge and sediment with water content higher than 20% using a Crison pHmeter (EPA,
2004).
The surface area of the sediment was determined using the multipoint BET analysis on a
Micromeritics ASAP 2010 (Accelerated Surface Area and Porosity System) system. The mercury
porosimeter Micromeritics AutoPore IV 9500 Series was used to determine the external bed
porosity of the sediment. Two measurements were made per sample. The BET surface area was
determined using the t-plot method and it is calculated as the value of the slope of the line in the
t-plot representation. The micropore volume was determined using the t-plot method and it is
calculated as the value of the intercept of the line in the t-plot representation. In the porosimeter,
the mercury was intruded into the sample tube under vacuum condition. The low pressure
analysis was conducted, following by the high pressure analysis. In the test, the surface tension
of mercury was 485 dynes/cm, and the contact angle of mercury was 130º. Porosimetry
equipment can typically measure a maximum pressure range between 0.10 and 60000 psi. This
pressure range corresponds to pore´ sizes from several hundreds of micrometers (low pressure)
to a few nanometers (high pressure).
Bulk density and skeletal density were determined by the mercury porosimetry. The volume of
mercury displaced at minimum pressure and that displaced at maximum pressure are used to
determine bulk density and skeletal density, respectively. From the graphic representation of
Cumulative Intrusion as a function of Pore size Diameter, the external bed porosity, macropore
porosity and external surface porosity are obtained. The particle density was measured following
the method described in Black, C.A. (1965). The particle size distribution representation was
obtained by sieve analysis.
97
The major crystalline sediment phases were determined by X-ray diffraction analysis (Siemens
D5000 diffractometer), using Cu Kα radiation and operating at 30 mA and 50 kV. Total content of
metals, organic matter and total organic carbon in the sediment were analyzed. Sediment for
metal analysis was dried at 60 ºC and ground to a powder with an agate mortar and pestle. After
digestion with aqua regia for two hours at 95 ºC, element concentrations were determined using
ICP-OES by an external laboratory (Activation Laboratories, Canada). Organic matter was
measured by loss on ignition (LOI) according to the DIN 38414-3 method. Total organic carbon
(TOC) was analyzed according to UNE 77321. Selective chemical extractions were performed in
duplicate on the sediment to determine the amounts of humic and fulvic acids. The humic and
fulvic fractions were determined with a batch method derived from the currently recommended
procedure of the International Humic Substances Society (IHSS) (Swift, 1996; Thurman and Malcolm,
1981). In addition, the amounts of Fe- and Al-(hydr)oxides were estimated in duplicate by the
sodium dithionite-sodium citrate with NaHCO3 buffer system (Mehra and Jackson, 1960).
3.3. Leaching tests
3.3.1. Leaching solutions
The leaching solutions employed for the leaching tests were deionized water, natural seawater
(pH 8) and acidified seawater (pH 5, 6, 7). Using different values of pH for the leaching solutions,
the environmental conditions that may be encountered in these marine systems under different
CO2 leakage scenarios are mimicked.
The filtered (0.45 µm) natural seawater used in these tests was supplied by the Maritime
Museum of Cantabria, Spain. The natural seawater at pH 8 was acidified to get pH values of 7, 6
and 5. The use of seawater at different grades of acidification represents ocean acidification due
to leakages from a CO2 storage site, with pH 5 as the worst expected local scenario based on
literature (Carey et al., 2009; Jacquemet et al., 2011). Some parameters of the natural seawater
employed in these experiments are presented in Table 3.1.
The seawater was acidified to the pH value required (pH 7, 6 or 5) using the AT Control System
(Fig. 3.4). Pure CO2 gas was brought in contact with natural seawater in a reactor as fine
98
bubbles. A pH controller (AT Control System) monitored the pH and controlled the CO2 bubbling
from a CO2 gas supply. Once the required pH in the reactor is reached, the CO2 supply was
stopped via an automated feedback relay system and the acidified seawater is employed
immediately in the leaching tests. Using this method it was possible to supply large quantities of
CO2-acidfied seawater at a constant pH (precision of ± 0.1 pH units).
Table 3.1. Main parameters of the natural seawater

pH 7.8-8
Conductivity 54.3 mS/cm
Ionic strength 0.61 M
Salinity 35 ‰
Density 1.03 kg/L
Cl 21000 mg/L (2.10 %)
Na 12484 mg/L
Figure 3.4. AT Control System used to acidify seawater
99
3.3.2. Leaching tests procedure
Availability test (NEN 7341):
The metal content potentially available for leaching from the sediment was determined according
to the standardized availability test NEN 7341:1995. The availability test NEN 7341:1995,
“Leaching characteristics of solid (earthy and stony) building and waste materials. Leaching tests.
Determination of the availability of inorganic components for leaching”, describes a method for
determining the availability for leaching of inorganic components from solid (earthy and stony)
building and waste materials.
The purpose of this standard is to indicate what quantity of a particular component may leach out
from a material exposed to extreme conditions in an aerobic environment. The availability for
leaching determines the maximum quantity of each component that is potentially available for
leaching at pH 4 and pH 7, with relevance as asymptotic value at which leaching can tend in the
long term.
For this test, the material is fine-ground to a grain size of <125 µm. The test involves two
consecutive extractions at 10 rpm with deionized water acidified by HNO3 at L/S=50 L/kg at pH 7
and pH 4, respectively, each for 3 hours. The eluates are then filtered, mixed and analyzed (Fig.
3.5).
100
Sample dried at 60 º C and sieved at <125 µm

1st
Sample weight (m1) = 16 ± 2 g X

L/S = 50 L/kg T
mtot = beaker + m1 + stirring rod + deionized water
R
A
C
Keep pH at 7 ± 0.5 for 3 h adding V1 (volume of HNO3 1 M) while stirring T
I
O
Stop stirring and keep for 15 min N
Filter the suspension through 0.45 µm membrane filter → Extract 1 (E1)
Keep residue and membrane filter
Sample + Membrane filter + Residue + Stirring rod → Clean with deionized

water and continue adding until mtot ± 1 g
2nd
E
Keep pH at 4 ±0.5 for 3 h adding V2 (Volume of HNO3 1M) while stirring X
T
R
Stop stirring and keep for 15 min
A
Filter the suspension through 0.45 µm membrane filter → Extract 2 (E2)
C
T
Extracts obtained (E1 and E2) are transfered and preserved for cation and I
anion analyses O
N
Calculate the availability of each component of interest
Figure 3.5. Availability test procedure
101
Equilibrium leaching tests (EN 12457):
The purpose of the equilibrium test EN 12457:2002 “Characterization of waste. Leaching.

Compliance test for leaching of granular waste materials and sludges” is to provide acceptance
criteria for waste in a controlled site. The standard is based on the hypothesis that the equilibrium
is reached between the liquid and solid phases during the duration of the test. The leaching tests
EN 12457-1, 2 consist of a single extraction with a liquid-to-solid ratio (L/S) of 2 and 10 L/kg,
respectively (Fig. 3.6).
According to the standard, an amount of solid sample corresponding to a specific dry weight
value is placed into a flask. Leaching solution is then added to the material (grain size <4 mm) to
obtain L/S ratios of 10:1 or 2:1 and the mixture is shaken by end-over-end rotation at 10 rpm for
24 h (Fig. 3.7).
The dry residue (wdr) of the test sample is determined on a separate test portion. The dry residue
is determined at 105 ± 5 ºC and it is calculated as follows (Eq. 3.2):

wdr = 100. Eq. 3.2
wdr is the dry residue of the material expressed as a percentage (%);

md is the mass after drying expressed in grams (g);
mr is the mass before drying expressed in grams (g)
The moisture content (MC) is calculated with the following expression (Eq. 3.3):

MC = 100. Eq. 3.3
These two parameters (wdr and MC) help to calculate the amount of solid sample and leaching
solution volume used in the leaching tests at each L/S ratio (Eqs. 3.4 and 3.5):

!"#$

Amount of solid sample = 100. Eq. 3.4
102
*+ A
Leaching solution volume = %L/S ) . Fixed dry weight value for each B ratio Eq. 3.5
,--
Solid sample sieved at <4 mm
Calculation of wdr and MC → Solid sample amount

and liquid volume determinations
Addition of the liquid volume to the solid sample

placed in the flask
Stir for 24 h and 10 rpm
Filter the suspension through 0.45 µm membrane filter
Figure 3.6. Equilibrium leaching test procedure
Equilibrium leaching tests at L/S=2, 4, 10, 15, 20, 30 and 40 L/kg following EN 12457 were
performed. Higher L/S ratios than 10 were studied in order to determine the leaching
mechanisms. Leaching tests used deionized water, natural seawater at pH 8 and acidified
seawater at pH 7, 6 and 5 as leaching solutions. The elutriate test (L/S=4 L/kg) is a simplified
simulation of the dredging and disposal process wherein predetermined amounts of dredging site
waste and sediment are mixed together to approximate a dredged material slurry. The leachate
obtained from L/S=4 L/kg test is used in bioassays to study the effect of the release of chemicals
on biota. In this test, sample and leaching solution in an L/S ratio of 4 are subjected to agitation at
12 rpm for 30 min (Plumb, 1981).
103
Figure 3.7. Equilibrium leaching tests at different L/S ratios performed in the laboratory
Column leaching tests (CEN/TS 14405):
The standard test CENT/TS 14405 “Characterization of waste. Leaching behavior test. Up-flow
percolation test” describes a method to determine the release of constituents from waste packed
in a column with a leaching solution percolating through it.
The test portion of the sediment to be tested (about 1 kg of saturated sediment per column) is
packed in a column in a few consecutive steps. According to the standardized leaching method,
before starting the test, the column is completely saturated with the leaching solution and then the
saturated material is left for a period of three days to equilibrate the system. Continuously
saturated columns are run up-flow to avoid channeling and plugging. The leaching solution is
percolated in up-flow through the column at a specified flow rate up to a fixed L/S ratio. All
leachate exiting the column is collected at specific L/S ratios of 0.1, 0.2, 0.5, 1, 2, 5 and 10 L/kg.
In the test, equilibrium conditions at the outlet of the column are verified after equilibration by
measuring a pH deviation when the first eluate is collected (Fig. 3.8). The dry mass (m0) of the
test portion in the column is determined according to the Eq. 3.2 (md=m0) in order to calculate the
fraction volumes of the eluates exiting the column (Table 3.2). The test itself is finished when the
L/S ratio of 10 L/kg dry matter is reached. Deionized water, natural seawater at pH 8 and acidified
seawater at pH 7, 6 and 5 were used as leaching solutions. Prior to the leaching experiments all
104
laboratory material is acid washed and bottles, columns and pipes are conditioned with deionized
water or seawater.
Solid sample sieved at < 4 mm
Calculation of wdr → Fraction volumes of the eluates determination
Sediment is packed in the column in a few steps
Column saturation and left the column for 3 days to equilibrate the system
Start the test → Continuously up-flow rate at 110 mL/h
Check equilibrium condition : pH (15 mL of first eluate) - pH (Rest volume of

first eluate) < 0.5 pH units
Collect the eluate samples at the specified L/S ratio
Filter the suspension through 0.45 µm membrane filter
Figure 3.8. Column leaching test procedure
105
Table 3.2. Collection of eluate fractions according to CEN/TS 14405

Fraction number V (L)=[L/S (L/kg)m0(kg)]
1 (0.1 ± 0.02)m0
2 (0.1 ± 0.02)m0
3 (0.3 ± 0.03)m0
4 (0.5 ± 0.05)m0
5 (1 ± 0.1)m0
6 (3 ± 0.1)m0
7 (5 ± 0.1)m0
The column leaching procedure is carried out according to CEN/TS 14405, with modification of
the column dimensions. Columns used are made of methacrylate with 15 cm diameter and 4 cm
filling height, fitted with nylon filters in bottom and top sections (Tsiatsios, 2005). This modified
version of the standard procedure was used in order to avoid clogging that occurs with 5 cm
diameter and 30 cm height standard columns where expansion of the electrical double layer of
clay and silt particles resulted in no flow and the test had to be discontinued. An additional
advantage of using the 15 cm diameter column is that less time is needed to complete the test
maintaining the same linear velocity (Fig. 3.9). The columns were specifically designed for
evaluation of fine-grained sediment and dredged material leaching potential (Myers et al., 1991). In
general, as the high ionic strength pore water was washed out by low ionic strength eluent, the
diffuse double layers around the particles increased, causing the particles to deflocculate, which
allowed these particles to be transported out of the sediment (Brannon et al., 1991).
Nylon filter papers were used at the top and bottom of the column to assist in uniform distribution
of the leaching solution at the column inlet and to prevent sediment from being removed from or
blocking the column outlet and tubing that connected the column outlet with the syringe pumps.
The up-flow rate through the columns, obtained by a multichannel peristaltic pump (Masterflex
7524-55 L/S pump), was set at 110 mL/h, which corresponds with a linear velocity of 15 ± 2
cm/day through the empty column according to CEN/TS 14405. Furthermore, an extra L/S point
at 4 L/kg was collected in the column leaching tests in order to compare with the equilibrium
leaching test results. Thus, the L/S ratios collected in the column leaching tests were 0.1, 0.2, 0.5,
1, 2, 4, 5 and 10 L/kg (Fig. 3.10).
106
Figure 3.9. Column parts
Figure 3.10. Column leaching tests performed in the laboratory
pH dependence leaching test (CEN/TS 14429):
The standard test CEN/TS 14429:2005 “Characterization of waste. Leaching behaviour tests.
Influence of pH on leaching with initial acid/base addition” determines the influence of pH on the
leaching behavior of inorganic constituents from a waste material. Equilibrium condition as
107
defined in the standard is established by addition of pre-determined amounts of acid or base to

reach desired end pH values. The acid and base neutralization capacity (ANC/BNC) test CEN/TS
15364 “Characterization of waste. Leaching behaviour tests. Acid and base neutralization
capacity test”, which determines the overall buffering capacity of the material, is also determined
at the same time to obtain the acid/base neutralization curves (Fig. 3.11).
The amounts of acid or base needed to cover the pH range can be derived from the results of a
preliminary titration from available experimental data on the material to be tested or from an
arbitrary division of the predetermined maximum consumption of acid and base.
For the pH dependence leaching test, the leaching solution with predetermined amounts of acid
(HNO3) or base (NaOH) is added to subsamples at L/S=10 L/kg and 10 rpm for 48 h in three
stages at 0, 30 and 120 minutes (t0, t0+30min, t0+2h) (Fig. 3.12). The test is made on material with a
grain size of 95% less than 1 mm. The pH of the leachate is measured after each stage and the
equilibrium verified. According to the standard, at least 8 final pH-values are required, covering at
the minimum the range pH 4 to pH 12 (both included) including the natural pH (without acid or
base addition). The maximum difference between two consecutive pH values shall not exceed 1.5
pH units. The equilibrium condition as defined in the standard is verified at the end of the
extraction period. The deviation between pH at t0+44h and pH at t0+48h shall not exceed 0.3 pH
units, which is the limit for achieving equilibrium condition.
108
Solid sample sieved at <1 mm
Addition of the predeterminated amounts of HNO3 or NaOH to the

leaching solutions
1º stage: t0 = Sample + 1/3 of leaching solution

Stir at 10 rpm
2º stage: Stop stirring

t0+30 min = addition of 1/3 leaching solution
Stir at 10 rpm
3º stage: Stop stirring

t0+120 min = addition of 1/3 leaching solution
L/S = 10 L/kg
Stir at 10 rpm
Stop stirring
t0+44h = Measure pH
Stir at 10 rpm
Stop stirring
t0+48h = Measure pH
Check equilibrium condition pH48h-pH44h < 0.3 pH units
Final pH-values covering the whole pH range
Filter each suspension through 0.45 µm membrane filter
Figure 3.11. pH dependence leaching test procedure
A modified pH dependence leaching test is carried out using deionized water and seawater as
leaching solutions. The sediment sample used was sieved through 2 mm mesh as for the other
109
leaching tests performed. According to the standard, 8 final values are needed in the range of pH
4 to pH 12. In this case, the whole pH range (0-14) is considered.
Figure 3.12. pH dependence leaching test performed in the laboratory
3.3.3. Analyses of the leachates
Each sample leachate was filtered through a 0.45 µm pore size nitrocellulose filtration membrane
and divided in two subsamples, one for measuring pH, conductivity and DOC and the other one
acidified for determining element concentrations (Cl-, As, Cd, Cr, Cu, Ni, Pb and Zn).
A Crison pHmeter GLP 22 with electrode, accurate to 0.01 pH units was used for pH
measurement of all leachates. Electrical conductivity of the leachates was measured using a
Crison Conductimeter Basic 30. DOC analysis was performed following UNE-EN 1484 with a total
organic carbon Schimadzu TOC-V Analyzer, where the difference method TOC=TC-TIC was
applied. Chloride analysis was carried out using a titration with AgNO3 with an automatic titrator
Metrohm 701 KF Titrino.
Cation analyses were carried out using an Agilent 7500 ce ICP-MS and ICP-OES Perkin Elmer
Optima 3200 RL. A rhodium (Rh) internal standard was applied to the samples for the ICP-MS
analyses. The spectroscopic interferences on As were corrected with the Agilent 7500 ce ICP-MS
equipment using He collision mode.
110
3.4. Modeling of the leaching results
3.4.1. Empirical modeling
For column leaching tests, DOC and metal experimental leaching evolutions as a function of L/S,
pH or both parameters are fitted. Thus, a stepwise strategy with different analysis approaches is
conducted to fit DOC and metal concentrations in leachates; from the simplest empirical analysis,
using the lowest number of adjustable parameters without physical meaning, to semi empirical
analysis, using mathematical expressions with parameters with physical meaning.
Using simple empirical analysis, DOC and metal cumulative releases with L/S are described with
simple (exponential and linear) expressions fitting the experimental evolutions observed (Eqs. 3.6
and 3.7).
C
E
DOC (mg/L) = a %D. Eq. 3.6
Metal release (µg/kg) = aL/S Eq. 3.7
Using empirical analysis, metal and DOC experimental column releases are fitted at once with
L/S and initial pH by simple mathematical expressions (Eqs. 3.8 and 3.9) and three adjustable
parameters.
C H
DOC (mg/kg) = a FG E %D. Eq. 3.8
C C
Metal release (µg/kg) = a%D.FG
E +c%D. Eq. 3.9
Using semi empirical analysis, DOC and metal cumulative releases are adjusted to L/S (Eqs. 3.10
and 3.11). This expression has been previously used to model experimental column leaching
data as a plug flow reactor with continuous dispersion (van der Sloot et al., 1997; Cappuyns and
Swennen, 2008) and to model release at a given exposure time of a waste material in the field (van
der Sloot et al., 1996). This equation can be used to compare the matrix retention parameter (k) and
the availability (AVB) for different elements in different contaminated materials; in this sense, the
111
use of this approach allows to interpolate column leaching data (cumulative release) with time (or
L/S ratio), with physical meaning of the adjusted parameters (k and AVB).
L
% .

M
DOC (mg/kg) = AVBI1 ) K N O Eq. 3.10
L
% .

M
Metal release (µg/kg) = AVBI1 ) K N O Eq. 3.11
The analysis of experimental leaching data in general has been studied from different
approaches, from empirical to analytical fitting of data, using different mathematical expressions
and models.
3.4.2. Mathematical modeling of column leaching results with Aspen Custom Modeler
A dynamic kinetic model of the evolution of Pb and Zn concentrations with L/S when natural
seawater at pH 8 and CO2 acidified seawater at pH 5, 6 and 7 are used as leaching solutions in
contact with contaminated sediment is developed using Aspen Custom Modeler software. The
model considers the mass transfer from the bulk liquid phase to the particle surface and the solid-
phase surface diffusion within the particle itself. The Freundlich equation has been used for the
description of the equilibrium process and the parameters have been estimated by the model.
Previous studies pointed out the elevated Pb and Zn concentrations in this estuary exceeding the
recommended values for estuarine sediment and being described as a heavily polluted area
(Álvarez-Guerra et al., 2007; Coz et al., 2008).
The determination of the mathematical model, that describes metal release under changing
environmental conditions, can provide a way forward for site-specific risk assessment in the short,
medium and long term and for developing appropriate and cost-effective, prevention, mitigation
and remediation strategies. Thus, the advection-diffusion model is considered to take into
account the net rate of production of mobile contaminant caused by chemical reactions and
sorption/desorption process for simulating the flow-through leaching conditions.
112
Sorption/desorption processes using fixed-bed reactors also use diffusion-advection equations to

simulate the behavior of different contaminants in natural systems. It is widely accepted that slow
sorption and desorption processes are due to diffusion–limited transport of solutes to sorption
sites inside particles or soil aggregates.
The differential mass balance for the metal in the packed bed is based on the following
hypotheses: (i) there are no radial gradients, (ii) isothermal operation, (iii) constant liquid velocity
through the bed, and (iv) linear combination of the mass-transfer resistances corresponding to the
external mass transfer, from the liquid film to the particle surface, and the solid diffusion within the
particle itself.
3.4.3. Geochemical modeling with Visual MINTEQ
Geochemical models have been used over the last years as a tool to simulate the behavior of
components in different matrices (Halim et al., 2005; Vink and Meeussen, 2007; Moberly et al., 2010; Rocca et
al., 2012). Among others, Visual Minteq has been extensively used for geochemical modeling to
simulate the leaching behavior of contaminants from sediment (Cappuyns et al., 2007; Shtiza et al.,
2009; Charriau et al., 2011; Meck et al., 2011; Van De Moortel et al., 2011). The chemical equilibrium model
Visual MINTEQ (ver. 2.61) is used to assess metal leaching by comparing model predictions to
experimental data from pH dependence leaching tests and to model the dominant speciation of
each component of interest as a result of aqueous reactions, solid phases and physico-chemical
phenomena.
Based on the major phases of the sediment under study and literature (Charriau et al., 2011; Romero
et al., 2008), the input data consist of the total concentration of the following major components
Ca2+, Mg2+, Al3+, Fe3+ and Ba2+ and the following inorganic metal binding ligands PO43-, CO32-,
H4SiO4, SO42-, SO32- and Cl-. Furthermore, model input files are composed of the total
concentrations or maximum concentrations obtained in the pH dependence leaching tests of the
elements of interest (As, Cd, Cr, Cu, Ni, Pb, Zn) and the respective pH values, in the 0-14 range.
Possible solid phases are selected to calculate the leachate composition in equilibrium. The ionic
strength of the seawater and Na+ and Cl- ions are also taken into account to model the metal
behavior with seawater. Furthermore, Cd, Cr, Cu, Ni and Zn leaching results are modeled by
113
surface adsorption to Fe- and Al-(hydr)oxides using the Generalized Two Layer Model (GTLM) of
Dzombak and Morel (Dijkstra et al., 2004, 2006a,b, 2008, 2009; Butler et al., 2009; John et al., 2010, 2011; van
der Sloot and van Zomeren, 2012) and the specific surface area of 600 m2/g (Apul et al., 2005, 2010;
Huijgen and Comans, 2006; Sader et al., 2011; Jung et al., 2012). Fe- and Al-(hydr)oxides are summed and
used as input for HFO assuming that 1 mol of Al is representative of 1 mol of Fe. The molecular
weight of 89 g of HFO/mol of Fe recommended by Dzombak and Morel (Dzombak and Morel, 1990) is
used to calculate the concentration of HFO from the extracted Fe and Al (Meima and Comans, 1998;
van der Sloot and van Zomeren, 2012). In previous works, the total amount of amorphous hydrous ferric
oxide was calculated as an approximation from Fe concentration (Cornelis et al., 2008). The DOC-
metal binding models (NICA-Donnan model, Gaussian model and SHM model), available in
Visual MINTEQ, are used for the assessment of metal-organic complexation. These models use
the experimental humic and fulvic acid concentrations measured in the sediment.
The output database includes the metal predicted speciation in mol/L and also the saturation
index (SI), which allows the prediction of the main phases that control the solubility of the
components of interest (Cornelis et al., 2008).
3.5. Discussion of results
3.5.1. Sediment characterization results
The studied sediment presents a water content (θ) value of 65%, with wet mass (mr) and dry
mass (md) values of 150.37 g and 85 g, respectively. The pH value measured is 7.40.
The physicochemical properties of the sediment are presented in Table 3.3. The hysteresis cycle
(Fig. 3.13) shows two different curves for the adsorption and desorption processes, suggesting
laminar shape for the sediment particles. This figure corresponds to a type II isotherm. The
reversible type II isotherm is typical of a non-porous material with macro-porous and flat surfaces.
It indicates uniform surface energy, multilayer adsorption and infinite adsorption as pressure
approaches saturation. The type II isotherm represents unrestricted monolayer-multilayer
adsorption. The shapes of hysteresis (Fig. 3.13) loops have often been identified with specific
pore structures. In this case, it is identified with the type H3 loop, which does not exhibit any
114
limiting adsorption at high p/po, and it is observed with aggregates of plate-like particles giving
rise to slit-shaped pores (Sing, 1982). The BET surface area obtained is low for a microporous
material, thus the value obtained pointed out that this material presents nor micropores neither
mesopores. The bulk density, particle density, skeletal density and particle porosity of the
sediment are parameters determined by the mercury porosimeter (Fig. 3.14). From Figure 3.15,
the external bed porosity, macropore porosity and external surface porosity are obtained.
Table 3.3. Physiochemical properties of the sediment

Parameter Value
BET surface area (m2/g) 7.11 ± 0.05
Molecular cross-sectional area (nm2) 0.16
External surface area (m2/g) 7.82
Total pore volume (cm3/g) 0.022
Macropore volume (cm3/g) 0.022
Bulk density (g/cm3) 0.91
Particle density (g/cm3) 2.96
Skeletal density (g/cm3) 2.32
External bed porosity (cm3/cm3) 0.60
Particle porosity (cm3/cm3) 0.000056
Macropore porosity (cm3/cm3) 0.26
External surface porosity (cm3/cm3) 0.32
Mean particle diameter (cm) 0.0085
Thickness range (Å) 3.50-5.00
Type of isotherm II
Type of hysteresis loop H3
The particle size distribution representation (Fig. 3.16) is obtained with the values presented in
Table 3.4, being R the percentage of particles smaller than a given size.
115
Table 3.4. Particle size distribution values

Mean diameter, di (mm) R (%) Cumulative R (%) Ri/di
2 0 0 0
1.5 0.05 0.05 0.0003
0.875 0.16 0.21 0.0018
0.575 6.99 7.15 0.1216
0.35 14.67 21.66 0.4191
0.25 8.5 23.17 0.34
0.18 7.01 15.51 0.3894
0.1115 41.2 48.21 3.6951
0.0315 21.42 62.62 6.8
Mean particle diameter (mm) = 0.085
MCRUZ SED 1 (4/9/12) - Desorption
14 MCRUZ SED 1 (4/9/12) - Adsorption

MCRUZ SED 1 (4/9/12) - Desorption
12
10
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95
Figure 3.13. Isotherm linear plot of the BET analysis
116
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
Intrusion for Cycle 1 Extrusion for Cycle 1

0.05
0.00
1 10 100 1,000 10,000
Figure 3.14. Cumulative intrusion as a function of pressure of the mercury porosimetry

0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10

0.05
0.00
100,000 10,000 1,000 100 10
Figure 3.15. Cumulative intrusion as a function of pore size diameter of the mercury porosimetry
117
70
60
50
Cumulative R (%)
40
30
20
10
0
0 0,5 1 1,5 2 2,5
Diameter (mm)
Figure 3.16. Particle size distribution
Figure 3.17 shows the major crystalline sediment phases (Romero et al., 2008). It can be seen that
the sediment contains quartz (SiO2) and Ca-containing phases as calcite (CaCO3), anhydrite
(CaSO4) and dolomite (CaMg(CO3)2) are also detected.
Figure 3.17. X-ray diffraction patterns from Suances sediment (Q=quartz; □=CaMg(CO3)2;
∆=CaCO3).
Sediment concentration of the major elements, expressed as oxide, total metal content and
concentration of elements considered in this study (As, Cd, Cr, Cu, Ni, and Pb) are shown in
Figure 3.18. The major elements expressed as oxides represent 98.6% of the total sediment
mass in dry weight. Quartz represents 57% of the total mass, aluminium oxide 8% and calcium
oxide, which is usually present as calcite and dolomite, 7%. The organic matter content as Total
Organic Carbon (TOC) is 1.74%. Sediment samples have high concentrations of Zn (4030 mg/kg)
118
and Pb (407 mg/kg), whereas As, Cd, Cr, Cu and Ni concentrations range from 10 to 60 mg/kg.
The high carbonate content of the sediment suggests a relatively high acid neutralization
capacity. The Suances estuary sediment has become a major reservoir for Zn, Pb and Cd, with
high number of toxic samples and provides a potential source for a present-day secondary
pollution due to mechanical effects and/or bio-geochemical remobilization. Therefore, the
Suances estuary should be classified as highest priority site with regard to pollution when
considering remediation decisions. The selective chemical extractions performed on the sediment
show that the sediment presents 15.14 and 1.67 mg/g of Fe- and Al-(hydr)oxides, respectively;
and 121 mg/L of humic acids and 791 mg/L of fulvic acids.
100 10000
10
1000
%
mg/kg
1
100
0,1
10
0,01
1
10000
1000
100
mg/kg
10
0,1
0,01
0,001
AuAgAs Ba Be Bi Br CdCo Cr Cs Cu Hf Hg Ir Mo Ni Pb RbSb Sc Se Sr Ta Th U V W Y Zn Zr La Ce NdSmEu Tb Yb Lu Hg
Figure 3.18. a) Sediment concentrations of major elements (expressed as oxides) and organic
matter (expressed as LOI and TOC); b) Concentration of elements (As, Cd, Cr, Cu, Ni, and Pb)
considered in this study; and c) Total metal content of the sediment samples.
119
The chemical characterization of the sediment confirms the high content of pollutants of the
samples leading to an environmental characterization of the matrix. A variety of tools may be
used to assess the environmental significance of pollution in sediment (Alvarez-Guerra et al., 2007).
Table 3.5 summarizes the sediment legal framework used to characterize the sediment. In Spain,
the recommendations for the management of dredged materials in Spanish Ports proposed by
CEDEX (1994) are based on the Action Levels (AL) approach. The sediment quality guidelines
(SQGs) use quantitative environmental quality standards (Long et al., 1995), being one of the most
common approaches the effects range–low (ERL) and effects range–median (ERM). Another
approach uses leaching tests to assess compliance with landfill waste acceptance criteria or
guidelines for secondary material recycling. In the EU legal framework, limiting values of the total
content and chemical concentrations in the equilibrium tests EN12457-1,2 and column test
CEN/TS 14405 at L/S=0.1 L/kg are considered as the acceptance criteria for different classes of
landfills (EU, 2003).
Table 3.5 shows that Pb and Zn are about fifteen- and forty-threefold higher than the regional
background values for estuarine sediment, respectively, proposed by Viguri et al. (2007).
According to the CEDEX (1994) recommendations, the sediment exceeds the action level I for Pb
and the action level II for Zn and Cd, so it can be described as heavily polluted (category III). In
relation to the SQGs values, the sediment exceeds the ERM values for Zn, Pb and Cd, and is in
the range where adverse biological effects frequently occur. In addition, levels of As, Cd, Cr, Cu
and Ni exceed the ERLs values corresponding to the 10th percentile of chemical concentrations
associated with adverse biological effects. On the other hand, Table 3.5 shows [C/Climit], which is
the ratio between the experimental concentration of the metals in different compliance leaching
tests and the limit concentration for acceptance of waste in inert landfills. All the concentrations
are actually below the EU limit value for disposal in inert landfills or [C/Climit] <1. The
contradictions of the characterization results in function of the used criteria, point out the
importance of sediment characterization in the conditions of seawater acidification close to the
real situation that would be reached in potential leakages of CO2 from CCS.
120
Table 3.5. Concentration of metals in sediment with reference values for comparison (CEDEX,
1994; Long et al., 1995; Viguri et al., 2007) and [C/Climit] ratio between the experimental concentration (C
in mg/kg) and legal threshold acceptance value (Climit in mg/kg) in inert landfill obtained in
different compliance leaching tests (EU, 2003).
Concentration (mg/kg) 50 11 58 40 25 407 4030
Regional Background (Viguri et

23 ± 5 -- 101 ± 26 14 ± 2 16 ± 2 26 ± 4 92 ± 26
al., 2007)
Action Levels for dredged material management (CEDEX, 1994)
Action Level I 80 1.0 200 100 100 120 500
Action Level II 200 5.0 1000 400 400 600 3000
SQGs (Long et al., 1995)
ERL 8.2 1.2 81 34 20.9 46.7 150
ERM 70 9.6 370 270 51.6 218 410
Relative leaching concentration [C/Climit] from the compliance leaching tests according to the
waste acceptance in Inert landfill criteria (EU, 2003)
L/S = 2 (Equilibrium test)

0.123 0.009 0.032 0.153 0.055 0.006 0.023
L/S = 10 (Equilibrium test)
0.224 0.04 0.025 0.031 0.067 0.006 0.022
L/S = 0.1 (First eluate of column
0.096 0.014 0.034 0.216 0.261 0.028 0.153
test)
The availability results for the elements considered in this study of the sediment samples are
presented in Figure 3.19. With respect to the total concentration, the highest difference is found
for Cd and the lowest for As, Ni and Zn, being the most mobile elements.
121
1000
100
Availability (mg/kg)
10
0,1
0,01
Figure 3.19. Availability results of As, Cd, Cr, Cu, Ni, and Pb for the studied sediment
The pH titration curve of the ANC/BNC test (Fig. 3.20) shows that 0.8 eq/kg of NaOH were added
to reach pH 12, 0.1 eq/kg of HNO3 to reach pH 7 and 2.4 eq/kg of HNO3 to reach pH 4. The
ANCpH4 value is within the range of values reported in literature (Lager et al., 2005; Rigol et al., 2009).
The sediment has a lower BNC (0.8 eq/kg of NaOH increased pH by 4.6 units) than ANC (1 eq/kg
of HNO3 decreased pH by 2 units); this pattern can be explained by the high carbonate content.
14
12
10
8
pH
6
4
2
0
-1 -0,5 0 0,5 1 1,5 2 2,5 3
Acid added (eq/kg)
Figure 3.20. Equivalents of acid/base per kilogram of sediment in the ANC/BNC leaching test
122
3.5.2. Equilibrium leaching test results
The initial pH of the leaching solution and its evolution during the equilibrium leaching tests at
different L/S ratios is the most important variable in metal leaching processes; in addition, the
DOC and the conductivity of the solution may influence metal leaching. Average values of pH
(Standard Deviation, SD < 0.40 pH units), conductivity (Relative Standard Deviation, RSD < 10%)
and DOC (RSD < 25%) from triplicate equilibrium leaching tests at L/S ratios of 2, 4 and 10 L/kg
are shown in Figure 3.21. The final leachate pH of the equilibrium tests (Fig. 3.21a) using
deionized water shows a pH close to 8 for the three tested L/S ratios; with seawater, the final pH
is more acid for the lower initial pH for the three L/S ratios. However, the final pH ranges with
seawater from 6.8 to 8, because of the high acid neutralization capacity of the sediment. Figure
3.21b shows that conductivity remains rather constant at about 55 mS/cm in the leaching tests
with seawater, close to the natural seawater conductivity as expected. On the contrary, for
deionized water, conductivity decreases as L/S increases, i.e. when less solid is available. It is
shown that DOC (mg/L) decreases in general with increasing L/S ratio (Fig. 3.21c). The highest
DOC values are obtained with seawater at pH 8 and the lowest DOC values (up to two orders of
magnitude lower) with deionized water. However, when DOC is presented as release per sample
mass (mg/kg) as a function of L/S ratio (Fig. 3.21d), DOC increases with L/S for all leaching
solutions used due to more DOC is dissolved per unit sample mass when less sediment sample
is available.
123
8,5 70
60
8 50
40
pH
7,5
30
7 20
10
6,5 0
2 4 10 2 4 10
a L/S (L/kg) b
L/S (L/kg)
250 1400
1200
200
1000
DOC (mg/kg)
DOC (mg/L)
150 800
600
100
400
50 200
0 0
2 4 10 2 4 10
c d L/S (L/kg)
L/S (L/kg)
Figure 3.21. a) pH, b) conductivity, c) DOC (mg/L) and d) DOC (mg/kg) results for equilibrium
leaching tests using deionized water and seawater at different pH as leaching solutions.
Higher L/S ratios than 10 have been used to simulate different scenarios of sediment in contact
with acidified seawater in a potential CO2 leakage (Townsend et al., 2006; Ndiba and Axe, 2010). The
obtained results for As, Cd, Cr, Cu, Ni, Pb and Zn show, for nearly all studied pHs, the decrease
in leachate metal concentration (µg/l) with increased L/S. This may have been largely caused by
a stronger dilution of the leachate with increased L/S after depletion of the exchangeable fraction
(Ndiba and Axe, 2010). Figures 3.22a-d show the average metal concentration, in µg/L, and metal
release, in µg/kg, with L/S ratio at different pH values for Cd (RSD < 25%) and Ni (RSD < 20%),
respectively. Release of the different inorganic species when represented as a function of L/S
ratio may be availability or solubility controlled (Al-Abed et al., 2008). The effect of the change of L/S
ratio gives an indication of whether solubility-controlled or diffusion-controlled leaching prevails.
However, often a mixture of control processes dominates (van der Sloot, 2000; Kosson et al., 2002).
Only metals with linear fitting values of R2>0.7 are used to describe the leaching behavior with
L/S (increase, constant or decrease). According to this, only Cd, Ni and Zn show dominant control
124
mechanisms at specific pH values and leaching agents; for the rest of the studied cases, no clear
dominant leaching mechanism exists. Cd and Ni present solubility control mechanism for
deionized water and natural seawater. Availability control mechanism is shown by Cd (seawater
at pH 6, 7, 8), Ni (deionized water, seawater pH 6) and Zn (seawater at pH 6). The results
obtained are similar to the behavior previously observed in the leaching of metals from treated
sediment using leaching tests at L/S between 5 and 100 (Ndiba and Axe, 2010) and from waste
working with leaching tests at L/S ranging from 2 to 20 (Townsend et al., 2006).
10 100
1 10
Cd (µg/L)
0,1 Cd (µg/kg) 1
0,01 0,1
0 10 20 30 40 50 0 10 20 30 40 50
a b
1000 10000
100 1000
Ni (µg/kg)
Ni (µg/L)
10 100
1 10
0,1 1
0 10 20 30 40 50 0 10 20 30 40 50
c d
Figure 3.22. Leaching metal results of equilibrium tests as a function of L/S: a) Leached
concentration (µg/L) of Cd; b) Release (µg/kg) amount of Cd; c) Leached concentration (µg/L) of
Ni; b) Release (µg/kg) amount of Ni.
125
3.5.3. Column leaching test results
Average values of pH (Standard Deviation, SD < 0.15 pH units), conductivity (Relative Standard
Deviation, RSD < 10%) and DOC (RSD < 25%) of the leaching solution from triplicate column
leaching tests are shown in Figure 3.23. Using seawater at pH 6, 7 and 8, the final leaching
solution pH after 56 h (L/S=10) is 7.6 ± 0.07 in all cases due to the buffer capacity of the
seawater. At pH 5 the continuous feeding of H3O+ ions and the not buffering capacity of the liquid
system, triggers the dissolution of carbonate which stabilizes the pH at 6.8 after approximately 11
hours (L/S=2). Using CO2 acidified seawater at pH 6, a low acidity change ∆pH=–0.1 is found,
similar to the pre-industrial variations in ocean global acidity (Caldeira and Wickett, 2003), meanwhile
using CO2 acidified seawater at pH 5, a high ∆pH=–0.9 is found (Fig. 3.23a). Important negative
effects are expected at local scale in scenarios with advective flow of CO2 acidified seawater at
pH ≤ 5, in contact with carbonate rich contaminated core sediment. Conductivity values obtained
(Fig. 3.23b) are almost constant at the natural seawater value of 55 mS/cm, for all acidified
seawater leaching solutions used and for all fractions collected at different L/S ratios; in the case
of deionized water, as expected, conductivity decreases as L/S increases. DOC decreases
steeply until L/S=1 L/kg (Fig. 3.23c) and then more slowly, showing two different behaviors; a fast
release of DOC at low L/S ratios (0.1-1 L/kg), which approaches typical pore water solutions, due
to the organic matter solubilization, and a reduced release at high L/S ratios that can be attributed
to the reduced availability of the DOC after their initial dissolution (van der Sloot et al., 2001); this
different behavior with L/S ratio is more noticeable at pH 8. When DOC (mg/L) is plotted as a
function of the initial pH (Fig. 3.23d), it appears that DOC remains almost constant (32.8 ± 4.3
mg/L) up to pH around 7.5; from then, DOC increases steeply with pH up to 550 mg/L. The
results are however scattered. For deionized water, low DOC mobility is obtained, probably due
to the lower ionic strength and lower complexation degree. These results show the importance of
DOC leaching at seawater natural pH and slightly acidic conditions that would be occur shortly
after a large CO2 leakage; in the first steps of this leakage, the agitation of sediment by the CO2
bubbling at seawater natural pH would mobilize high quantities of DOC and, in latter steps, would
complex metals mobilized by the gradual seawater acidification.
126
9
70
60
8
50
40
pH
7
30
20
6
10
0
5 0 2 4 6 8 10 12
0 2 4 6 8 10 12
a b L/S (L/kg)
L/S (L/kg)
600 600
80
500 60
500
DOC (mg/L)
400
DOC (mg/L)
400 40
300 20 300
200 0 200
0 2 4 6 8 10 12 Deionised water
100 100
0
0
6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 8,2
0 2 4 6 8 10 12
c d pH
L/S (L/kg)
Figure 3.23. a) pH, b) conductivity, c) leachate concentration of DOC (mg/L) as function of L/S;
experimental data were fitted with TableCurve 3D 4.0 Systat software; d) leachate concentration
of DOC (mg/L) as function of pH in column leaching tests.
The DOC experimental leaching data can be fitted with L/S by the simple decreasing exponential
expression of Equation 3.6, obtaining the correlation coefficients (R2) shown in Table 3.6.
C
E
DOC (mg/L) = a % .
D
Eq. 3.6
Table 3.6. Adjustable parameters (a, b) and correlation coefficients (R2) for Eq. 3.6.
P
R
DOC (mg/L) = a %Q. Seawater pH 5 Seawater pH 6 Seawater pH 7 Seawater pH 8
a 29.3 32.5 82.3 257.9
b 0.30 0.27 0.46 0.43
R2 0.98 0.98 0.99 0.99
127
The mass cumulative release of DOC (mg/kg) has been fitted semi-empirically as a function of
L/S ratio by Equation 3.10 (van der Sloot et al., 1997; Cappuyns and Swennen, 2008) and empirically as a
function of initial pH and L/S ratio (Fig. 3.24a) by Equation 3.8.
C H
DOC (mg/kg) = a FG E % .
D
Eq. 3.8
L
% .

M
DOC (mg/kg) = AVBI1 ) K N O Eq. 3.10
The availability (AVB) in Eq. 3.10 is the maximum available DOC concentration obtained in the
equilibrium L/S=10 L/kg test with seawater at pH 8 (872.8 mg/kg), and the adjustable parameter k
is the matrix retention parameter (L/kg). The results of the fittings in Table 3.7 show lower DOC
retention parameters at higher pH values. The parameters values a=1.3 10-4, b=7, and c=0.5 in
Eq. 3.8 corroborate the larger influence of pH than L/S, and leads to a reasonable fitting with
R2=0.96 and a parity plot graph (Fig. 3.24b) with <10% error.
Table 3.7. Adjustable parameters and correlation coefficients (R2) for DOC (mg/kg) release
obtained after fitting experimental values to Eq. 3.10.
P
% .

Q
DOC (mg/kg) = AVBIS ) T U O Seawater pH 5 Seawater pH 6 Seawater pH 7 Seawater pH 8
k (L/kg) 46.5 41.7 21.7 3.2
R2 0.99 0.92 0.80 0.97
128
1000
900
800 800
900
Simulated DOC (mg/kg)

700
800
DOC (mg/kg)
600
700 500 600
DOC (mg/kg)
600 400
500 300 400
400 200
300 100
200 0 200
100 7. 5
0 7
9 6. 5 0
8 7 6 5
6 pH 0 200 400 600 800 1000
4 3 5. 5
L/ S
a 2 1 05
Experimental DOC (mg/kg)
Seawater pH 5 Seawater pH 6 Seawater pH 7 Seawater pH 8
Figure 3.24. a) DOC (mg/kg) cumulative release as a function of L/S ratio and pH of leaching
solution in column leaching tests. b) Parity plot (10% confidence interval regression) of
experimental and simulated DOC (mg/kg) concentrations.
The cumulative metal release for column leaching tests as a function of L/S is shown in Figures
3.25a-g. It appears that the cumulative element release increases with L/S until the end of the
test at L/S=10 L/kg. This was also observed by other authors who suggested that metals would
probably leach in larger amounts, if exposed for longer L/S durations (Delay et al., 2007; Gardner et al.,
2007; Al-Abed et al., 2008). Figure 3.25h shows the metal behavior with pH at L/S=10 L/kg: i) As
increases with the pH of the leaching solution; ii) Cd, Ni, Pb and Zn present metal releases in
seawater in the pH sequence pH 5 > 6 > 7 > 8; iii) for Cu, the highest metal release is found at
the lowest pH (seawater at pH 5), for the other pH values, the higher the pH the higher the metal
release; iv) for Cr, the release is almost constant as a function of pH.
129
1000 100
100 10
Cd (µg/kg)
As (µg/kg)
1
10 150
10
100 0,1 8
6
1 50
0,01
4
2
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
0,1 0,001
0 2 4 6 8 10 12 0 2 4 6 8 10 12
a b
100 100000
10000
Cr (µg/kg)
Cu (µg/kg)
10 1000
100
80
100
60 60000
1 40 10 40000
20 20000
0 1
0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
0,1 0,1
0 2 4 6 8 10 12 0 2 4 6 8 10 12
c d
Figure. 3.25. a-d) Cumulative experimental (Exp) and simulated (Simul) release of As, Cd, Cr,
and Cu in column (Col) and equilibrium (Eq) leaching tests using deionized water (DW) and
seawater (SW) at pH values of 5, 6, 7 and 8 as leaching solutions vs. L/S ratio. The cumulative
experimental (Exp) release of metals in column (Col) leaching tests is indicated by the smaller
linear scale inner figures. The cumulative simulated (Simul) release of metals in column (Col)
leaching tests is indicated by the larger logarithmic scale figures. Concentration results from
equilibrium (Eq) leaching tests are presented with larger size symbols.
130
10000 10000
1000 1000
Pb (µg/kg)
100
Ni (µg/kg)
100
500
10 4000
10 400 3000
300 1 2000
200
1 100
0,1
1000
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
0,1 0,01
0 2 4 6 8 10 12 0 2 4 6 8 10 12
e f
1000000 L/S = 10 L/kg

100000
100000
10000
Cumulative metal
As
10000
release (μg/kg)
1000 Cd
Zn (µg/kg)
1000
100 Cr
100 150000
100000 Cu
10 10
50000 Ni
1 0 1
0 2 4 6 8 10 12 Pb
0,1 0,1 Zn
0 2 4 6 8 10 12 4 5 6 7 8 9
g h
L/S (L/kg) pH
Figure. 3.25. e-g) Cumulative experimental (Exp) and simulated (Simul) release of Ni, Pb and Zn
in column (Col) and equilibrium (Eq) leaching tests using deionized water (DW) and seawater
(SW) at pH values of 5, 6, 7 and 8 as leaching solutions vs. L/S ratio. The cumulative
experimental (Exp) release of metals in column (Col) leaching tests is indicated by the smaller
linear scale inner figures. The cumulative simulated (Simul) release of metals in column (Col)
leaching tests is indicated by the larger logarithmic scale figures. Concentration results from
equilibrium (Eq) leaching tests are presented with larger size symbols; Figure 3.25. h)
Experimental cumulative release of the studied metals in column leaching tests as a function of
initial pH at L/S=10 L/kg obtained from Figures 3.25a-g.
131
Equations 3.7, 3.9 and 3.11 have been used to fit empirically the cumulative release of metals,
obtaining good correlation coefficients of the experimental data (Table 3.8, 3.9 and 3.10,
respectively).
Metal release (µg/kg) = a·L/S Eq. 3.7

𝐿 𝐿
Metal release (µg/kg) = a·� �·𝑝𝐻 −𝑏 +c·� � Eq. 3.9
𝑆 𝑆
𝐿
�𝑆�
−𝑘
Metal release (µg/kg) = AVB·�1 − 𝑒 � Eq. 3.11
Table 3.8. Parameters and correlation coefficients (R2) for the cumulative metal release in column
leaching tests at L/S ≤ 10 L/kg with the different leaching solutions used (Eq. 3.7).
pH 5 pH 6 pH 7 pH 8
M (µg/kg) = a·L/S
a R2 a R2 a R2 a R2
As 3.3 0.99 6.8 0.99 6.9 0.99 8.4 0.98
Cd 0.9 0.99 0.045 0.99 0.047 0.92 0.026 0.99
Cr 7.2 0.99 4.8 0.99 3.8 0.99 3.9 0.99
Cu 4974 0.99 112.8 0.99 103.8 0.99 216.5 0.89
Ni 40.2 0.99 8.3 0.98 6.6 0.99 3.5 0.99
Pb 390.7 0.98 3.4 0.97 1.6 0.98 1.2 0.98
Zn 10150 0.99 780.6 0.89 479.9 0.96 295.7 0.98
Table 3.9. Fitting parameters and correlation coefficients (R2) for the cumulative metal release in
column leaching tests (Eq. 3.9).
𝑳 𝑳
M (µg/kg) = a·� �·𝒑𝑯−𝒃 +c·� � As Cd Cr Cu Ni Pb Zn
𝑺 𝑺
a 11.2 1.9·109 1.7·106 2.3·1011 1.8 ·108 1.1·1015 1.9·1014
b -0.6 13.3 8.6 11.2 9.6 17.8 14.7
c -25.8 0.027 5.7 46.1 5.9 -2.6 451.9
R2 0.96 0.99 0.99 0.96 0.99 0.99 0.98
132
The use of Eq. 3.11, where availability, AVB (µg/kg), is the maximum cumulative metal release at
L/S=10 L/kg obtained at any of the studied pH, leads to obtain the matrix retention factors (k) at
each pH (Table 3.10) that match the wide range of values previously reported for metal release
from different solid matrices (van der Sloot, 1996; Cappuyns and Swennen, 2008).
Table 3.10. AVB values, adjustable parameters (k) and correlation coefficients (R2) for each metal
for the cumulative metal release in column leaching tests at L/S ≤ 10 L/kg for the different
leaching solutions used (Eq. 3.11).
𝑳
�𝑺�
Metal release (µg/kg) = AVB·�𝟏 − 𝒆− 𝒌 � pH 5 pH 6 pH 7 pH 8
Metal AVB (µg/kg) k (L/kg) R2 k (L/kg) R2 k (L/kg) R2 k (L/kg) R2
As 130 35.1 0.99 11.7 0.98 9.3 0.98 5.6 0.95
Cd 9 6.1 0.93 161 0.99 130 0.93 205 0.99
Cr 71.14 5.9 0.94 8.3 0.96 9.1 0.96 7.6 0.96
Cu 50028 10.1 0.99 365 0.99 339.9 0.99 139.7 0.90
Ni 389.8 5.8 0.94 34.7 0.97 37.8 0.99 65.3 0.99
Pb 3764 5.8 0.93 908.5 0.98 1671 0.98 2013 0.98
Zn 96731 5.6 0.95 98.5 0.90 139.5 0.96 200.1 0.98
Figure 3.26 shows the final results of the geochemical model with Visual MINTEQ in seawater by
solid curves together with the leaching concentrations (µg/L) of the studied metals in the column
leaching tests. The model prediction in the case of As, Cd, Cr, Ni and Zn experimental leaching
column data present good results, however, these results are less good for Cu and Pb. However,
the performance of pH dependence leaching tests in the whole pH range and the determination of
the concentration of Fe- and Al-(hydr)oxides as well as the concentration of the fulvic and humic
acids of the sediment is proposed in order to improve the evaluation and modeling of metal
release with pH.
133
100 100
10
10
As (μg/L)
Cd (μg/L)
1
1
0,1
0,1 0,01
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
1000 10000
1000
100
Cu (μg/L)
Cr (μg/L)
100
10
10
1
1 0,1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
1000 1000
100
100
Ni (μg/L)
Pb (μg/L)
10
10
1
1 0,1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8 6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH pH
100000
10000
Zn (μg/L)
1000
100
10
1
6,2 6,4 6,6 6,8 7 7,2 7,4 7,6 7,8 8
pH
Column Experimental Visual MINTEQ Modeling
Fig. 3.26. Visual MINTEQ model predictions (solid curves) of metal leaching concentrations
(µg/L) as a function of final pH in column leaching tests.
134
The comparison between column and equilibrium (L/S=2, 4 and 10 L/kg) leaching tests values is
shown in large size symbols in log scale Figures 3.25a-g as metal release (µg/kg) and in Figure
3.27 as metal leaching (µg/L). Column and equilibrium concentration ratio trends as a function of
L/S and pH, show two general trends in the leaching results comparison: i) the highest
differences have been found at higher L/S ratios for all metals and pHs, and ii) Cr, Cu, and Zn
show the highest differences at the lower pH 5, but on the contrary As, Ni and Pb show the
highest differences at the higher pH 8. From these results, it can be concluded that column and
equilibrium leaching tests results are not entirely comparable, possibly due to the difference in the
experimental procedure (contact time, L/S ratio, agitation and static/dynamic conditions) (Bin-
Shafique et al., 2006; Simon et al., 2008; Cetin et al., 2012). However, the results obtained from both group
of tests, proposed as Tier 4a and 4b, are complementary (Payán et al., 2012a,b, 2013).
10000 Zn
1000 Zn Cu
Ccolumn (µg/L)
100 Pb
Ni
Ni
Cr
10 Pb
50:1
Cr
10:1 Cu
1 Cd
As
1:1 Cd
0,1 1:10
1:50
0,01
0,01 0,1 1 10 100 1000 10000
Ceq (µg/L)
DW-L/S2 DW-L/S4 DW-L/S10
Figure 3.27. Comparison of metal concentrations from column (C column ) and equilibrium (C eq )
leaching tests using different leaching solutions (deionized water-DW, and seawater-SW at pH 5,
6, 7 and 8) and different L/S ratios (2, 4 and 10).
135
The column leaching tests can be useful to simulate the contact of acidified seawater with
contaminated sediment. Taking into account the high content of Pb and Zn in the studied
sediment, a deeper analysis of the column leaching data for these elements is proposed.
The model is expressed mathematically by Equations 3.12-3.14; Eq. 3.12 expresses the mass
balance for component i. The first term of Eq. 3.12 represents the accumulation of the solute in
the bulk liquid, the second term represents the accumulation of the metal in the solid, the third
term is the convective (or advective) flow and the term in the right-hand part of the equation is
due to the axial dispersion and diffusion (dispersive transport).
∂Ci �1-ε� ∂Cs,i ∂Ci ∂2 Ci

+ρp · ∙ +v · = �E+Dm,i �· Eq. 3.12
∂t ε ∂t ∂z ∂z2
Where C i is the concentration of the metal in the liquid, Cs i is the concentration of the metal in
the sediment, v is the average velocity of the liquid through the column, ρ p is the density of the
sediment, ε is the porosity of the packing, E is the axial dispersion coefficient and D m,i is the
diffusivity of the metal in the liquid phase.
Equation 3.13 describes the mass transport for component i in the liquid interphase and Eq. 3.14
is the mass transport in the solid phase for component i.
∂Cs,i
ρp ·�1-ε�· = kF · ap ·�Ci -Ci,eq � Eq. 3.13
∂t
∂Csi 5 �1-εp � Def,i

= · ap ·�Csi -Csi,eq � Eq. 3.14
∂t rp
Where C i,eq is the equilibrium concentration of the metal in the liquid, Cs i,eq is the equilibrium
concentration of the metal in the solid, ε p is the porosity of the particle, D ef,i is the effective
diffusion coefficient in the solid, k F is the mass transport coefficient in the liquid phase, r p is the
radium of the particle and a p is the surface area of the particle. The mass transport in the liquid
phase is negligible since the mass transport in the solid phase is much lower than in the liquid
phase, therefore Eq. 3.13 can be neglected.
136
The final mathematical expression of the column leaching test is expressed by Eq. 3.15.
π·r2p ∂Csi 5 �1-εp � Def,i

· = · ap ·�Csi -Csi,eq � Eq. 3.15
Ms ∂(L/S) rp
In relation to the solid-liquid equilibrium of the metal (M) under study, the Freundlich isotherm (Eq.
3.16) is considered as the equilibrium expression, with the Freundlich adjustment parameters
((1/n) i and b i ).
M2+ (s) ⇄ M2+ (aq)
1
�n�
Csi,eq = bi ∙Ci,eqi Eq. 3.16
Where Csi,eq , Ci,eq are the equilibrium concentrations of the metal in the solid and liquid,
respectively. The parameters (1/n) i and b i depend on the pH and the simplest case, lineal
dependence, is assumed in the model.
In general, other pieces of work (Kalbe et al., 2007; Grathwohl and Susset, 2009) about the modeling
behavior of compounds in leaching tests consider a linear constant distribution coefficient
between the solid and liquid phase. In this work, a general equilibrium expression, such as the
Freundlich equation, has been selected in order to apply the model to a greater range of metal
concentrations.
The mathematical modeling of the column leaching test for Pb and Zn requires the equilibrium
expression in the liquid-solid (Eq. 3.15) which depends on the pH through the Freundlich
adjustment parameters (n and b) in Eq. 3.16. The change of pH from the inlet value (5, 6, 7 or 8)
to the final value in the collection vessel implies a gradient of pH in the column to be considered
in the development of the mathematical model through Eqs. 3.15 and 3.16 (Payán et al., 2012b).
The resolution of the proposed dynamic model and the estimation of the corresponding
parameters are done using Aspen Custom Modeler software which enable us to solve rigorous
models and to make parameter estimation simultaneously. The adjustment of the model
137
parameters is carried out using an NL2SOL algorithm for least-square minimization of the
deviation between experimental and theoretical data. The column has been simulated using four
steps and it was checked that, using a greater number of steps, the same results were obtained.
The dynamic model consists of a two unit-model: the packed bed column and the sample
collection vessel. The outlet stream of the column is collected in a mix tank, represented by Eq.
3.17.
d(CT
i ·V) Q d(CT
i ·V)
= · L = Q·CT i,in Eq. 3.17
dt Ms d(S)
Where CT i is the concentration of metal (i) in the sample collection vessel, V is the liquid volume
of the tank, CT i,in is the concentration of metal in the inlet stream of the tank.
Table 3.11 shows the estimated values of the Freudlinch parameters (Eq. 3.16), 1/n and b, for Zn
and Pb for the solid–liquid equilibrium. Figure 3.28 represents the solid-liquid simulated
equilibrium curves of each metal calculated using the parameters shown at Table 3.11.
Table 3.11. Values of the Freudlich parameters for the solid –liquid equilibrium (Eq. 3.16).
Zn Pb
pH
1/n b 1/n b
5 0.408 1.564 0.500 2.572
6 0.291 1.550 0.290 0.327
7 0.278 1.466 0.273 0.265
8 0.265 1.383 0.251 0.205
6,00E-02 2,50E-03
5,00E-02 2,00E-03
[Pb(s)]eq mol/kg
[Zn(s)]eq mol/kg
4,00E-02
1,50E-03
3,00E-02
1,00E-03
2,00E-02
1,00E-02 5,00E-04
0,00E+00 0,00E+00
0,00E+00 2,00E-06 4,00E-06 6,00E-06 0,00E+00 5,00E-09 1,00E-08 1,50E-08
[Zn(L)]eq mol/L [Pb(L)]eq mol/L
pH = 8 pH = 7 pH = 6 pH = 5
Figure 3.28. Simulated solid–liquid equilibrium curves for all studied pHs
138
The values of the effective diffusion parameters in the solid for both metals are estimated by
resolution of the previous equations through comparison with the experimental values, obtaining
the following values: Def,Zn=1.21 10-12 m2/s and Def,Pb=1.56 10-13 m2/s.
Equation 3.18 indicates the relation between the effective diffusion coefficient (Def,i) and the solid-
phase surface diffusion coefficient (Ds,i) considering that diffusion in the pores is negligible.
d(
, )
D, =
, d( , )
Eq. 3.18
where Ds,i is the solid-phase surface diffusion coefficient and d(Csi,eq)/d(Ci,eq) is the slope of the
liquid-solid equilibrium isotherm.
Metal diffusion in the solid can be controlled by diffusion in the pores, by diffusion in the surface
of the solid or by both of them. For the case under study, diffusion on the solid-phase surface is
the limiting step since the Suances sediment is a non-porous solid and low effective diffusion
coefficients are obtained. It is widely accepted that slow sorption and desorption processes are
due to diffusion-limited transport of solutes to sorption sites inside the particles or soil aggregates
(Olmstead and Weber, 1990). Other authors have demonstrated that intraparticle solid diffusion is the
rate-limiting step in the sorption of Cd and Zn to microporous oxides (Diban et al., 2007). Therefore,
we can conclude that the value of effective diffusion parameter obtained in the solid for Zn and Pb
is related to the value of surface diffusion in the solid phase (Eq. 3.18).
Effective diffusivity in the solid phase is a constant value but the solid-phase surface diffusivity
depends on the pH since dCsi,eq/dCi,eq is different for each pH value as shown in Figure 3.28.
Table 3.12 shows the solid-phase surface diffusivity values for each pH and metal. Solid-phase
surface diffusivity is 4-100 times higher for Zn than for Pb. The value of the solid-phase surface
diffusivity increases when pH decreases (Table 3.12), which indicates that surface diffusivity is a
function of site density and this is consistent with the energy activation theory.
139
Table 3.12. Solid-phase surface diffusivity values for each pH and metal (Eq. 3.18).
Zn Pb
pH d(Csi,eq)/d(Ci,eq) d(Csi,eq)/d(Ci,eq)
Ds (m2/s) Ds (m2/s)
(kg/m3) (kg/m3)
5 3.53105 1.4810-18 5.22105 5.0910-19
6 1.36106 3.8210-19 2.12107 1.2510-20
7 1.61106 3.2310-19 3.49107 7.6210-21
8 1.90106 2.7410-19 4.68107 5.6710-21
Figure 3.29 shows the experimental and simulated results obtained by the model presented. The
good agreement between experimental and simulated results can also be observed in the parity
plot in Figure 3.30. The statistical parameters of the comparison between experimental and
simulated data for all pH values together are calculated by the software: standard error of
estimate is 2.964 10-6 for Zn and 4.532 10-8 for Pb, and percentage variation is 99.5 for Zn and 99
for Pb. For a total number of 36 samples of each metal, only 4 samples for Zn and Pb have a
relative error higher than 15%. The good agreement shown in the figures and the good statistical
parameter values confirm that this model can be applied for Pb and Zn metal leaching from
sediment under acidic conditions (Payán et al., 2013).
140
2,00E-04 2,50E-06
pH = 5 pH = 5
1,60E-04 2,00E-06
[Pb] (mol/L)
[Zn] (mol/L)
1,20E-04 1,50E-06
8,00E-05 1,00E-06
4,00E-05 5,00E-07
0,00E+00 0,00E+00
0 5 10 15 0 5 10 15
2,50E-05 3,00E-07
pH = 6 pH = 6
2,00E-05 2,50E-07
[Pb] (mol/L)
2,00E-07
[Zn] (mol/L)
1,50E-05
1,50E-07
1,00E-05
1,00E-07
5,00E-06 5,00E-08
0,00E+00 0,00E+00
0 5 10 15 0 5 10 15
1,60E-05 1,00E-07
pH = 7 pH = 7
1,20E-05 8,00E-08
[Zn] (mol/L)
[Pb] (mol/L)
6,00E-08
8,00E-06
4,00E-08
4,00E-06
2,00E-08
0,00E+00 0,00E+00
0 5 10 15 0 5 10 15
3,00E-05 5,00E-08
2,50E-05 pH = 8 pH = 8
4,00E-08
[Zn] (mol/L)
[Pb] (mol/L)
2,00E-05
3,00E-08
1,50E-05
2,00E-08
1,00E-05
5,00E-06 1,00E-08
0,00E+00 0,00E+00
0 5 10 15 0 5 10 15
Figure 3.29. Simulated and experimental results of the metal concentration at the collection
vessel with L/S ratio for different CO2 acidified seawater pH values (5, 6, 7 and 8).
141
2,00E-04 2,50E-06
2,00E-06
1,50E-04
1,50E-06
[Zn]est
[Pb]est
1,00E-04
1,00E-06
5,00E-05
5,00E-07
0,00E+00 0,00E+00
0,00E+00 5,00E-05 1,00E-04 1,50E-04 2,00E-04 0,00E+00 1,00E-06 2,00E-06
[Zn]exp [Pb]exp
Figure 3.30. Parity plots of the simulated and experimental results of the metal concentration with
L/S ratio for all pH values.
3.5.4. pH dependence leaching test results
The pH is one of the most important parameters in the metal leaching process. In the next
paragraphs, the results obtained from the modified pH dependence leaching test in the whole pH
range (0-14) using deionized water and seawater as leaching solutions are presented.
Figure 3.31 shows the changes in pH after the addition of acid (positive scale) or base (negative
scale) for all the samples which reach the equilibrium condition. The experimental results show
that the sediment has a low neutralization capacity to base addition and a relatively high acid
neutralization capacity due to the high carbonate content. The buffering capacity of the seawater
influences the test due to the fact that a slightly higher amount of acid or base is needed to
achieve the same pH value. The pH values considered to report the pH dependence leaching test
results (pH 4, 7 and 12) for deionized water and seawater show higher eq/kg values for seawater
(Fig. 3.31), highlighting the slightly stronger buffer capacity with respect to deionized water. In
addition, the smoother curve obtained when using seawater as leaching solution is due to the
buffer capacity of the seawater itself. To cover the whole pH range, 16 and 18 final values were
needed for deionized water and seawater as leaching solutions, respectively. In this way, the
maximum difference between two consecutive pH values <1.5 pH units condition was achieved.
142
16
14
12
BNC pH12, S = - 1.38
10 BNC pH12, D = - 0.44
pH 6 ANC/BNC pH7, S = 0.66

ANC/BNC pH7, D = 0.23
4
2 ANC pH4, S = 3.97
ANC pH4, D = 3.58
0
-7 -5 -3 -1 1 3 5 7 9 11
eq/kg
DEIONIZED WATER SEAWATER
Figure 3.31. pH vs. eq/kg of sediment in the pH dependence leaching test when using deionized
water and seawater. D: Deionized water; S: Seawater.
The number of replicates at each eq/kg sample needed in order to obtain two replicates that
reach the equilibrium condition (pH48h-pH44h<0.3) in the pH dependence leaching test is quite
different. Around 1.5 times more replicates are necessary to complete the test with seawater than
with deionized water. Thus, the equilibrium condition is difficult to achieve, especially for
seawater, being the basic range and the neutral point the most problematic ones. It was also
demonstrated that a 48 h experiment was not sufficient for a thorough assessment of metal
leaching thus longer time tests at 96 h have been performed with sediment samples to assess
changes in leaching behavior when pH changes occur (Cappuyns and Swennen, 2008; Shtiza et al.,
2009). Taking this into account, longer duration tests (96 h) were done in order to check the
equilibrium condition with seawater at different periods of time based on CEN/TS 14429. For the
96 h tests with seawater, only two replicates were performed at each eq/kg point. For the
sediment studied, the performance of longer time tests does not help to reduce the number of
replicates to achieve the equilibrium condition (∆pH<0.3). The titration curve (pH vs. eq/kg) of the
48 and 96 h pH dependence leaching tests for seawater (Fig. 3.32) shows that for the basic zone
(from -2.5 eq/kg to 0 eq/kg), the pH values obtained with the 48 h test are higher than the ones
obtained with the 96 h test, except only for the -2.5 eq/kg point. The opposite happens for the
acidic zone (from 0 eq/kg to 4.5 eq/kg). Thus, the use of the leaching test at longer times
decreases the pH in the basic zone and increases it in the acidic zone, i.e., neutralizes the pH
value due to the buffer capacity of this leaching agent.
143
14
12
10
8
pH
6
0
-3 -2 -1 0 1 2 3 4 5
eq/kg
pH 48h pH 96h
Figure 3.32. pH vs. eq/kg of sediment for the tests performed until 48 h and 96 h with seawater.
Previous results showed the importance of DOC leaching with seawater at natural pH and with
slightly acidic conditions that would occur shortly after a large CO2 leakage. Figure 3.33 shows
the DOC (mg/L) release during the pH dependence leaching test. The DOC increase with pH is
noticeable from pH 8. It can be seen that DOC values are slightly higher in the acid pH range
than in the neutral pH range. When comparing the DOC results obtained with deionized water
and seawater, it can be seen that the values of the pH dependence leaching test match
reasonably, with more variability from pH 12 for both kinds of water. Thus, the DOC release
depends basically on the pH of the water and there is only a significant influence of the type of
water used at basic pH conditions. The DOC leaching for deionized water and seawater has been
fitted together to an empirical mathematical expression in order to predict the DOC leaching
behavior with pH (Fig. 3.33). The DOC behavior with pH follows a polynomial equation with a
correlation coefficient value R2 of 0.84.
144
500
DOC (mg/L) = 6.21·pH2 – 67.85·pH + 192.08
450
R² = 0.84
400
350
DOC (mg/L)
300
250
200
150
100
50
0
0 2 4 6 8 10 12 14 16
pH
Deonized water Seawater DOC Fitting
Figure 3.33. DOC (mg/L) experimental release with pH and fitting curve for deionized water and
seawater.
The metal leaching results for the pH dependence leaching tests in the whole pH range (Figs.
3.34 and 3.35) show that some elements (Cd, Cr, Ni, Pb and Zn) present a drop in concentration
between pH 0 and neutral pH. There is a general increase from neutral pH toward strongly
alkaline pH values (As, Cr, Cu, Ni, Pb and Zn), which is less pronounced that the previous drop.
This behavior results in typical V-shaped leaching curves observed for the majority of the
contaminants. Cationic or amphoteric metals as Cd, Cr, Ni, Pb and Zn are generally more soluble
at low pH values where metal sorption to variably charged surfaces is generally weaker than at
neutral pH values. The element As behaves as an oxyanion, showing not only a minimum but
also a maximum concentration and a high release at basic pH due to the negatively charged
surfaces above the point zero charge, when the sorption of anions is less favorable (Rigol et al.,
2009). Cu presents more similar shape behavior to DOC than the other elements. The slightly
higher Cu release at alkaline pH values can be explained by the dissolution of organic matter and
the complexation of dissolved Cu by DOC (Ahmad et al., 2012). DOC leaching is higher than metal
leaching in the whole pH range, except for Zn. Metal leaching for deionized water and seawater
presents similar results and tendencies, showing a slightly higher release in the case of deionized
water. Furthermore, seawater concentration results fluctuate more with pH, mainly in the neutral
and basic range due to its high buffer capacity.
145
Figures 3.34 and 3.35 show the metal leaching and modeling results for the pH dependence
leaching tests in the whole pH range using deionized water and seawater as leaching solutions.
The higher leaching with deionized water is more pronounced at alkaline pH values (i.e., As, Cu,
Pb). On the contrary, metal leaching with seawater is higher at acidic pH values for Cd, Cr, Ni and
Zn. The modeling results with deionized water and seawater show metal concentrations in the
same order of magnitude with respect to the experimental results for most metals. Only As and,
Cr and Cd with seawater, present differences of up two or three orders of magnitude at certain pH
values. These results are in good agreement with the previous leaching test modeling using
deionized water, most importantly for Cd, Ni, Pb and Zn. However, for As, Cd and Pb, some
differences are presented between the leaching solutions.
According to the modeling results (Fig. 3.34), for deionized water, As may precipitate as
BaHAsO4:H2O at pH 7-12 and Ca3(AsO4)2:4H2O at pH 10-13 (Payán et al., 2012a). For seawater, As
may precipitate as BaHAsO4:H2O at pH 3.5-14 (Payán et al., 2012a). The mobility of As in seawater
is lower than in deionized water. This could be due to the higher content of alkaline earth metals
such as Ca and Mg in seawater associated with organic matter that can be involved in the
adsorption of these metals (Maher and Butler, 1988). For Cd, modeled and experimental leaching
curves present not very similar shapes. Cr may precipitate as Cr2O3(c) (Payán et al., 2012a) and
MgCr2O4(s) at pH 10-14 with both leaching solutions. Experimental data for Cr show a similar
dissolution pattern as a function of pH than the model predicted. For Cd and Cr, there are six
experimental values in the pH range of 6-12 and 5-10, respectively, close to the detection limit of
0.3 µg/L for Cd and 1 µg/L for Cr; therefore the experimental concentration results are higher
than the modeling results in this pH range. For the Ni modeling, it appears that Ni(OH)2 is the
controlling phase for Ni at pH 10-14 (Dijkstra et al., 2004; Payán et al., 2012a) for deionized water and
seawater. Modeled and experimental data for Ni agree acceptably well in the whole pH range. Pb
may precipitate as chloropyromorphite(c) (Pb5(PO4)3Cl) at pH 2.5-12, plumbgummite
(PbAl(PO4)2(OH)5:H2O) at pH 3.5-10.5, Pb(OH)2(s) at pH 9.5-14 for both deionized water and
seawater; however, new solid phases as hydrocerrusite (Pb2(OH)2CO3) at pH 10-12, and
Pb2(OH)3Cl(s) at pH 11-12.5 are found for deionized water (Dijkstra et al., 2004; Navarro et al., 2011;
Ahmad et al., 2012; Payán et al., 2012a). In the case of seawater at high pH values, as well as for As,
the higher content of alkaline earth metals such as Ca and Mg can increase the adsorption of this
metal in organic matter (Maher and Butler, 1988). The DOC influence on Pb leaching is taken into
146
account using the Gaussian model. The match between modeled and experimental Pb data is
quite good in the whole pH range. The controlling phases for Zn are hydrozincite
(Zn5(CO3)2(OH)6) at pH 8.5-10.5 and zincite (ZnO) at pH 9.5-14 (Payán et al., 2012a) for both
leaching solutions. The agreement between modeled and experimental Zn data is quite good in
the whole pH range.
1000000 1000000
100000 100000
10000 10000
1000 1000
Cd (µg/L)
As (µg/L)
100
100
10
10 1
1 0,1
0,1 0,01
0,01 0,001
0,001 0,0001
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
pH pH
1000000 1000000
100000 100000
10000 10000
1000 1000
Cr (µg/L)
Ni (µg/L)
100 100
10 10
1 1
0,1 0,1
0,01 0,01
0,001 0,001
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
pH pH
1000000 1000000
100000 100000
10000 10000
1000 1000
Zn (µg/L)
Pb (µg/L)
100 100
10 10
1 1
0,1 0,1
0,01 0,01
0,001 0,001
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
pH pH
Deionized water Modeling Deionized water
Seawater Modeling seawater
Figure 3.34. Experimental and modeled results of metal leaching as a function of pH for the pH
dependence leaching test using deionized water and seawater as leaching solutions.
147
For Cu, the DOC influence on the Cu leaching is taken into account using the NICA-Donnan
model. Different authors have considered active DOM to DOC ratios [DOMactive/DOC] from 1.65 to
0.25 (Dijkstra et al., 2004, 2009; Apul et al., 2010; Charriau et al., 2011). The consideration of only fulvic
acids (FA), only humid acids (HA) or a combination of both, to quantify the active DOM, has been
assumed in different pieces of work, showing in some cases modeling results that differ slightly
between these considerations (Charriau et al., 2011; Sader et al., 2011). Cu release is modeled with the
ratio of active DOM to DOC equal to 1, chosen after the consideration of different active DOM to
DOC ratios, from the default value of 1.65 in Visual MINTEQ, to 0.7. Furthermore, three different
situations are considered for the modeling based on the experimental results of HA and FA
obtained. The first case considers that 87% of active DOM is FA and 13% HA (according to the
experimental results), the second case, considers that the active DOM is only HA and, the last
one considers that the active DOM is only FA. The best results are obtained with the second
consideration of 100% HA as active DOM (Fig. 3.35). Cu shows high affinity for organic matter in
soils and sediment, particularly humic acids and formation of carbonate and hydroxyl soluble
complexes (Dijkstra et al., 2004; Nordmyr et al., 2008). Furthermore, the consideration of the active
DOM as 100% HA is supported by the extremely high affinity of Cu for adsorption to HA relatively
to the other surfaces (Kinniburg et al., 1999; Dijkstra et al., 2004).
1000
100
Cu (µg/L)
10
0,1
0 2 4 6 8 10 12 14
pH
Deionized water Seawater Model (HA+FA)-D Model (HA+FA)-S
Model (HA)-D Model (HA)-S Model (FA)-D Model (FA)-S
Figure 3.35. Experimental and modeled results of Cu leaching as a function of pH for the pH
dependence leaching test using deionized water and seawater as leaching solutions. D:
Deionized water; S: Seawater.
148
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157
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CONCLUSIONS AND FUTURE WORK
Conclusions and future work
160
4. CONCLUSIONS AND FUTURE WORK
4.1. Conclusions
The main conclusions of this doctoral thesis can be summarized in the following points:
o The superficial sediment samples of Suances (Spain), an area proposed as a potential

CO2 store site, present high quantities of contaminants, especially Zn and Pb, confirmed
by a thorough environmental and physico-chemical characterization of the sediment. In
this sense, the evaluation through different leaching tests in the risk assessment task will
be useful in a Carbon Capture and Storage (CCS) context.
The use of a variety of modified leaching tests designed by CEN/TC 292 for waste
materials is valid to provide a better knowledge of the key parameters controlling the
mobility of contaminants from marine sediment under different acidification conditions.
Leaching tests using a wide range of contact configuration, pH values, contact time, and
leaching solutions, allow to simulate different scenarios and the prediction of the DOC,
As, Cd, Cr, Cu, Ni, Pb and Zn releases.
o The initial pH value of the leaching solution used is slightly neutralized by the seawater-
carbonate rich sediment system; although under CO2 acidified seawater at pH 5,
considered as the worst expected local leakage scenario, important negative effects are
expected at local scale. Leaching tests reach a lowest pH of 6.8 for seawater leachates.
The strong influence of seawater acidification on metal leaching from sediment due to
CO2 leakage is emphasized with the increase in metal concentrations. Compared to the
natural seawater pH (pH 8), at pH 7.3, metal concentrations could increase by about 45%
and, at pH 6.8, by 66-82%.
o Leaching tests show that the DOC release is important at natural pH and slightly acidic
conditions in seawater; in a CO2 leakage scenario the CO2 bubbling in seawater would
mobilize high quantities of DOC and, in latter steps, would complex metals mobilized by
the gradual seawater acidification.
161
o The equilibrium leaching test results for the metals under study show, for nearly all
studied pHs, the decrease in leachate metal concentration with increased L/S. The study
of the dominant control mechanisms in the leachates shows that Cd and Ni present
solubility control mechanism for deionized water and natural seawater; however, Cd
(seawater at pH 6, 7, 8), Ni (deionized water, seawater pH 6) and Zn (seawater pH 6)
present availability control mechanism.
o The column leaching test results show that the cumulative element release increases
with L/S until the end of the test at L/S=10 L/kg. Element concentrations as a function of
the final leachate pH of the column leaching tests show a decreasing behavior with pH at
neutral and slightly basic pH values for Cd, Cu, Ni, Pb and Zn. However, As and Cr have
an increasing tendency and near constant behavior with pH, respectively, as it was
expected due to their oxyanionic behavior. A dynamic kinetic model of the evolution of Pb
and Zn concentrations with L/S has been proposed to model column metal release when
natural seawater and CO2 acidified seawater at pH 5, 6, 7 and 8 are used as leaching
solutions. Using Aspen Custom Modeler software, the effective solid diffusion values
Def,Zn=1.21 10-12 m2/s and Def,Pb=1.56 10-13 m2/s are obtained. A good agreement between
experimental and modeled concentration values confirms that the developed model can
be applied for Pb and Zn leaching from contaminated sediment under acidic conditions.
o The performance of the pH dependence leaching test with acidified seawater permits to
determine the release of contaminants in different acidification conditions of the marine
environment due to CO2 leakages from CCS sites and accidental acid spills in seawater.
The geochemical modeling of the experimental data using Visual MINTEQ allows to
predict the chemical species in leachates from sediment at different pH values obtaining
reasonable results with regard to As, Cd, Cr, Ni, Pb and Zn elements. The geochemical
model is carried out based on the mineralogy, surface adsorption to Fe- and Al-
(hydr)oxides (HFO) and metal-DOC binding models. The obtained geochemical results
show metal concentrations in the same order or one order of magnitude more with
respect to the experimental results for most metals. Furthermore, the results give minor
differences between seawater and deionized water for As, Cd and Pb. The modeling of
Cu release with the ratio of [active DOM/DOC]=1, and the consideration of the active
DOM as 100% humic acids (HA) leads to the best prediction results.
162
4.2. Future work
Based on the results presented in this doctoral thesis, the following points are considered for
future research:
o Development of pHstat leaching tests (CEN/TS14997) to simulate and to predict the

behavior trends and availability of metals in sediment in a wide pH range. The pHstat test
provides information on the kinetics of acid neutralization and metal release at different
pH values under specified experimental conditions. The leaching test working at constant
pH with different S-L-G contact configurations is proposed in order to improve the metal
release assessment and the subsequent modeling of the metal mobility behavior.
o Complete the Tier approach assessment of the contaminants mobility by the diffusion test
for monolithic materials, obtaining an interpretation of contaminant releases based on the
superficial area and the leaching mechanisms.
o Kinetic evaluation of the mobility and toxicity of metals at depth. The use of pressurized
mesoscale experiments at different leakage rates is proposed to determine the kinetic
toxicity of sediment exposed at CO2 leakage over time. The Titanium tank (TiTank) at the
Norwegian University of Science & Technology (Dr. M. Ardelan), was developed specially
to study the impact of CO2 leakage on the marine ecosystem. This experimental vessel
offers a continuous monitoring of CO2 leakage impact on marine ecosystem under fully
controlled water flow rate, CO2 fluxes, and various pressure conditions, which
corresponds to an ocean depth of 300 meters.
o Integration of the risk assessment results associated to the metal leaching from
contaminated sediment with other lines of evidence as bioavailability, bioaccumulation of
contaminants, biomarkers of response to the changes in the concentration of metals and
toxicity due to the CO2 leakage. These results will contribute in the risk management step
to design a Tier testing for the development of a decision-making framework of CO2
storage sites.
163
164
APPENDIX.
DISSEMINATION OF RESULTS
Appendix. Dissemination of results
166
APPENDIX. DISSEMINATION OF RESULTS
The complete references of the scientific papers and international congress communications
directly related to this doctoral thesis are presented next:
SCIENTIFIC PAPERS:
1. Payán, M.C., Verbinnen, B., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012.
Potential influence of CO2 release from a carbon capture storage site on release of trace metals
from marine sediment. Environmental Pollution 162, 29-39. [JCR IF2011: 3.746; Environmental Science
Q1]
2. Payán, M.C., Galan, B., Coz, A., Vandecasteele, C., Viguri, J.R., 2012. Evaluation
through column leaching tests of metal release from contaminated estuarine sediment subject to
CO2 leakages from Carbon Capture and Storage sites. Environmental Pollution 171, 174-184.
[JCR IF2011: 3.746; Environmental Science Q1]
3. Payán, M.C., Galan, B., Ruiz, G., Coz, A., Viguri, J.R., 2013. Pb and Zn release from
intertidal marine sediment in contact with acidified CO2 seawater: mathematical model for column
leaching tests. Chemical Engineering Science 95, 85-93. [JCR IF2011: 2.431; Chemical Engineering Q1]
4. Payán, M.C., Martín-Torre, M.C., Verbinnen, B., Coz, A., Vandecasteele, C., Viguri, J.R.,
2013. Geochemical modeling of the pH dependence metal leaching behavior of contaminated
marine sediment. Journal of Environmental Management. Under review on April 14, 2013.
INTERNATIONAL CONGRESS COMMUNICATIONS:
1. Riba, I., Fernandez de la Reguera, D., Alvarez-Guerra, M., Payán, M.C., Blasco, J.,
DelValls, T.A., Viguri, J.R. Impact of injection and storage of CO2 in marine sediments.
An integrative approach. SETAC Europe: 19th Annual Meeting. 31 May-4June, 2009,
Göteborg.
167
2. Payán, M.C., Coz, A., Galan, B., Viguri, J.R. Potential mobilisation of heavy metals from
marine sediments due to the effects of CO2 leakages from marine CCS systems. SETAC
Europe: 20th Annual Meeting. 23-27 May 2010, Seville.
3. Payán, M.C., Coz, A., Galan, B., Viguri, J.R. Leaching tests as useful tools to
characterise contaminated marine sediments mobility under CO2 leakages from CCS
technology. 19th International Congress of Chemical and Process Engineering and 7th
European Congress of Chemical Engineering ECCE-7. 28 August-1 September 2010,
Prague.
4. Payán, M.C., Coz, A., Vandecasteele, C., Galan, B., Viguri, J.R. Analysis and modeling
of trace elements release from contaminated marine sediment in contact with geological
sequestration systems CO2 leakages. 8th European Congress of Chemical Engineering
and 1st European Congress of Applied Biotechnology ECCE/ECAB 2011. 25-29
September 2011, Berlin.
5. Payán, M.C., Ruiz, G., Galán, B., Andrés, A., Coz, A., Viguri, J.R. Kinetic model of Pb
and Zn release from marine sediment of Cantabria using column leaching tests. 4th
International Conference on Engineering for Waste and Biomass Valorisation. 10-13
September 2012, Porto.
168
169
170

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Universidad de Cantabria

Escuela Técnica Superior de Ingenieros Industriales y de

ANÁLISIS Y MODELADO DEL COMPORTAMIENTO DE LIXIVIACIÓN

ANALYSIS AND MODELING OF METAL RELEASE FROM CONTAMINATED

Programa Oficial de Doctorado en Ingeniería Química y de Procesos (BOE núm. 36, de 10 de

María Cruz Payán Fraile

Javier R. Viguri Fuente

Alberto Coz Fernández Santander, Abril 2013

Y finalmente, aquí está la tesis y aquí termina una etapa.

1.1. Global climate change and possible mitigation options 19

1.2. The Carbon Capture and Storage (CCS) technology 20

1.2.1. The CCS three-step process 21

1.2.2. Legal framework for CCS 22

1.2.3. CCS projects around the world 23

1.3. CO2 sequestration in sub-seabed geological structures 24

1.4. Risk assessment and management of storage of CO2 streams in geological

1.4.1. Risk of CO2 leakages in the marine environment 31

1.5. The leaching process 33

1.5.1. Objectives and principles of leaching tests 33

1.5.2. Basic characterization tests 34

1.5.3. Compliance tests 35

1.6. Modeling of the leaching tests results 36

1.7. Objectives and thesis structure 38

3. PROCEDURES AND MATERIALS USED. OVERALL SUMMARY OF RESULTS AND

3.1. Tier approach procedure 93

3.2. Sediment characterization 94

3.2.1. Area of study: Suances estuary 94

3.2.2. Sediment sampling and characterization 96

3.3. Leaching tests 98

3.3.1. Leaching solutions 98

3.3.2. Leaching tests procedure 100

3.3.3. Analyses of the leachates 110

3.4. Modeling of the leaching results 111

3.4.1. Empirical modeling 111

3.4.3. Geochemical modeling with Visual MINTEQ 113

3.5. Discussion of results 114

3.5.1. Sediment characterization results 114

3.5.2. Equilibrium leaching test results 123

3.5.3. Column leaching test results 126

3.5.4. pH dependence leaching test results 142

3.6. References 149

4. CONCLUSIONS AND FUTURE WORK 159

4.1. Conclusions 161

4.2. Future work 163

APPENDIX. DISSEMINATION OF RESULTS 165

Durante el secuestro geológico, el CO2 se almacena por atrapamiento hidrodinámico, mineral o

Sequestration of CO2 in sub-seabed geological formations is currently among techniques

1. 1. Global climate change and possible mitigation options

1.2. The Carbon Capture and Storage (CCS) technology

1.2.1. The CCS three-step process

1.2.2. Legal framework for CCS

Table 1.2. Applicable international, European and Spanish legislations on CCS

1.2.3. CCS projects around the world

Figure 1.4. Potential subterranean structures for CO2 storage in Spain

1.3. CO2 sequestration in sub-seabed geological structures

o Assessment of the suitability of a potential injection-site for permanent containment of

in the sediment-seawater interface, leading to biogeochemical alteration in marine ecosystems. In

Seawater (upper Acidification of seawater Total acid-leachable and

Batch reactions of water Quartz-rich alluvial Continuous CO2 bubbling

1.4.1. Risk of CO2 leakages in the marine environment

1.5. The leaching process

1.5.1. Objectives and principles of leaching tests

o Tests of basic characterization aim at obtaining information on characteristic properties of