Geoquímica Aplicada 17 (2002) 517-568

[Link]/locate/apgeochem
revisión

Una revisión de la fuente, el comportamiento y la distribución

de arsénico en aguas naturales

PL * Smedley, DG Kinniburgh
British Geological Survey, Wallingford, Oxon OX10 8BB, Reino Unido

Recibido el 1 de marzo de 2001; aceptado 26 de de octubre de de 2001

manejo editorial de R. Fuge

Abstracto

El intervalo de concentraciones que se encuentran en las aguas naturales es grande, que van desde menos de 0,5 metro gl 1 a más de 5000
metro gl 1. Las concentraciones típicas en agua dulce son menos de 10 metro gl 1 y frecuentemente menos de 1 metro gl 1. En raras ocasiones, se encontraron
concentraciones mucho más altas, sobre todo en las aguas subterráneas. En tales zonas, más del 10% de los pozos puede ser 'un ff ected' (definido como los que
superan 50 metro gl 1) y en el peor de los casos, esta cifra puede superar el 90%. Bien conocido de alta Como zonas de aguas subterráneas se han encontrado en
Argentina, Chile, México, China y Hungría, y más recientemente en Bengala Occidental (India), Bangladesh y Vietnam. La magnitud del problema en términos de
población se expone a altas concentraciones Como es mayor en la cuenca de Bengala con más de 40 millones de personas en el agua que contiene 'excesiva' Como
potable. Estos gran escala 'natural' Como áreas problemáticas de agua subterránea tienden a ser encontrados en dos tipos de medio ambiente: FI rstly, en el interior o
cuencas cerradas en zonas áridas o semiáridas, y en segundo lugar, lo que reduce fuertemente acuíferos a menudo derivados de aluvión. Ambos entornos tienden a
contener sedimentos geológicamente jóvenes y estar en áreas planas, bajas donde el agua subterránea flujo es lento. Históricamente, estos son mal acuíferos barrió fl y
cualquier medida que liberan de los sedimentos tras el entierro ha sido capaz de acumular en el agua subterránea. las aguas subterráneas rico en arsénico también se
encuentran en áreas geotérmicas y, en una escala más localizada, en las áreas de la actividad minera y donde se ha producido la oxidación de minerales de sulfuro. El
contenido A partir de los materiales de acuíferos en las principales acuíferos problema no parece ser excepcionalmente alta, siendo normalmente en el intervalo 1-20 mg
kg 1. Parece que hay dos gatillos '' distintas que pueden conducir a la liberación de Como a gran escala. El primero es el desarrollo de condiciones en entornos
semi-áridas o áridas pH alto (> 8,5) por lo general como resultado de los ECTS e ff combinados de meteorización mineral y altas tasas de evaporación. Este cambio de
pH conduce o bien a la desorción de adsorbe Como (especialmente como especies (V)) y una serie de otros elementos formadores de aniones (V, B, F, Mo, Se y U) de
óxidos minerales, especialmente los óxidos de Fe, o que les impide ser adsorbido. El segundo gatillo es el desarrollo de condiciones fuertemente reductoras a valores de
pH casi neutras, lo que conduce a la desorción de A partir de óxidos minerales y a la disolución reductora de los óxidos de Fe y Mn, también conduce a Como liberación.
De hierro (II) y As (III) son relativamente abundantes en estas aguas subterráneas y SO 4 las concentraciones son pequeñas (típicamente de 1 mg l 1 o menos). Grandes
concentraciones de fosfato, bicarbonato, silicato y materia orgánica, posiblemente, puede mejorar la desorción de Como debido a la competencia por los sitios de
adsorción. Un rasgo característico de alta subterránea como áreas es el alto grado de variabilidad espacial en concentraciones como en las aguas subterráneas. Esto
significa que puede ser di fi culto, o imposible, predecir de forma fiable la concentración probable de Como en un pozo en particular a partir de los resultados de los
pozos vecinos y significa que no hay otra alternativa que analizar cada pocillo. El arsénico, un ff acuíferos ejadas están restringidas a ciertos ambientes y parecen ser la
excepción y no la regla. En la mayoría de los acuíferos, la mayoría de los pozos es probable que sean Una ff reflejado, incluso cuando, por ejemplo, que contienen altas
concentraciones de Fe disuelto. # 2002 Publicado por Elsevier Science Ltd. Todos los derechos reservados.

* Autor correspondiente. Fax: + 44-1491-692345.

Dirección de correo electrónico: pls@[Link] (PL Smedley).

0883-2927 / 02 / $ - see front matter # 2002 Publicado por Elsevier Science Ltd. Todos los derechos reservados. PI I: S0883- 2927
(02) 00018- 5
518 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

Contenido

1. Introducción ............................................... .................................................. .................................................. ........ 519

2. El arsénico en aguas naturales ............................................ .................................................. ......................................... 520

2.1. especiación acuosa ................................................ .................................................. ...................................... 520
2.2. Abundancia y distribución ............................................... .................................................. ......................... 520
2.2.1. la precipitación atmosférica ................................................ .................................................. ............... 521
2.2.2. Agua de rio ................................................ .................................................. ...................................... 523
2.2.3. Agua de lago................................................ .................................................. ....................................... 524
2.2.4. El agua de mar y estuarios ............................................... .................................................. ...................... 525
2.2.5. El agua subterránea ................................................. .................................................. .................................. 525
2.2.6. drenaje de la mina ................................................ .................................................. .................................. 525
2.2.7. porewaters sedimentos ................................................ .................................................. ........................ 525
2.2.8. campo de petróleo y otras salmueras .............................................. .................................................. .................... 526
2.3. Distribución de especies de arsénico en cuerpos de agua ........................................... .................................................. . 526
2.4. Impacto de la cinética redox sobre la especiación de arsénico ........................................... .................................................. . 527

3. Fuentes de arsénico ............................................. .................................................. .................................................. 528 ..

3.1. Minerales ................................................. .................................................. .................................................. .... 528
3.1.1. Los principales minerales de arsénico ............................................... .................................................. ..................... 528
3.1.2. minerales de la roca de formación de .............................................. .................................................. ...................... 529
3.2. Rocas, sedimentos y suelos ............................................. .................................................. ............................. 530
3.2.1. Rocas ígneas................................................ .................................................. ................................... 530
3.2.2. Rocas metamórficas ................................................ .................................................. ......................... 530
3.2.3. Rocas sedimentarias ................................................ .................................................. ........................... 530
3.2.4. sedimentos no consolidados ................................................ .................................................. ............... 532
3.2.5. Los suelos ................................................. .................................................. ................................................ 533
3.2.6. Contaminada sur fi ciales depósitos ............................................... .................................................. ........ 533
3.3. La atmósfera ................................................ .................................................. ........................................... 533

4. interacciones de agua mineral ............................................ .................................................. ....................................... 533

4.1. Controles sobre la movilización de arsénico .............................................. .................................................. ................... 533
4.2. asociaciones de arsénico en los sedimentos .............................................. .................................................. .................. 534
4.3. sedimentos reducidos y el papel de los óxidos de hierro .......................................... .................................................. . 534
4.4. la liberación de arsénico de suelos y sedimentos después de la reducción .......................................... ............................. 537
4.5. La especiación de elementos en los sedimentos y el papel de las técnicas de extracción selectiva ..................................... 538
4.6. Transporte de arsénico ............................................... .................................................. ..................................... 539

5. entornos de aguas subterráneas con altas concentraciones de arsénico .......................................... ..................................... 542
5.1. Distribución mundial de los problemas del agua subterránea de arsénico ............................................ ....................................... 542
5.2. La reducción de entornos ................................................ .................................................. ............................... 543
5.2.1. Bangladesh y la India (Bengala Occidental) ........................................... .................................................. .... 543
5.2.2. Taiwán ................................................. .................................................. ............................................ 547
5.2.3. el norte de China ................................................ .................................................. ................................ 547
5.2.4. Vietnam ................................................. .................................................. .......................................... 547
5.2.5. Hungría y Rumania ............................................... .................................................. ..................... 548
5.3. ambientes oxidantes áridas ............................................... .................................................. ......................... 548
5.3.1. Méjico................................................. .................................................. ............................................ 548
5.3.2. Chile ................................................. .................................................. ............................................... 548
5.3.3. Argentina ................................................. .................................................. ........................................ 549
5.4. oxidante mixto y entornos reductores ............................................. .................................................. 549 ..
5.4.1. El suroeste de [Link]. .............................................. .................................................. ........................... 549
5.5. fuentes geotérmicas ................................................ .................................................. ..................................... 550
5.6. mineralización de sulfuro de arsénico y los problemas relacionados con la minería .......................................... ............................ 551
5.6.1. Tailandia ................................................. .................................................. ......................................... 551
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5.6.2. Ghana................................................. .................................................. ............................................. 551

5.6.3. Estados Unidos ................................................ .................................................. ................................... 551
5.6.4. Otras areas ................................................ .................................................. ...................................... 551

6. Las características comunes de las áreas problemáticas del agua subterránea de arsénico ......................................... ............................................. 552

6.1. Una perspectiva hidrogeoquímico ............................................... .................................................. .................. 552

6.2. La fuente de arsénico .............................................. .................................................. ..................................... 552
6.3. movilización del arsénico gatillo geoquímica necesaria ........................................... .................................. 552
6.3.1. La desorción a pH alto en condiciones oxidantes ........................................... ................................ 553
6.3.2. desorción de arsénico y disolución debido a un cambio de condiciones reductoras .................................... 554
6.3.3. Reducción de la superficie de los minerales de óxido de ........................................... .......................................... 555
6.3.4. Reducción de la fuerza de unión entre las superficies de arsénico y minerales ......................................... ...... 555
6.3.5. la disolución de minerales ................................................ .................................................. .......................... 556
6.4. subterránea de transporte de flujos histórica ............................................. .................................................. ....... 556
6.5. futuros desarrollos en la investigación de arsénico ............................................. .................................................. ........ 558
6.6. Identificación de 'en riesgo' los acuíferos ........................................... .................................................. ..................... 558

7. Observaciones finales .............................................. .................................................. ............................................... 559

Expresiones de gratitud................................................. .................................................. .................................................. . 560

Referencias ................................................. .................................................. .................................................. .............. 560

1. Introducción una variedad de fuentes, dependiendo de la disponibilidad local: agua

superficial (ríos, lagos, embalses y lagunas), aguas subterráneas (acuíferos)
El reciente hallazgo de que las aguas subterráneas de grandes áreas de y el agua de lluvia. Estas fuentes son muy variables en términos de riesgo
Bengala Occidental, Bangladesh y otros países están fuertemente enriquecidos como. Junto a las fuentes puntuales evidentes de contaminación como,
con A medida que ha llevado a una reevaluación de los factores que controlan la altas concentraciones se encuentran principalmente en las aguas
distribución de As en el entorno natural y las formas en que medida puede subterráneas. Estos son en el que el mayor número de, como todavía sin
movilizarse. El arsénico es un elemento ubicuo que se encuentra en la atmósfera, identificar fi ed, las fuentes son susceptibles de ser encontrado. Por tanto,
los suelos y rocas, aguas naturales y organismos. Se movilizó a través de una esta revisión se centra en los factores que controlan las concentraciones de
combinación de procesos naturales, tales como reacciones de la intemperie, la As en las aguas subterráneas. Sin embargo, los autores también revisan la
actividad biológica y las emisiones volcánicas, así como a través de una gama de ocurrencia de Como en una amplia gama de aguas naturales ya que estos
actividades antropogénicas. Como la mayoría de los problemas ambientales son el indirectamente pueden estar involucrados en la formación de las aguas
resultado de la movilización en condiciones naturales. Sin embargo, el hombre ha subterráneas As-ricos y también pueden proporcionar un fondo útil contra el
tenido un importante impacto adicional a través de la actividad minera, la que ver las aguas subterráneas como concentraciones. Además,
combustión de combustibles fósiles, el uso de pesticidas arsenicales, herbicidas y
desecantes de cultivo y el uso de Como como un aditivo para la alimentación del
ganado, en particular para aves de corral. Aunque el uso de productos arsenicales
tales como pesticidas y herbicidas ha disminuido significativamente en las últimas Tras la acumulación de pruebas para el E ECTS ff toxicológicos crónicos
décadas, su uso para la conservación de la madera sigue siendo común. El de As en el agua potable, recomendables y se reducen los límites
impacto sobre el medio ambiente del uso de compuestos arsenicales, al menos regulatorios de muchas autoridades. El valor de referencia de la OMS para
localmente, se mantendrá durante algunos años. Como en el agua potable se redujo provisionalmente en 1993 De 50 a 10 metro
gl 1. El nuevo valor recomendado se basa en el aumento de la conciencia de
la toxicidad de Como, en particular su carcinogenicidad, y sobre la
capacidad de medir de forma cuantitativa (OMS, 1993). Si la base estándar
para la evaluación de riesgos aplicado a los productos químicos industriales
De las diversas fuentes de As en el medio ambiente, el agua potable, se aplicaron a medida, la concentración máxima admisible sería aún más
probablemente, representa la mayor amenaza para la salud humana. Como en bajo. La concentración máxima admisible CE (MAC) para Como en el agua
el aire, particularmente a través de la exposición ocupacional, también ha dado potable ha sido
lugar a problemas de salud conocidos en algunas áreas. El agua potable se
deriva de
520 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

reducido a 10 metro gl 1. El límite japonés para el agua potable es también 10 metro gl 1 arcilla o materia orgánica. En contraste, la mayoría de oxianiones incluyendo
mientras que la concentración máxima aceptable provisional para agua potable arseniato tienden a ser menos fuertemente adsorbidos como que aumenta el pH
canadiense es 25 metro gl 1. El límite de US-EPA también se redujo De 50 a 10 metro gl (Dzombak y Morel, 1990). En algunas condiciones, al menos, estos aniones
1 en enero de 2001, tras un prolongado debate sobre el límite más apropiado. Sin pueden persistir en solución a concentraciones relativamente altas (decenas de metro
embargo, esta regla es ahora (septiembre de 2001) siendo reconsiderado teniendo gl 1)
en cuenta las implicaciones de alto costo a la industria del agua de Estados Unidos, incluso a valores de pH casi neutras. Por lo tanto los elementos
que se estima en $ 200 millones por año. Mientras que muchas autoridades oxyanionforming tales como Cr, As, U y Se son algunos de los contaminantes
nacionales están tratando de reducir sus límites de acuerdo con el valor de traza más comunes en las aguas subterráneas.
referencia de la OMS, muchos países y de hecho todos un ff eja los países en En relación con los otros elementos formadores de oxianión-, como es uno
desarrollo, siguen funcionando en la actualidad al 50 metro gl 1 estándar, en parte de los más problemáticos en el medio ambiente debido a su movilidad relativa
debido a la falta de instalaciones de prueba adecuados para concentraciones más en un amplio intervalo de condiciones redox. El selenio es móvil como el
bajas. selenato (SEO 42 ) oxianión en condiciones oxidantes pero está inmovilizado en
condiciones de reducción, ya sea debido a la adsorción más fuerte de su
forma reducida, selenito (SEO 32 ), o debido a su reducción al metal. El cromo de
Hasta hace poco, como a menudo no estaba en la lista de los componentes manera similar puede ser movilizada como especies oxianión estables Cr (VI)
en agua rutinariamente analizados por laboratorios nacionales, los servicios de en condiciones oxidantes, sino que forma catiónicos Cr (III) especies en la
agua y las organizaciones no gubernamentales (ONG) y de lo que el cuerpo de reducción de ambientes y por lo tanto se comporta como otros cationes traza
la información potable sobre la distribución de As en el agua potable no es tan (es decir, es relativamente inmóvil a valores de pH casi neutras). Otros
conocida como para muchos otros componentes del agua potable. En los oxianiones tales como molibdato, vanadato, uranilo y renato también parecen
últimos años, se ha hecho evidente que tanto el valor de referencia de la OMS y ser menos móvil en condiciones reductoras. En entornos reductores S-rico,
las normas nacionales actuales son bastante frecuencia superados en las muchos de los metales traza también forman sulfuros insolubles. El arsénico
fuentes de agua de consumo, y, a menudo de forma inesperada manera. De se distingue por ser relativamente móvil bajo condiciones reducidas. Se puede
hecho, As y F son ahora reconocidos como los contaminantes inorgánicos más encontrar a concentraciones en el mg l 1 gama cuando todos los otros
graves en el agua potable en una base mundial. En las zonas de alta Como elementos formadores de oxianión-están presentes en el metro gl 1 distancia.
concentraciones, el agua potable es una fuente potencialmente importante de
Como en la dieta y por lo que su detección temprana es de considerable
importancia.

potencial redox (Eh) y el pH son los factores más importantes que

controlan Como especiación. En condiciones oxidantes, H 2 AsO 4 es dominante
a pH bajo (menor de aproximadamente pH 6,9), mientras que a pH más alto,
2. El arsénico en aguas naturales HASO 42 se convierte en dominante (H 3 AsO 40 y AsO 43 puede estar presente en
condiciones extremadamente ácidas y alcalinas, respectivamente). Bajo
2.1. especiación acuosa condiciones de reducción a pH menor de aproximadamente pH 9,2, las
especies no cargadas arsenito H 3 AsO 30 predominará (Fig 1;. Brookins, 1988;.
El arsénico es quizás único entre los metaloides pesados ​y elementos Yan et al, 2000). Las distribuciones de la especie como una función del pH se
formadores de oxianión-(por ejemplo As, Se, Sb, Mo, dan en la Fig. 2. En la práctica, la mayoría de estudios en los datos de
V, Cr, U, Re) en su sensibilidad a la movilización a los valores de pH encontrados especiación informe literatura sin consideración del grado de protonación. En
típicamente en las aguas subterráneas (pH 6.5 a 8.5) y bajo tanto oxidante y presencia de concentraciones extremadamente altas de reducción de S,
condiciones reductoras. El arsénico puede ocurrir en el medio ambiente en varios disueltos As-sulfuro de especies pueden ser significativa. La reducción,
estados de oxidación ( 3, condiciones ácidas favorecen la precipitación de oropimente (Como 2 S 3), rejalgar
0, 3 y 5), pero en las aguas naturales se encuentra principalmente en forma (culo) u otro sulfuro de minerales que contienen coprecipitados Como (Cullen
inorgánica como oxianiones de arsenito trivalente [As (III)] o pentavalente arseniato y Reimer, 1989). Por lo tanto las aguas de alta Como no se espera que
[As (V)]. formas orgánicos como pueden ser producidos por la actividad biológica, donde hay una alta concentración de sulfuro libre (Moore et al., 1988).
sobre todo en las aguas superficiales, pero rara vez son cuantitativamente
importantes. No obstante formas orgánicas pueden ocurrir donde las aguas son
significativamente afectados por la contaminación industrial.

La mayoría de los metales traza tóxicos se producen en solución como cationes

(por ejemplo, Pb 2+, Cu 2+, Ni 2+, Discos compactos 2+, Co 2+, Zn 2+) que por lo general cada vez 2.2. Abundancia y distribución
más insolubles a medida que aumenta el pH. Al pH casi neutro típico de la mayoría
de las aguas subterráneas, la solubilidad de la mayoría de los cationes de metales Las concentraciones de As en agua dulce varían en más de cuatro
traza está severamente limitada por precipitación como, o coprecipitación con, un órdenes de magnitud (Tabla 1) en función de la fuente de Como, la cantidad
óxido, hidróxido, carbonato o mineral de fosfato, o más probablemente por su fuerte disponible y el medio ambiente geoquímico local. En condiciones naturales,
adsorción al metal hidratado óxidos, el mayor rango y las más altas concentraciones de As son
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 521

Fig. 1. Diagrama de Eh-pH para acuosa Como especies en el sistema Como-O 2 -H 2 O en

25 C y la presión total de 1 bar.

encontrado en las aguas subterráneas, como resultado de la fuerte influencia de

las interacciones agua-roca y la mayor tendencia en los acuíferos de las
condiciones físicas y geoquímicas siendo favorable para la movilización y
acumulación. El intervalo de concentraciones para muchos cuerpos de agua es
grande y por lo tanto los valores 'típicos' son di culto FFI para derivar. Muchos
estudios de Como se informó en la literatura también se han dirigido
preferentemente áreas de problemas conocidos y por lo tanto reportado rangos
son a menudo extrema y no representativo de las aguas naturales como un
todo. No obstante, la siguiente recopilación de datos para rangos de
concentraciones que se encuentran en varias partes de la hidrosfera y litosfera
da una indicación general de los intervalos de concentración esperados y su
variación en el medio ambiente.

Fig. 2. (a) El arsenito y (b) la especiación arseniato como una función del pH (fuerza
iónica de aproximadamente 0,01 M). condiciones redox se han elegido de tal manera que
2.2.1. la precipitación atmosférica el estado de oxidación indicado domina la especiación en ambos casos.
El arsénico entra en la atmósfera a través de las aportaciones de la erosión
eólica, las emisiones volcánicas, baja temperatura
volatilización de los suelos, aerosoles marinos y la contaminación y se
devuelve a la superficie de la tierra por deposición húmeda y seca. Los operaciones de la fundición, la combustión de carbón y las emisiones volcánicas son

aportes antropogénicos más importantes son de operaciones de la fundición generalmente más altos. Andreae (1980) encontrado precipitaciones potencialmente un ff

y combustión de combustibles fósiles. El Como parece consistir ected por fundición y la quema de carbón de tener como las concentraciones de alrededor

principalmente As (III) 2 O 3 las partículas de polvo (Cullen y Reimer, 1989). de 0,5 metro gl 1 ( Tabla 1), aunque las concentraciones más altas (promedio 16 metro gl 1) se

Nriagu y Pacyna (1988) estimaron que las fuentes antropogénicas de han encontrado en lluvia recogida en Seattle unos 35 km a sotavento de una fundición de

arsénico atmosférica (alrededor de 18.800 toneladas 1) ascendió a alrededor Cu (Crecelius, 1975). Los valores dados para acumulación de nieve de Arizona (Tabla 1;

del 70% del global de la atmósfera Como fundente. Si bien se acepta que Barbaris y Betterton, 1996) también son probablemente ligeramente por encima de las

estas fuentes antropogénicas tienen un impacto importante en el aire Como concentraciones de referencia a causa de entradas potenciales de aire A partir de

composiciones, su influencia en el ciclo global Como no está bien fundiciones, plantas de energía y el polvo del suelo. En general, sin embargo, las fuentes

establecida. de suspensión en el aire Como en la mayoría de las naciones industrializadas están

limitadas como resultado de las medidas de control de contaminación del aire. A no ser

concentraciones basales de Como en las precipitaciones y la nieve en las zonas rurales significativamente contaminado

son invariablemente bajo en típicamente menos de 0,03

metro gl 1 ( Tabla 1). Las concentraciones en zonas un ff reflejada por

522 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

tabla 1
Las concentraciones típicas Como en aguas naturales

cuerpo de agua y la ubicación Como media concentración o rango de Referencia

( metro gl 1)

Lluvia de línea de

base agua

Marítimo 0.02 Andreae (1980)

Terrestre (w [Link].) 0,013-0,032 Andreae (1980)
Coastal (Medio Atlántico, [Link].) 0,1 (<0,005 a 1,1) Scudlark y la Iglesia (1988)
Nieve (Arizona) 0,14 (0,02 a 0,42) Barbaris y Betterton- (1996)

No de línea de base:

lluvia terrestre 0.46 Andreae (1980)

la lluvia de Seattle, impactado por la fundición de cobre dieciséis Crecelius (1975)

Línea de base

agua de río

Varios 0,83 (0,13-2,1) Andreae et al. (1983); Froelich et al. (1985); Seyler y Martin
(1991)
Noruega 0,25 (<0,02 a 1,1) Lenvik et al. (1978)
[Link]. Sureste 0,15-0,45 Waslenchuk (1979)
Estados Unidos 2.1 Sonderegger y Ohguchi (1988)
Dordoña, Francia 0.7 Seyler y Martin (1990)
Río Po, Italia 1.3 Pettine et al. (1992)
ríos europeos contaminados 4,5-45 Seyler y Martin (1990)
Danubio, Baviera 3 (1-8) Quentin y Winkler (1974)
schelde de captación, Bélgica 0,75-3,8 (hasta 30) Andreae y Andreae (1989)
Como las aguas subterráneas de alta influido: el
norte de Chile, norte de Chile 190-21800 Ceres Ca' et al. (1992)
400-450 Sancha (1999)
rdoba Co', Argentina 7-114 Lerda y Prosperi (1996)

Geotérmica influida
Sierra Nevada, [Link]. Waikato, 0.20-264 32 Benson y Spencer (1983) McLaren y
Nueva Zelanda (28-36) 44 Kim (1995) Robinson et al. (1995)
Missouri Ríos, [Link]. Madison y (19-67) 10-370 Nimick et al. (1998)

Minería influida
Ron Phibun, Tailandia Ashanti, 218 (4.8-583) 284 Williams et al. (1996)
Ghana (<2-7900) Smedley et al. (1996)
Columbia Británica, Canadá 17,5 (<0,2 a 556) Azcue et al. (1994)

Línea de base agua

del lago

Colombia británica 0,28 (<,2-0,42) Azcue et al. (1994, 1995)

Ontario 0.7 Azcue y Nriagu (1995)
Francia 0,73-9,2 (alto Fe) Seyler y Martin (1989)
Japón 0,38-1,9 Baur y Onishi (1969)
Suecia 0,06-1,2 Reuther (1992)

Geotérmica influida
el oeste de [Link]. ,38-1.000 Benson y Spencer (1983)

Minería influida
Territorios del Noroeste, Canadá Ontario, 270 (64-530) Bright et al. (1996) Azcue y Nriagu
Canadá 35-100 (1995)

Línea de base agua de

estuario

Fiordo de Oslo, Noruega 0,7-2,0 Abdullah et al. (1995)

Saanich Inlet, Columbia Británica 1.2-2.5 Peterson y Carpenter (1983)

( Continúa en la siguiente página)

 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 523

Tabla 1 ( continuado)

cuerpo de agua y la ubicación Como media concentración o rango de Referencia

( metro gl 1)

Rho ne estuario, Francia 2.2 (1.1 a 3.8) Seyler y Martin (1990)

Krka estuario, Yugoslavia 0,13-1,8 Seyler y Martin (1991)

La minería y la industria influida

Estuario del Loira, Francia Tamar hasta 16 Seyler y Martin (1990) Howard et al.
estuario, Reino Unido Escalda 02.07 a 08.08 (1988) Andreae y Andreae (1989)
estuario, Bélgica 1.8 a 4.9

Agua de mar

Profunda Pacífico y Malasia 1,0-1,8 Cullen y Reimer (1989) Yusof et al.

costera costa atlántica España 1,0 (0,7-1,8) (1994) Navarro et al. (1993) Maher
Costera Australia 1,5 (0,5-3,7) (1985)
1.3 (1.1 a 1.6)

El agua subterránea

la línea de base del Reino Unido < 0,5-10 Edmunds et al. (1989)
provincias como ricos (por ejemplo, cuenca de 10-5000 Das et al. (1995); BGS y DPhe (2001); Nicolli et al. (1989);
Bengala, Argentina, México, el norte de China, Smedley et al. (2001a); Del Razo et al. (1990); Luo et al.
Taiwán, Hungría) (1997); Hsu et al. (1997); Varsa' nyi et al. (1991)

las aguas subterráneas contaminadas con la minería 50-10.000 Wilson y Hawkins (1978); Welch et al. (1988); Williams et al.
(1996)
El agua geotérmica < 10-50,000 Baur y Onishi (1969); White et al., (1963), Ellis y Mahon
(1977)
planta herbicida arsenical, Texas 408.000 Kuhlmeier (1997a, b)

drenaje de la mina

Various, [Link]. < 1-34,000 Plumlee et al. (1999)

Montaña de hierro hasta 850.000 Nordstrom y Alpers (1999)
Montes Urales 400.000 Gelova (1977)

agua intersticial del sedimento

La línea de base, Estuario sueca 1,3-166 Widerlund y Ingri (1995)

La línea de base, arcillas, Saskatchewan, Canadá 3,2-99 Yan et al. (2000)

La línea de base, sedimentos de la plataforma Amazon hasta 300 Sullivan y Aller (1996)
Minería-contam'd, Columbia Británica 50-360 Azcue et al. (1994)
Embalse de relaves, Ontario, Canadá 300-100.000 McCreadie et al. (2000)

campo de petróleo y salmuera relacionada

Ellis piscina, Alberta, Canadá 230 White et al. (1963)

Searles lago salmuera, California hasta 243.000 White et al. (1963)

con fuentes industriales de As, la precipitación atmosférica contribuye pequeños también han encontrado concentraciones medias bajas de aproximadamente 0,25
cuerpos cuanto a aguas superficiales y subterráneas. metro gl 1 en los ríos de drenaje basamento en Noruega, el ser más bajo en las
cuencas en las rocas del Precámbrico. Waslenchuk (1979) encontraron
2.2.2. agua de rio concentraciones en las aguas de los ríos del sudeste de [Link]. en el rango
Las concentraciones basales de As en las aguas de los ríos también son 0,15-0,45 metro gl 1 ( Tabla 1).
bajos (del orden de 0,1-0,8 metro gl 1 pero puede ser de hasta ca. 2 metro gl 1; Tabla
1). Varían de acuerdo a la composición de la recarga superficial, la contribución Concentraciones relativamente altas de origen natural como puede ocurrir en
de la base de flujo y la litología lecho de roca. Las concentraciones en el extremo algunas áreas como resultado de entradas de fuentes geotérmicas o aguas
inferior de la gama se han encontrado en los ríos que desembocan bedrocks subterráneas de alto como. Las concentraciones de arsénico en las aguas de los
Como los pobres. Seyler y Martin (1991) encontraron concentraciones promedio ríos de las zonas geotérmicas se han reportado por lo general en torno al 10-70 metro
de río tan bajas como 0,13 metro gl 1 gl 1

(Por ejemplo, [Link]. occidental y Nueva Zelanda; McLaren y Kim, 1995;

en la región de Krka de Yugoslavia, donde el lecho de roca es As-pobre Robinson et al, 1995;. Nimick et al, 1998;. La tabla 1), aunque las
caliza karstic (Tabla 1). Lenvik et al. (1978) concentraciones más altas han sido
524 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

encontró. Nimick et al. (1998), por ejemplo encontrados como aguas residuales. Sin embargo, la concentración de As en el agua de la mayor parte de la
cuenca de captación estaba en el intervalo 0,75 a 3,8 metro gl 1
concentraciones de hasta 370 metro gl 1 en el agua del río Madison (Wyoming
y Montana) como resultado de aportes geotermales del sistema geotérmico y no significativamente di ff Erent de las concentraciones de referencia. Durum
de Yellowstone. Wilkie y Hering (1998) también encontraron et al. (1971) informaron de concentraciones en 727 muestras de aguas
concentraciones en el intervalo desde 85 hasta 153 metro gl 1 en Hot Creek superficiales de los Estados Unidos. Si bien el 79% de las muestras tuvo como
(afluente del río Owens, California). Algunos río riega un ff ected por la concentraciones por debajo de la (bastante alto) límite de detección de 10 metro gl
actividad geotérmica muestran variaciones estacionales distintas en la 1, la concentración más alta observada, 1100 metro gl 1, fue encontrado en Sugar
concentración medida. Las concentraciones en el río Madison se han Creek, Carolina del Sur, aguas abajo de un complejo industrial.
señalado a ser más alta durante condiciones de bajo fl ujo. Esto se ha
atribuido a un mayor aporte de agua geotérmica durante momentos de baja
flujo y dilución de ff runo resorte en los momentos de alta ow fl (Nimick et El arsénico también puede derivarse de los desechos de las minas y colas de la
al., 1998). En el sistema del río Waikato de Nueva Zelanda, Como máximos minería. Azcue y Nriagu (1995) encontraron concentraciones de línea de base en el
río Moira, Ontario de 0,7 metro gl 1
fueron encontrados en los meses de verano. Estos aumentos fueron ligados
a la reducción microbiana de temperatura controlada de As (V) a As (III) con aguas arriba de la influencia de las colas de trabajos mina de oro. Aguas
el consiguiente aumento de la movilidad de As (III) (McLaren y Kim, 1995). abajo, las concentraciones aumentaron a 23
metro gl 1. Azcue et al. (1994) encontraron concentraciones de hasta 556 metro gl 1 ( promedio
17,5 metro gl 1) en los arroyos adyacentes a los depósitos de relaves en la Columbia
Británica. Williams et al. (1996) y Smedley et al. (1996) observó alta Como
Aumento de las concentraciones también se presentan en algunas aguas de concentraciones (típicamente alrededor de 200-300 metro gl 1) en las aguas
río de las zonas áridas donde el agua de la superficie está dominada por la base superficiales una ff ected respectivamente por las actividades mineras Au-Sn- y.
de río flujo. Las aguas superficiales resultantes a menudo tienen un alto pH y la Aunque a menudo implica notables aumenta por encima de las concentraciones de
alcalinidad. Por ejemplo, en las aguas superficiales de la cuenca del río Loa del referencia, tales anomalías tienden a ser relativamente localizada alrededor de la
norte de Chile (área Antofagasta, Atacama desierto), Ceres Ca' et al. (1992) fuente de la contaminación, principalmente debido a la fuerte adsorción un nidad FFI
encontraron concentraciones de origen natural Como que oscila entre 190 y de minerales de óxido, especialmente óxido de Fe, porque como bajo oxidante,
21.800 metro gl 1. El alto Según concentraciones se correlacionaron bien con la neutral a condiciones ligeramente ácidas.
salinidad. Mientras entradas geotérmicas es probable que hayan tenido un
impacto importante en las composiciones químicas de las aguas del río en esta
área (Sección 5.5), la concentración por evaporación de la base de fl agua de río
dominado-ow es también probable que sea importante en las condiciones áridas. 2.2.3. agua de lago
Aumentó a medida que las concentraciones (hasta 114 metro gl 1) También se han Las concentraciones de As en aguas del lago son típicamente cerca o inferiores
reportado en las aguas del río desde el centro de Argentina, donde las a los encontrados en el agua del río. las concentraciones de línea de base se han
concentraciones regionales de las aguas subterráneas, como (y pH, alcalinidad) encontrado en <1 metro gl 1 en Canadá (Azcue y Nriagu, 1995;. Azcue et al, 1995). Al
son altas (Lerda y Prosperi, 1996). igual que con las aguas de los ríos, el aumento de las concentraciones se
encuentran en el lago las aguas A ff ected por el agua geotérmica y por la actividad
minera. Los rangos de 100-500 normalmente metro gl 1 se han reportado en algunas
áreas de minería y hasta 1000 metro gl 1 en áreas geotérmicas (Tabla 1). Las
Aunque la roca madre tiene inevitablemente una influencia en río-agua como concentraciones de arsénico en la minería-a ff aguas del lago reflejada no siempre
las concentraciones, las concentraciones en ríos con más valores de pH típico y son altas sin embargo, como la eliminación de la solución se puede lograr e ff caz
alcalinidad (c. PH 5-7, alcalinidad <100 mg l 1 como HCO 3) no muestran las por adsorción sobre óxidos de Fe en condiciones neutras a ligeramente ácido.
concentraciones extremadamente altas que se encuentran en las aguas Azcue et al. (1994), por ejemplo, que se encuentra en concentraciones en lago
subterráneas debido a la oxidación y la adsorción de As especies en el canadiense aguas de un ff ected por la minería e ffl uente similares no a aquellos
sedimentos de río, así como la dilución por recarga superficial y ff runo. Las una ff ected por la minería e ffl uente, en cada caso aproximadamente 0,3 metro gl 1.
concentraciones de arsénico en muestras de agua del río siete fromBangladesh
han sido reportados en el rango <0,5-2,7

metro gl 1 pero con una muestra que tiene una alta concentración de 29 metro gl 1 ( BGS y Alto como concentraciones también se encuentran en algunos alcalinas
DPhe, 2001). El valor más alto observado es significativamente por encima de las lagos-cuenca cerrada como resultado de la evaporación extrema y / o
concentraciones de referencia de la media mundo (Tabla 1), pero es mucho más baja que entradas geotérmicos. Mono Lago en el California, [Link]., por ejemplo,
algunos de los valores que se encuentran en las aguas subterráneas. tiene concentraciones de disuelto Como de 10.000-20.000 metro gl 1, con
valores de pH en el rango de 9,5-10 como resultado de las aportaciones de
Aumentos significativos en las concentraciones de As de aguas fluviales fuentes geotérmicas y la erosión de las rocas volcánicas seguido de
también pueden ocurrir como resultado de la contaminación de uents ffl evaporación (Maest et al., 1992).
industriales o de aguas residuales e. Andreae y Andreae (1989) encontraron
concentraciones de hasta 30 metro gl 1 en el agua del río Senne, Bélgica, que es También hay mucha evidencia para estratificación de cationes de las
un ff ected por entradas de fuentes urbanas e industriales, en particular concentraciones como en algunas aguas del lago como resultado de la variación de las
condiciones redox (Aggett y O'Brien, 1985). Azcue y
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 525

Nriagu (1995) encontró que las concentraciones aumentaron con la profundidad y, a veces sustancialmente menor. Sin embargo, los valores citados en la
(hasta 10 m) en las aguas del lago desde Ontario, probablemente debido a una literatura muestran una gama muy grande de
relación creciente de As (III) a As (V) con una profundidad y un influjo de < 0,5-5000 metro gl 1 ( es decir, cuatro órdenes de magnitud). Este rango se produce
porewaters sedimentos mineros contaminados en la interfase agua-sedimento. en condiciones naturales. Las altas concentraciones de como se encuentran en las
Las concentraciones fueron mayores en verano, cuando se observó la aguas subterráneas en una variedad de entornos. Estos incluyen tanto oxidante (en
proporción de As (III) a ser mayor. O empobrecido 2 los niveles de las aguas del condiciones de alto pH) y acuíferos reductoras y zonas un ff ected por geotérmica, la
lago de fondo, como resultado de la productividad biológica durante los meses minería y la actividad industrial. concentración por evaporación también puede
de verano son una causa probable de la más alta en concentraciones en las aumentar las concentraciones sustancialmente. La mayoría de alta como provincias
aguas del lago más profundas. de aguas subterráneas son el resultado de fenómenos naturales de medida. Los
casos de contaminación mininginduced Como son numerosas en la literatura, pero
tienden a ser localizados. Los casos de industrialmente inducida Como la
contaminación (incluyendo que a partir de la agricultura) pueden ser graves
2.2.4. El agua de mar y estuarios localmente (Tabla 1), pero ocurrencias son relativamente raros. ocurrencias de
Como promedio concentraciones en el agua de mar abierto generalmente muestran poca arsénico en el agua subterránea se discuten con más detalle en la sección 5.
variación y son típicamente alrededor de 1,5 metro gl 1

(Tabla 1). Las concentraciones en el agua de estuario son más variables, como
resultado de la variación de los aportes fluviales y la salinidad o redox gradientes
pero también son generalmente bajos, en general menos de 4 metro gl 1 en
condiciones naturales. Peterson y Carpenter (1983) encontraron concentraciones 2.2.6. drenaje de la mina
entre 1.2 a 2.5 En las condiciones extremadamente ácidas de algún drenaje ácido de
metro gl 1 en aguas de Saanich Inlet, Columbia Británica. Valores por debajo de 2 metro minas, que pueden tener valores de pH negativos (Nordstrom et al., 2000),
gl 1 fueron encontrados en Oslofjord, Noruega (Abdullah et al, 1995;. Tabla 1). Las se encuentran altas concentraciones de una amplia gama de solutos,
concentraciones son comúnmente más alta cuando los aportes fluviales son un ff incluyendo Fe y As. La más altos registrados Como concentración de
ected por uente ffl industrial o la minería e (por ejemplo Tamar, Schelde, Loire 850.000 metro gl 1 es de una SEEP ácido en la mina Richmond en Iron
estuarios; Tabla 1) o por el agua geotérmica. A diferencia de algunos otros Mountain, California (Nordstrom y Alpers, 1999). En una compilación de
elementos traza tales como B, la intrusión salina del agua de mar en un acuífero es algunos 180 muestras de drenaje de mina de los [Link]., Plumlee et al.
poco probable que conduzca a un aumento signi fi cativo de Como en el eja un ff (1999) informaron de concentraciones que van de los límites de detección
aguas subterráneas. (<1 metro gl 1 o más) a 340,000 metro gl 1, de nuevo los valores más altos de
ser de la mina de Richmond. Gelova (1977) también informó de una
acciones arseniato muchas características químicas con fosfato y, por tanto, concentración A partir de 400 000 metro gl 1 de los montes Urales. Disuelto
en las aguas marinas y de estuario óxicas, agotamientos en fosfato en las aguas Como en aguas de mina de ácido se elimina rápidamente como el Fe se
superficiales biológicamente productivas se reflejan por agotamiento en el oxida y se precipita y los Como barrido a través de la adsorción. En Iron
arseniato. Arseniato de los mínimos de concentración a menudo coincide con Mountain, una planta de neutralización e fi ciente elimina los metales Como
máximos fotosintética se evidencia por las altas concentraciones de clorofila un ( Cullen y para la eliminación segura.
y Reimer, 1989). Varios estudios han señalado las variaciones en el
comportamiento de Como durante la mezcla de estuario. Algunos han informado
de la conducta conservadora. En el no contaminado estuario Krka de
Yugoslavia, Seyler y Martin (1991) observaron un aumento lineal en total Al igual
que con el aumento de la salinidad que van desde 0,13 metro gl 1 en aguas dulces 2.2.7. porewaters sedimentos
a 1,8 metro gl 1 O Shore ff (es decir, el valor del agua de mar). Sin embargo, otros Algunas concentraciones altas de Como se han encontrado en porewaters
estudios han observado el comportamiento no conservadora (salidas de mezcla extraídos de sedimentos no consolidados y, a menudo formar fuertes
simple) en estuarios debido a procesos tales como di ff usion de porewaters de contrastes a las concentraciones observadas en las aguas superficiales
sedimentos, coprecipitación con óxidos de Fe o entradas antropogénicas (por suprayacentes (por ejemplo Belzile y Tessier, 1990). Widerlund y Ingri (1995)
ejemplo Andreae et al, 1983;. Andreae y Andreae, encontraron concentraciones en el intervalo desde 1,3 hasta 166 metro gl 1 en
porewaters del río Kalix estuario del norte de Suecia. Yan et al. (2000)
encontrado en concentraciones en el intervalo de 3,2 a 99

1989). La floculación fl de óxidos de Fe en la interfaz freshwatersaline es una metro gl 1 en porewaters de sedimentos de arcilla en Saskatchewan, Canadá
consecuencia importante de los aumentos en el pH y la salinidad. Esto puede (Tabla 1). Aumento de las concentraciones se han encontrado en porewaters un
dar lugar a importantes disminuciones en el Como reflujo a los océanos (Cullen ff ected por entradas geotérmicos. Aggett y Kriegman (1988) encontraron Como
y Reimer, 1989). concentraciones de hasta 6430 metro gl 1 en porewaters anóxicas de Nueva
Zelanda. incluso mayores concentraciones se encuentran en porewaters de los
2.2.5. El agua subterránea sedimentos de un ff ected por la contaminación minera (relaves, depósitos ricos
las concentraciones de fondo de As en las aguas subterráneas son en la mayoría de en minerales). McCreadie et al. (2000) reportaron Como concentraciones de
los países de menos de 10 metro gl 1 ( por ejemplo Edmunds et al, 1989 para el Reino Unido.; hasta 100.000 metro gl 1 en
Welch et al., 2000 para los [Link].)
526 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

porewaters extraídos de colas en Ontario (Tabla 1). En tales casos, alta especies para análisis de laboratorio más tarde. Alternativamente, la
intersticial Como concentraciones son más propensos a estar vinculado a los preservación con HCl y ácido ascórbico ha sido exitosa aunque esto puede
fuertes gradientes de redox que se producen por debajo de la interfase destruir ácido monomethylarsonic (MMAA) si está presente.
agua-sedimento, a menudo sobre escalas de profundidad de centímetros. El
entierro de la materia orgánica fresca y el derrame lento di ff de O 2 a través del En el agua de lluvia, los estados de oxidación de As presente variarán de
sedimento conduce a la reducción de las condiciones justo debajo de la acuerdo con la fuente. Esto es probable que sea dominante As (III) 2 O 3 cuando se
interfase agua-sedimento. Esto fomenta la reducción de As (V) y la desorción derivan de las fundiciones, la combustión de carbón y fuentes volcánicas, aunque
de los óxidos de Fe y Mn, así como la disolución reductiva de estos minerales. las especies orgánicas pueden derivarse por volatilización de los suelos, arsina (As
Hay mucha evidencia para el ciclismo de Como entre porewaters de (-III) H 3)
sedimentos poco profundas y aguas superficiales suprayacentes en respuesta puede derivar de LLS tierra fi y la reducción de suelos, tales como turba, y
a variaciones temporales en las condiciones redox. arseniato puede derivar de aerosoles marinos. Las formas reducidas serán
sometidos a la oxidación por O 2 en la atmósfera y reacciones con SO
atmosférica 2 o o 3
Sullivan y Aller (1996) llevaron a cabo un elegante estudio de los ciclos de es probable (Cullen y Reimer, 1989).
medida en los sedimentos superficiales de la plataforma costa o FF del En agua de mar óxico, el como es típicamente dominado por As (V), aunque
Amazonas situada lejos de los centros de población. Midieron intersticial algunos As (III) es invariablemente presentes y se vuelve de creciente
como y concentraciones de concentración Fe pro fi les así como de importancia en las aguas del fondo anóxicas. Ratios de As (V) / As (III) son
sedimentos como y Fe (II). Hubo frecuentemente un pico bien típicamente en el rango de 10-100 en agua de mar abierto (Andreae, 1979;
correlacionado-in disolvió As y Fe concentraciones de algunos 50- 150 cm Peterson y Carpenter, 1983;. Pettine et al, 1992). Arsénico (V) debería existir
debajo de la superficie, con concentraciones en el pico promedio de principalmente como HASO 42- y H 2 AsO 4- en el intervalo de pH del agua de mar
aproximadamente 135 metro gl 1 y alcanzando un máximo de 300 metro gl 1, mucho (pH alrededor de 8,2;. las figuras 1 y 2) y As (III) principalmente como las
mayor que a partir de los ambientes costeros marinos. El disuelto Como especies neutras H 3 AsO 3. Proporciones relativamente altas de H 3 AsO 3 se
relación molar / Fe variada, pero era típicamente de aproximadamente 1: 300. encuentran en la superficie aguas oceánicas (Cullen y Reimer, 1989;. cortador
Disuelto Como varió inversamente con fácilmente lixiviable (M HCl 6) Como et al, 2001). Estos coinciden con zonas de productividad primaria. Los
en el sedimento y el aumento directamente con fase sólida Fe (II). En estos aumentos en especies orgánicas Como también han sido registrados en estas
sedimentos, se creía que los óxidos de Fe a ser una fuente mucho más zonas, como resultado de las reacciones de metilación por el fitoplancton.
importante de As de óxidos de Mn.

Las proporciones relativas de Como especies son más variables en las

2.2.8. campo de petróleo y otras salmueras aguas de estuario debido a redox y la salinidad variable y entradas terrestres
están disponibles para Como en el aceite de campo y otras salmueras de datos (Howard et al, 1988;.. Abdullah et al,
limitados, pero algunos informes publicados sugieren que las concentraciones 1995). Sin embargo, todavía están dominados por As (V). Andreae y Andreae
pueden ser muy altos. White et al. (1963) reportaron una disuelto Como (1989) encontrado As (V) / As (III) proporciones que varían entre 5-50 en el
concentración de 230 metro gl 1 en una Na-HCO 3 las aguas subterráneas de un aceite estuario Schelde de Bélgica con las proporciones más bajas de zonas anóxicas
de 1000 m fi eld profunda bien desde Ellis piscina, Alberta, Canadá. También donde entradas de uente e ffl industrial tenido un impacto. El aumento de las
informaron de una concentración de 5800 metro gl 1 Como en una salmuera proporciones de As (III) también resultan de entradas de uente e ffl mina
dominado-Na-Cl de Tisaku¨ rt, Hungría. salmueras compuesto a partir de los (Klumpp y Peterson, 1979). Las variaciones estacionales en la concentración
intersticios de los depósitos de sal de Searles Lake, California, tiene como medida y la especiación se han observado en los estuarios (Riedel, 1993). En las
concentraciones de hasta 243 mg l 1 ( Na 119 gl 1; White et al., 1963; Tabla 1). aguas de estuario estacionalmente anóxicas, las variaciones en las proporciones
relativas de As (III) y As (V) pueden ser grandes. Peterson y Carpenter (1983)
encontraron un cruce distinto en las proporciones de las dos especies al
aumentar la profundidad en respuesta a la aparición de condiciones anóxicas en
2.3. Distribución de especies de arsénico en cuerpos de agua las aguas de estuario de Saanich Inlet de la Columbia Británica. Arsénico (III)
representa sólo el 5% (0,10 metro gl 1) de la disuelto Como arriba la parte delantera
Como muchos estudios de especiación en las aguas naturales se han redox pero 87% (1,58 metro gl 1) Por debajo de eso. En las aguas marinas y de
llevado a cabo. La mayoría intento de separar las especies inorgánicas en As estuario, formas orgánicas son generalmente menos abundante, pero a menudo
(III) y As (V), por lo general por separación cromatográfica o haciendo uso de la se detectan, sin embargo, (por ejemplo, Riedel, 1993;. Howard et al, 1999). Las
relativamente lenta reducción de As (V) por Na borohidruro. Algunos estudios concentraciones de estos dependerán de la abundancia y especies de la biota
también miden la orgánica Como especies. El muestreo y técnicas analíticas presentes y de la temperatura.
requeridas no son triviales y no todavía bien establecida (Edwards et al., 1998).
Tanto la oxidación del As (III) y la reducción de As (V) se puede producir
durante el almacenamiento (Hall et al., 1999). La separación de las especies
puede ser llevada a cabo en el campo para evitar el problema de la
conservación En las aguas de lagos y ríos, As (V) también es generalmente la especie
dominante (por ejemplo Seyler y Martin, 1990; Pettine
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 527

et al., 1992), aunque se han encontrado signi fi variaciones estacionales de As (III) / As T proporciones que varían entre 0,1-0,9, pero son típicamente alrededor de
consideración en la especiación así como la concentración absoluta. Las 0,5-0,6 (DPhe / BGS / MML, 1999; Smedley et al, 2001b.). Ratios en la reducción de las
concentraciones y proporciones relativas de As (V) y As (III) varían de acuerdo aguas subterráneas a partir de Mongolia Interior son típicamente 0,6-0,9 (Smedley et al.,
a los cambios en las fuentes de entrada, condiciones redox y la actividad 2001a). Las concentraciones de formas orgánicas son generalmente bajos o

biológica. La presencia de As (III) se puede mantener en las aguas óxicas por insignificante en las aguas subterráneas (por ejemplo, Chen et al., 1995).

reducción biológica de As (V), en particular durante los meses de verano.

proporciones relativas más altas de As (III) se han encontrado en río se
extiende cerca de las entradas de As (III) dominadas por la industrial e ffl uente 2.4. Impacto de la cinética redox sobre la especiación de arsénico

(Andreae y Andreae, 1989) y en aguas con un componente de agua

geotérmica. Las reacciones redox son importantes para controlar el comportamiento
de muchas especies mayores y menores en las aguas naturales, entre ellos
Las proporciones de As (III) y As (V) son particularmente variable en lagos el de Como. Sin embargo, en la práctica, el equilibrio redox a menudo se
ed estratificación donde gradientes redox puede ser grande y estacionalmente logra sólo lentamente y el potencial redox tiende a ser controlado por los
variable (Kuhn y Sigg, 1993). Al igual que con las aguas de estuarios, distintos elementos principales (O, C, N, S y Fe). elementos sensibles a redox
cambios en la especiación como se producen en el lago per fi les, como menores y oligoelementos tales como As responder a estos cambios en
resultado de los cambios redox. Por ejemplo, en la estratificación ed, lugar de controlarlos. La lenta velocidad de muchas reacciones redox
hipersalina y hyperalkaline Lago Mono (California, [Link].), hay un predominio heterogénea se apoya en los estudios de Wersin et al. (1991), que estima
de As (V) en la capa óxica superior y de As (III) en la capa de reductor (Maest que la disolución reductiva completa de óxidos de Fe (III) en un lago suizo
et al., 1992; Oremland et al., sedimentos anóxicos se necesitarían más de 1 ka. Equilibrium cálculos
termodinámicos predicen que As (V) concentraciones deben ser mayores
2000). rápida oxidación de As (III) se produce como resultado de la actividad que las concentraciones de As (III) en todo menos en condiciones
microbiana durante las primeras etapas de la rotación lago (Oremland et al., fuertemente reductoras, es decir, donde SO 4 reducción está ocurriendo.
2000). La oxidación medida que se produce antes de la oxidación de Fe (II). A Mientras que esto es de hecho a menudo resulta ser el caso, tal
diferencia de lago Mono, la especiación de As en los lagos no se sigue comportamiento teórico no se sigue necesariamente cuantitativamente en
necesariamente que espera que a partir de consideraciones termodinámicas. las aguas naturales, donde las parejas di ff Erent redox pueden señalar di ff
Estudios recientes han demostrado que arsenito predomina en el epilimnio Erent implícita potenciales redox (valores de Eh), reflejando desequilibrio
oxidado de algunos lagos fi ed estratigráficas mientras arseniato puede persistir termodinámico (Seyler y Martin, 1989; Eary y Schramke, 1990; Kuhn y Sigg,
en el hipolimnio anóxica (Kuhn y Sigg, 1993; Newman et al., 1998). Las 1993). En Oslofjord, Noruega, As (III) se encontró en condiciones oxidantes
proporciones de Como especies también pueden variar de acuerdo a la (Abdullah et al., 1995). También, en agua de mar oxigenada, el As (V) / As
disponibilidad de partículas Fe y óxidos de Mn (Pettine et al., 1992; Kuhn y Sigg, (III) proporciones debe ser del orden de 10 15 -10 26 ( Andreae, 1979), mientras
1993). que se han encontrado relaciones medidas de 0,1-250, en gran parte con el
apoyo de transformaciones biológicas (Johnson y Pilson, 1975; Cullen y
Las formas orgánicas de Como son generalmente de menor importancia en las aguas Reimer, 1989). La oxidación del As (III) por O disuelto 2, llamada oxigenación,
superficiales. En las aguas del lago desde Ontario, Azcue y Nriagu (1995) han encontrado es una reacción particularmente lenta. Por ejemplo, Johnson y Pilson (1975)
concentraciones de As (III) de 7-75 metro gl 1, dieron vidas medias para la oxigenación de As (III) en agua de mar que va
As (V) de 19-58 metro gl 1 y sólo 0,01-1,5 metro gl 1 de como orgánicos. No obstante, desde varios meses a un año.
las proporciones de formas orgánicas de Como se puede aumentar como resultado
de reacciones de metilación catalizada por la actividad microbiana (bacterias,
levaduras, algas). Las formas orgánicas dominantes encontrados son ácido
dimetilarsínico
(DMAA; (CH 3) 2 AsO (OH)) y mono
ácido metilarsónico (MMAA; CH 3 AsO (OH) 2), donde As está presente en ambos
casos en el estado de oxidación pentavalente. Las proporciones de estas dos Otros estudios han demostrado la estabilidad de As (V) / As (III) relaciones durante

especies se han observado para aumentar en verano como resultado de una periodos de días o semanas durante el muestreo de agua cuando no se tomó ninguna

mayor actividad microbiana (por ejemplo, Hasegawa, 1997). Las especies especial cuidado para evitar la oxidación, lo que sugiere de nuevo las tasas de oxidación

orgánicas también pueden ser más prevalente cerca de la interfase relativamente lento. Andreae (1979) encontraron relaciones estables en agua de mar
agua-sedimento (Hasegawa et al., 1999). durante un máximo de 10 días (4 DO). Cereza et al. (1979) encontrado a partir de
estudios experimentales que / As (III) relaciones fueron estables en soluciones anóxicas
En las aguas subterráneas, la proporción de As (III) a As (V) puede variar en durante hasta 3 semanas, pero se produjo en escalas de tiempo más largos el As (V)
gran medida como resultado de las variaciones en la abundancia de sólidos con que los cambios graduales.
actividad redox, especialmente C orgánico, la actividad de los microorganismos y
el alcance de la convección y di ff usion de O 2 de la atmósfera. Al reducir Cereza et al. (1979) sugirieron que la mide como (V) / As (III) ratios en las
fuertemente acuíferos (Fe (III) - y SO 4- la reducción de los acuíferos), As (III) aguas naturales, especialmente las aguas subterráneas, podrían usarse como
típicamente domina, como se espera de la secuencia de redox. La reducción de un indicador de la redox ambiente (Eh) condiciones que los cambios redox son
las aguas subterráneas Como-ricos de Bangladesh han su fi cientemente rápida a ocurrir en períodos de años. Yan et al. (2000) también
han
528 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

concluido que los As (V) / As (III) relación puede ser utilizado como un siendo rápidamente catalizada por bacterias con constantes de velocidad
indicador redox fiable para sistemas de aguas subterráneas. Sin embargo, oscilan entre 0.02 y 0,3 días 1 ( Oremland et al., 2000). Metilado Como
este optimismo puede ser infundada desde Welch et al. (1988) encontraron especies también se oxidan fácilmente química y biológicamente (Abdullah
que el Eh calcula a partir de los As (V) - As (III) par ni estaba de acuerdo et al., 1995).
con que desde el Fe (II) - Fe (III) y otros pares redox ni con el Eh medido. Se sabe menos sobre la tasa de reducción en fase sólida de As (V) a As
Las mediciones de Eh en aguas naturales usando electrodos de Pt son (III) pero ha habido algunos estudios con suelos y sedimentos. La evidencia
conocidos por ser problemática (Lindberg y Runnells, 1984). Por lo tanto, de los suelos es que bajo condiciones moderadamente reductores (Eh <100
queda por ver la fiabilidad de la pareja redox como un indicador redox. Es mV) inducidas por inundación, As (V) se reduce a As (III) en cuestión de
claramente importante que cuando se hacen tales comparaciones, las días o semanas y se adsorbió As (V) se libera como As (III ) (Masscheleyn
mediciones Eh se llevan a cabo sin perturbar el entorno redox naturales et al, 1991;.. Reynolds et al,
(Yan et al.,
1999). Masscheleyn et al. (1991) encontrado a partir de experimentos de
laboratorio que algunos de los Como se publicó antes de Fe, implicando desorción
2000). En los casos en que el acuífero es fuertemente estratificación ed fi, el agua reductora a partir de óxidos de Fe en lugar de la disolución reductora. Hasta el 10%
subterránea flujo inducido por bombeo durante el muestreo o el uso también puede del total Como en el suelo finalmente se convirtió en soluble. Smith y Ja e'ff (1998)
conducir a la mezcla de aguas con di ff potenciales muy Erent redox. Tal vez el modelado como reducción (V) en los sedimentos bentónicos como una reacción de
más que puede decirse en la actualidad es que la existencia de As (III) implica la primer orden con respecto al arseniato, con una tasa ciente Coe FFI de 125 una 1.
reducción de las condiciones de alguna parte del sistema.

Los estudios de laboratorio muestran que la cinética de la oxigenación de

As (III) son más lentos en el intervalo ligeramente ácido, alrededor de pH 5
(Eary y Schramke, 1990), que es la razón por muestras de agua son a 3. Fuentes de arsénico
menudo se acidificó a aproximadamente este pH para preservar su en la
especiación situ. Eary y Schramke (1990) también dieron una ecuación de 3.1. minerales
velocidad empírica para la reacción en el rango de pH 8-12,5. Esto se basó
en la concentración (actividad) de la H 2 AsO 3- especies en solución. Sugirieron 3.1.1. Los principales minerales de arsénico

que la vida media de As (III) en las aguas naturales es 1-3 a, aunque la tasa El arsénico se produce como un constituyente principal en más de 200
puede ser mayor debido a la presencia de 'especies desconocidas acuosas' o minerales, incluyendo elemental como, arseniuros, sulfuros, óxidos,
partículas de óxido, especialmente óxidos de Mn. Ciertamente, existe arseniatos y arsenitos. Una lista de algunas de las más comunes como los
considerable evidencia de que los óxidos de Mn pueden aumentar la tasa de minerales se da en la Tabla 2. La mayoría son minerales de mineral o de sus
la oxidación (III) con vidas medias ser reducido a tan poco como 10-20 min productos de alteración. Sin embargo, estos minerales son relativamente
en presencia de partículas de óxido de Mn-(Oscarson et al, 1981;. Scott y raras en el medio ambiente natural. Las mayores concentraciones de estos
Morgan, 1995). Esto se utiliza con ventaja en la eliminación de As (III) a partir minerales se producen en zonas mineralizadas y se encuentran en estrecha
de agua potable (Driehaus et al., 1995). La velocidad de oxidación es asociación con los metales de transición, así como Cd, Pb, Ag, Au, Sb, P, W
independiente de la concentración de O disuelto 2 y Mo. El más abundante Como mineral mineral es arsenopirita, FeAsS. En
general se cree que la arsenopirita, junto con la otra dominante Assulphide
minerales rejalgar y oropimente, solamente se forman bajo condiciones de
alta temperatura en la corteza terrestre. Sin embargo, arsenopirita authigenic
(Scott andMorgan, 1995), la tasa siendo controlado por la velocidad de una ha informado en los sedimentos por Rittle et al. (1995) y oropimente
reacción de superficie. Se sabe menos sobre el papel de los óxidos de Fe en la Recientemente se ha informado que se han formado por precipitación
alteración de la cinética de oxigenación. oxidación fotoquímica y la reducción microbiana (Newman et al., 1998). Aunque a menudo presente en los
pueden ser factores adicionales en las aguas superficiales. partículas que depósitos de mineral, arsenopirita es mucho menos abundante que Arsenian
contienen titanio pueden ayudar a la foto-oxidación (Foster et al., 1998). ( 'As-rico') pirita (Fe (S, As) 2) que es probablemente la fuente más importante
de Como en zonas de mineral (Nordström, 2000).
En el entorno natural, las tasas tanto de As (III) reacciones de reducción
As (V) de oxidación y son controlados por los microorganismos y pueden
ser órdenes de magnitud mayor que en condiciones abióticas. Por ejemplo,
las muestras de agua estériles se han observado a ser menos susceptible a
los cambios de especiación que las muestras no estériles (Cullen y Reimer, Donde arsenopirita está presente en los minerales de sulfuro asociados con
1989). Wilkie y Hering (1998) encontraron que As (III) en la entrada aguas Au depósitos de sedimentos-alojado, que tiende a ser el mineral-temprana
geotérmica para corrientes en SW [Link]. oxida rápidamente aguas abajo formado, derivado de soluciones hidrotermales y formado a temperaturas
(pseudo fi rstorder vida media calculada en tan poco como 0,3 h) y se típicamente de 100 C o más. Esto es seguido por la formación de más raro
atribuyeron la rápida tasa a la mediación bacteriana. La reducción de As (V) pirita nativa Como ya partir de entonces Arsenian. Realgar y oropimente
a As (III) en el mono lago era también forman generalmente más tarde todavía. Esta secuencia paragenética a
menudo se refleja por la zonificación dentro de sulfuro
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 529

Tabla 2
Como principales minerales que se encuentran en la naturaleza

Mineral Composición Ocurrencia

arsénico nativo Como vetas hidrotermales

niccolite NiAs depósitos de veta y norites
rejalgar Culo depósitos de veta, a menudo asociados con oropimente, arcillas y calizas, también los depósitos de aguas termales

oropimente Como 2 S 3 venas hidrotermales, manantiales de agua caliente, productos de sublimación volcánicas

cobaltita CoAsS depósitos de alta temperatura, rocas metamórficas

arsenopirita FeAsS El más abundante Como mineral, predominantemente en las venas minerales

tennantita (Cu, Fe) 12 Como 4 S 13 vetas hidrotermales

enargita Cu 3 Culo 4 vetas hidrotermales
arsenolite Como 2 O 3 mineral secundario formado por la oxidación de la arsenopirita, arsénico nativo y otra como minerales

Claudetite Como 2 O 3 mineral secundario formado por oxidación de rejalgar, arsenopirita y otra como minerales
scorodite FeAsO 4. 2H 2 O mineral secundario
annabergite (Ni, Co) 3 ( AsO 4) 2. 8H 2 O mineral secundario
Hoernesite mg 3 ( AsO 4) 2. 8H 2 O mineral secundario, los residuos de la fundición

Haematolite (Mn, Mg) 4 Al (ASO 4) ( OH) 8

conichalcite CaCu (ASO 4) ( OH) mineral secundario
pharmacosiderite Fe 3 ( AsO 4) 2 ( OH) 3. 5H 2 O producto de oxidación de la arsenopirita y otra como minerales

minerales, con núcleos de arsenopirita zonificación a pirita y drenaje ácido de minas, y la presencia de Como problemas en torno a las minas
rejalgar-oropimente llantas Arsenian. Óxidos y sulfatos se forman en las de carbón y áreas de quema intensiva carbón.
últimas etapas de mineralización de mineral (Arehart et al., 1993). Alto como concentraciones se encuentran también en muchos minerales
de óxido y óxidos metálicos hidratados, ya sea como parte de la estructura
mineral o como especies sorbidos. Las concentraciones en óxidos de Fe
3.1.2. minerales de la roca de formación también pueden alcanzar valores de porcentaje en peso (Tabla 3), en
Aunque no es un componente principal, Como también es a menudo particular donde forman como los productos de oxidación de los minerales
presente en concentraciones variables en otros minerales comunes que primarios de sulfuro de Fe, que tienen un suministro abundante de As.
forman rocas. Como la química de Como sigue de cerca la de S, las mayores Adsorción de arseniato de óxidos de Fe hidratados es particularmente fuerte y
concentraciones del elemento tienden a ocurrir en minerales de sulfuro, de las cargas sorbidos puede ser apreciable incluso a muy bajo como
cuales la pirita es el más abundante. Las concentraciones en pirita, calcopirita, concentraciones en solución (Goldberg, 1986; Manning y Goldberg, 1996;
galena y marcasita pueden ser muy variables, incluso dentro de un grano Hiemstra y van Riemsdijk, 1996). Adsorción a hidratados óxidos de Al y Mn
dado, pero en algunos casos superar el 10 en peso.% (Tabla 3). El arsénico también puede ser importante si estos óxidos están presentes en cantidad
está presente en la estructura cristalina de muchos minerales de sulfuro como (por ejemplo, Peterson y Carpenter, 1983; Brannon y Patrick,
un sustituto de S. Además de ser un componente importante de cuerpos de
mineral, la pirita se forma también en ambientes sedimentarios de baja
temperatura bajo condiciones de reducción. Tal pirita autigénica juega un 1987). El arsénico también puede ser absorbido a los bordes de las arcillas y
papel muy importante en los ciclos geoquímicos de hoy en día. Está presente en la superficie de la calcita (Goldberg y Glaubig,
en los sedimentos de muchos ríos, lagos y los océanos, así como de muchos 1988), un mineral común en muchos sedimentos. Sin embargo, estas cargas son
acuíferos. La pirita forma comúnmente preferentemente en zonas de reducción mucho más pequeños en función del peso de los óxidos de Fe. reacciones de
intensa tales como raíces de las plantas alrededor enterradas u otros núcleos adsorción son responsables de las concentraciones relativamente bajas (y no
de materia orgánica en descomposición. A veces es presente en una forma tóxicas) de Como se encuentra en la mayoría de las aguas naturales.
característica como pirita framboidal. Durante la formación de esta pirita, es
probable que algunos de los Como soluble también se incorporarán. La pirita Las concentraciones de arsénico en minerales de fosfato son variables, pero
no es estable en sistemas aeróbicos y se oxida a óxidos de Fe con la también pueden alcanzar valores altos, por ejemplo hasta 1000 mg kg 1 en apatita
liberación de grandes cantidades de SO 4, acidez y los oligoelementos (Tabla 3). Sin embargo, los minerales de fosfato son mucho menos abundante que
asociados, incluyendo como. La presencia de la pirita como un componente los minerales de óxido y por lo tanto hacen una correspondientemente pequeña
menor en sulfuro de carbones ricos en última instancia es responsable de la contribución a la concentración medida en la mayoría de los sedimentos. El arsénico
producción de 'lluvia ácida' y también puede sustituir para el Si 4+, Alabama 3+, Fe 3+ y Ti 4+ en muchas estructuras
minerales y por lo tanto presente en muchos otros minerales que forman rocas,
aunque en concentraciones mucho más bajas. La mayoría de los minerales de
silicato comunes contienen
530 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

Tabla 3
Las concentraciones típicas Como en minerales comunes que forman rocas

Mineral Como intervalo de concentración (mg kg 1) referencias

Los minerales sulfurados:

Pirita 100-77,000 Baur y Onishi (1969); Arehart et al. (1993); Flota y Mumin
(1997)
pirrotita 5-100 Boyle y Jonasson (1973);
marcasita 20-126,000 Dudas (1984); Flota y Mumin (1997)
Galena 5-10.000 Baur y Onishi (1969)
esfalerita 5-17,000 Baur y Onishi (1969)
calcopirita 10-5000 Baur y Onishi (1969)

minerales de óxido

Hematites hasta 160 Baur y Onishi (1969)

óxido de Fe (undi ff erentiated) hasta 2000 Boyle y Jonasson (1973)
Fe oxihidróxido (III) hasta 76.000 Pichler et al. (1999)
Magnetita 2,7-41 Baur y Onishi (1969)
ilmenita <1 Baur y Onishi (1969)

minerales de silicato

Cuarzo 0.4-1.3 Baur y Onishi (1969)

Feldespato < 0,1-2,1 Baur y Onishi (1969)
Biotita 1.4 Baur y Onishi (1969)
Anfíbol 1.1 a 2.3 Baur y Onishi (1969)
olivino 0,08-0,17 Baur y Onishi (1969)
piroxeno 0,05-0,8 Baur y Onishi (1969)

minerales de carbonato
calcita 1-8 Boyle y Jonasson (1973)
Dolomita <3 Boyle y Jonasson (1973)
Siderita <3 Boyle y Jonasson (1973)

minerales de sulfato
El yeso / anhidrita < 1-6 Boyle y Jonasson (1973)
Baritina < 1-12 Boyle y Jonasson (1973)
jarosita 34-1000 Boyle y Jonasson (1973)

otros minerales
Apatito < 1-1000 Baur y Onishi (1969), Boyle y
Jonasson (1973)
Hálito < 3-30 Stewart (1963)
Fluorita <2 Boyle y Jonasson (1973)

alrededor de 1 mg kg 1 o menos. minerales de carbonato por lo general contienen menos de-alta como las aguas (Nicolli et al, 1989;.. Smedley et al,
de 10 mg kg 1 Como (Tabla 3). 2002). Esto puede relacionarse con la naturaleza reactiva de material volcánico
ácida reciente, especialmente fi ceniza de grano fino y su tendencia a dar lugar
3.2. Rocas, sedimentos y suelos a Na-ricas aguas subterráneas de alto pH (sección 5).

3.2.1. Rocas ígneas

Las concentraciones de arsénico en las rocas ígneas son generalmente 3.2.2. Rocas metamórficas
bajos. Ure y Berrow (1982) citaron un valor medio de Las concentraciones de arsénico en rocas metamórficas tienden a reflejar las
1,5 mg kg 1 para todos los tipos de rocas ígneas (mediocre). Promedios de tipos concentraciones en sus precursores ígneas y sedimentarias. La mayoría
Erent di ff se distinguen por el contenido de sílice (Tabla 4) son ligeramente contienen alrededor de 5 mg kg 1 o menos. rocas pelítico (pizarras, filitas) por lo
superiores a este valor, pero en general menos de 5 mg kg 1. vidrios volcánicos general tienen las concentraciones más altas con un promedio de ca. 18 mg kg 1 ( Tabla
son sólo ligeramente superior con un promedio de alrededor de 5,9 mg kg 1 4).

(Tabla 4). En general, hay relativamente poca rencia di ff entre los tipos de 3.2.3. Rocas sedimentarias
roca ígnea Erent di ff. A pesar de no tener concentraciones excepcionales de La concentración de As en rocas sedimentarias está típicamente en el
Como, rocas volcánicas, especialmente cenizas, están a menudo implicados intervalo de 5-10 mg kg 1 ( Webster, 1999), es decir, ligeramente por encima de la
en la generación abundancia terrestre media. Promedio
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 531

Tabla 4
Como típica concentraciones en las rocas, sedimentos, suelos y otros depósitos ciales sur fi

Rock / tipo de sedimento Como promedio la concentración y / o Ninguno de los Referencia

rango (mg kg 1) análisis

Rocas ígneas
rocas ultrabásicas (peridotita, dunite, kimberlita 1,5 (0,03 a 15,8) 40
etc)
rocas básicas (basalto) 2,3 (0,18 a 113) 78
rocas básicas (gabro, dolerita) 1,5 (0,06-28) 112 Onishi y Sandell (1955);
Intermedio (andesita, traquita, latita) 2,7 (0,5-5,8) 30 Baur y Onishi (1969);
Intermedio (diorita, granodiorita, sienita) 1,0 (0,09 a 13,4) 39 Boyle y Jonasson (1973);
rocas ácidas (riolita) 4.3 (3.2 a 5.4) 2 Ure y Berrow (1982);
rocas ácidas (granito, aplita) 1,3 (0,2-15) 116 Riedel y Eikmann (1986)
rocas ácidas (pitchstone) 1,7 (0,5-3,3)
vidrios volcánicos 5.9 (02.02 a 12.02) 12

Rocas metamórficas
Cuarcita 5.5 (2.2 a 7.6) 4
hornfels 5,5 (0,7-11) 2
Filita / pizarra 18 (0,5 a 143) 75 Boyle y Jonasson (1973)
Esquistos / gneis 1,1 (<0,1 a 18,5) dieciséis

Anfibolita y piedra verde 6,3 (0.4-45) 45

Rocas sedimentarias
esquisto Marino / lutolita 3-15 (hasta 490)
Shale (Mid-Atlantic Ridge) 174 (48-361)
esquisto no marinos / mudstone 3,0-12
Arenisca 4,1 (0.6-120) 15 Onishi y Sandell (1955);
Piedra caliza / dolomita 2,6 (0,1-20,1) 40 Baur y Onishi (1969);
fosforita 21 (0,4 a 188) 205 Boyle y Jonasson (1973);
formaciones de hierro y rica en Fe sedimentos 1-2900 45 Cronan (1972); Riedel y
Evaporitas (yeso / anhidrita) 3,5 (0,1-10) 5 Eikmann (1986); Welch et al.
carbones 0.3-35,000 (1988); Belkin et al. (2000)
esquistos bituminosos (Kupferschiefer, 100-900
Alemania)

sedimentos no consolidados
Varios 3 (0,6 a 50) Azcue y Nriagu (1995)
arena aluvial (Bangladesh) 2,9 (1.0-6.2) 13 BGS y DPhe (2001)
Aluvial barro / arcilla (Bangladesh) 6,5 (2,7-14,7) 23 BGS y DPhe (2001)
sedimentos del lecho del río (Bangladesh) 1.2 a 5.9 Datta y Subramanian (1997)
Sedimentos de los lagos, Lago Superior 2,0 (0,5-8,0) Allan y Ball (1990)
Sedimentos de los lagos, British Colombia 5,5 (0,9-44) 119 Cook et al. (1995)
Glacial, British Colombia 9,2 (1,9 a 170) Cook et al. (1995)
Mundo sedimentos fluviales promedio 5 Martin y pizca de campo (1983)
Arroyo y lago limo (Canadá) 6 (<1-72) 310 Boyle y Jonasson (1973)
sedimentos de loess, Argentina 5,4-18 Arribe' re et al. (1997);
Smedley et al. (2002)
sedimentos del margen continental 02.03 a 08.02 Legeleux et al. (1994)
(arcillosa, algunos anóxica)

suelos

Varios 7,2 (0,1 a 55) 327 Boyle y Jonasson (1973)

Turba del pantano y suelos 13 (2-36) 14 Ure y Berrow (1982)
suelos sulfatados ácidos (Vietnam) 6-41 25 Gustafsson y de estaño (1994)
suelos sulfatados ácidos (Canadá) 1,5-45 18 Dudas (1984); Dudas et al. (1988)
Los suelos cerca de los depósitos de sulfuros 126 (2-8000) 193 Boyle y Jonasson (1973)

Contaminada sur fi ciales depósitos

Minería contaminado con sedimento del lago, British 342 (80-1104) Azcue et al. (1994, 1995)
Colombia

( Continúa en la siguiente página)

532 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568

Tabla 4 ( continuado)

Rock / tipo de sedimento Como promedio la concentración y / o Ninguno de los Referencia

rango (mg kg 1) análisis

sedimentos contaminados balsa minera, Montana 100-800 Moore et al. (1988)

residuos de la mina, British Colombia 903 (396-2000) Azcue et al. (1995)
Los suelos y los suelos contaminados de colas-, Reino Unido 120-52,600 86 Kavanagh et al. (1997)
Relaves suelo contaminado, Montana hasta 1100 Nagorski y Moore (1999)
Industrialmente contaminadas sedimentos intermareales, [Link]. ,38-1.260 Davis et al. (1997)
Suelos por debajo de fábrica de productos químicos, [Link]. 1,3-4770 Hale et al. (1997)

lodos de depuradora 9,8 (2,4-39,6) Zhu y Tabatabai (1995)

sedimentos se enriquecen en medida relativa a las rocas ígneas. Arenas y también son relativamente enriquecido en As, con valores de hasta ca. 400 mg kg 1 habiendo
areniscas tienden a tener las concentraciones más bajas, lo que refleja la sido informadas.
baja medida que las concentraciones de los minerales dominantes: cuarzo y
feldespato. arenisca media, como concentraciones son alrededor de 4 mg 3.2.4. sedimentos no consolidados
kg 1 ( Tabla 4), aunque Ure y Berrow (1982) dio un valor medio más bajo de 1 Las concentraciones de As en sedimentos no consolidados no son
mg kg 1. notablemente di ff Erent de las de sus equivalentes endurecidos. Los lodos y
arcillas normalmente tienen concentraciones más altas que las arenas y
depósitos arcillosas tienen una gama más amplia y más alto promedio Como carbonatos. Los valores son típicamente 3-10 mg kg 1, dependiendo de la textura y
las concentraciones que areniscas, con un promedio típico de alrededor de 13 mineralogía (Tabla 4). Las concentraciones elevadas tienden a reflejar las
mg kg 1 ( Tabla 4; Ure y Berrow, 1982). Los valores más altos reflejan la mayor cantidades de pirita o los óxidos de Fe presente. Los aumentos también son
proporción de minerales de sulfuro, óxidos, materia orgánica y arcillas. esquistos comunes en las zonas mineralizadas. depósitos de placer en las corrientes pueden
negros tienen medida que las concentraciones en el extremo superior de la tener concentraciones muy elevadas como consecuencia de la abundancia de
gama, principalmente debido a su contenido de pirita mejorada. Los datos dados minerales de sulfuro. La media, como concentraciones para sedimentos de
en la Tabla 4 sugieren que los depósitos arcillosos marinos tienen corriente en Inglaterra y Gales están en el intervalo de 5-8 mg kg 1 ( AGRG, 1978).
concentraciones más altas que los depósitos no marinos. Esto también puede concentraciones similares también se han encontrado en los sedimentos de río
ser un reflejo de las distribuciones de tamaño de grano, con la posibilidad de una donde las concentraciones de las aguas subterráneas, como son altas: Datta y
mayor proporción de material de multa en O ff shore sedimentos pelágicos, así Subramanian (1997) encontraron concentraciones en los sedimentos del río
como erences sistemáticas di ff en el contenido de azufre y pirita. pizarras Ganges un promedio de 2.0 mg kg 1 ( distancia
marinas tienden a contener mayores concentraciones de S. procedencia de
sedimentos es también un factor probable. Particularmente alta Como se han
determinado las concentraciones de esquistos de configuración en medio del 1,2-2,6 mg kg 1), desde el río Brahmaputra promedio de 2.8 mg kg 1 ( variar
océano (mediados de Mesoatlántica promedio de 174 mg kg 1; Tabla 4). 1.4-5.9 mg kg 1) y desde el río Meghna un promedio de 3,5 mg kg 1 ( variar
1.3-5.6 mg kg 1).

Cook et al. (1995) encontraron concentraciones en los sedimentos del lago que
Las concentraciones en los carbones bituminosos y depósitos son oscilan entre 0,9 y 44 mg kg 1 ( la mediana de 5,5 mg kg 1) pero observaron que las
variables, pero a menudo alta. Las muestras de orgánica rica en esquisto concentraciones más altas estuvieron presentes hasta unos pocos kilómetros cuesta
(Kupferschiefer) de Alemania tienen Como concentraciones de 100-900 mg kg 1 abajo de las zonas mineralizadas. La concentración de línea de base superior para
( Riedel y Eikmann, 1986; Tabla 4). Algunas muestras de carbón se han estos sedimentos es probable que sea alrededor de 13 mg kg 1 ( percentil 90).
encontrado con concentraciones extremadamente altas hasta 35.000 mg kg 1 También encontraron concentraciones en glacial hasta de

(Belkin et al., 2000), aunque en general bajas concentraciones de 2.5-17 mg kg 1 1.9-170 mg kg 1 ( la mediana de 9,2 mg kg 1; Tabla 4) y tomó nota de las
fueron reportados por Palmer y Klizas (1997). Las rocas carbonatadas tienen concentraciones más altas hacia abajo con hielo de áreas mineralizadas (línea de
típicamente bajas concentraciones, reflejando las bajas concentraciones de los base superior, el percentil 90 o, 22 mg kg 1). Relativa como se han observado
minerales constituyentes (aproximadamente 3 mg kg 1; Tabla 4). enriquecimientos en la reducción de sedimentos en los depósitos tanto cercanas a
la costa y continentalshelf (Peterson y Carpenter, 1986;. Legeleux et al, 1994).
Algunos de la más alta observada medida que las concentraciones se Legeleux et al. (1994) observaron concentraciones crecientes con la profundidad
encuentran en ironstones y rocas Fe-ricos. James (1966) cotejada datos (hasta 30 cm) en los sedimentos de la plataforma continental como resultado de la
para ironstones de diversas partes del mundo y se informaron como generación de condiciones cada vez más reductores. Las concentraciones
concentraciones de hasta 800 mg kg 1 en un oolita chamosite-limonita de la variaron entre los sitios, pero en general aumentaron con la profundidad en el
antigua URSS. Boyle y Jonasson (1973) dieron concentraciones de rocas intervalo
Fe-ricos hasta 2900 mg kg 1 ( Tabla 4). fosforita
2.3-8.2 mg kg 1 ( Tabla 4).
 PL Smedley, DG Kinniburgh / Geoquímica Aplicada 17 (2002) 517-568 533

3.2.5. suelos el tipo mineral (Krause y Ettel, 1989). Existe cierta confusión en el análisis
Las concentraciones basales de As en suelos son generalmente del de estas relaciones de solubilidad entre disolución congruentes, disolución
orden de 5-10 mg kg 1. Boyle y Jonasson (1973) citan una concentración incongruente y las reacciones de sorción / desorción. arsenolite Secundaria
media de la línea de base en los suelos mundiales de kg 7,2 mg 1 ( Tabla 4) y (Como 2 O 3) también es relativamente soluble. El arsénico unido a óxidos de
Shacklette et al. (1974) cita a un promedio de 7,4 mg kg 1 ( 901 muestras) Fe es relativamente inmóvil, en particular bajo condiciones oxidantes.
para suelos americanos. Ure y Berrow (1982) dieron un valor promedio
mayor de 11,3 mg kg 1. Las turbas y suelos de pantano pueden tener
concentraciones más altas (promedio 13 mg kg 1;
3.3. La atmósfera
Tabla 4), principalmente debido a la mayor prevalencia de fases minerales de
sulfuro en las condiciones reducidas. suelos sulfatados ácidos que se generan Las concentraciones de As en la atmósfera son por lo general bajo, pero
por la oxidación de la pirita en terrenos de sulfuros ricos tales como pizarras como se señaló anteriormente, se incrementan en las entradas de fundición y
pirıticos, venas minerales y manglares deshidratados también pueden ser otras operaciones industriales, la combustión combustible fósil y la actividad
relativamente enriquecidos en As. Dudas (1984) encuentran como volcánica. Concentraciones que asciende a alrededor de 10 5 -10 3 metro GM 3 se
concentraciones de hasta 45 mg kg 1 en los horizontes B de suelos sulfatados han registrado en zonas no contaminadas, aumentando a 0,003-0,18
ácidos derivadas de la erosión de las pizarras de pirita rica en Canadá. Las
concentraciones en el suprayacente lixiviados (E eluviales,) horizontes fueron metro GM 3 en zonas urbanas y mayor que 1 metro GM 3 cerca de las plantas
bajos (1.5-8.0 mg kg 1) como resultado de la volatilización o lixiviación de Como industriales (OMS, 2001). Gran parte de los Como atmosférica es de partículas.
para disminuir los niveles. Gustafsson y de estaño (1994) han encontrado Totales como velocidades de deposición se han calculado en el rango <1-1000 metro
GM 2 un 1
concentraciones elevadas de manera similar (hasta 41 mg kg 1) en suelos
sulfatados ácidos de la delta Mekong de Vietnam. dependiendo de las proporciones relativas de deposición húmeda y seca y la
proximidad a la contaminación de fuentes (Schroeder et al., 1987). Los valores
en el rango de 38 a 266 metro GM 2 un 1 ( 29-55% deposición seca) se estima para
Aunque la fuente dominante de Como en suelos es geológica, y por lo mediados de la costa atlántica (Scudlark y la Iglesia, 1988). Airborne Como se
tanto depende en cierta medida de la concentración en el material de la transfiere a los cuerpos de agua por deposición húmeda o seca y por lo tanto
roca madre, entradas adicionales pueden derivar localmente a partir de puede aumentar la concentración acuosa ligeramente. Sin embargo, hay poca
fuentes industriales tales como productos de combustión de fundición y evidencia que sugiera que la medida atmosférica representa una amenaza real
combustibles fósiles y fuentes agrícolas tales como pesticidas y fertilizantes para la salud fuentes de agua potable. Atmosférica como el resultado de la
de fosfato. Ure y Berrow (1982) citaron concentraciones en el intervalo combustión del carbón ha sido invocada como causa principal de cáncer de
366-732 mg kg 1 en suelos de huerta, como resultado de la aplicación de pulmón en partes de China (provincia de Guizhou), pero la amenaza es de la
pesticidas arsenicales histórica a los cultivos frutales. inhalación directa del humo fuego de carbón nacional y, especialmente, por el
consumo de alimentos secos sobre resolución de carbón fi domésticos, en lugar
de agua potable un ff ected por aportes atmosféricos (Finkelman et al., 1999).

3.2.6. Contaminada sur fi ciales depósitos

Las concentraciones de arsénico muy por encima de los valores basales se
han encontrado en los sedimentos y suelos contaminados por los productos de
la actividad minera, incluyendo residuos de la mina y uente e ffl. Las
concentraciones en colas pilas y suelos de colas contaminados pueden llegar 4. interacciones de agua mineral
hasta varios miles de mg kg 1 ( Tabla 4). Las altas concentraciones re fl ect no
sólo el aumento de la abundancia de minerales de sulfuro primarios como rica, 4.1. Controles sobre la movilización de arsénico

sino también arseniatos Fe secundarios y óxidos de Fe forman como productos

de reacción de los minerales de mineral de originales. Los minerales de sulfuro Como con la mayoría de los metales traza, la concentración de As en aguas
primarios son susceptibles a la oxidación en la pila de colas y los minerales naturales es, probablemente, normalmente controlado por alguna forma de
secundarios tienen diferentes solubilidad en oxidar las condiciones en las interacción-solución sólida. Esto es más claramente el caso de las soluciones del
aguas subterráneas y las aguas superficiales. Scorodite (FeAsO 4. 2H 2 O) es un suelo, aguas intersticiales y las aguas subterráneas, donde la relación sólido /
producto de oxidación de sulfuro común y su solubilidad se considera para solución es grande pero también es a menudo cierto en masas abiertas de agua
controlar en concentraciones en tales entornos de sulfuro oxidantes. Escorodita (océanos, lagos y embalses), donde la concentración de partículas sólidas es
es metaestable bajo la mayoría de condiciones de agua subterránea y tiende a pequeña, pero aún signi fi cativa. En estos cuerpos abiertos, las partículas pueden
disolverse incongruente, formando los óxidos de Fe y liberando Como en la ser de origen mineral y biológica. Es probable que en la mayoría de los suelos y
solución (Robins, 1987; Krause y Ettel, 1989). En la práctica, una amplia gama acuíferos, mineral-como las interacciones son probables a dominar sobre las
de Fe-como las relaciones de solubilidad mineral se encuentran que en parte interacciones de materia orgánica-AS, aunque la materia orgánica puede
se refieren a interactuar en cierta medida a través de sus reacciones con las superficies de los
minerales. Conocer los tipos de interacción implicado es
534 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

importante porque esto va a gobernar la respuesta de la medida a los cambios en componentes minerales, óxidos de Fe son probablemente los adsorbentes más
la química del agua. También determinará el enfoque de modelado requerido para importantes en los acuíferos de arena debido a su mayor abundancia y la
hacer predicciones acerca de posibles cambios en el futuro y para la comprensión fuerte unión a un infinito FFI. Sin embargo, Al óxidos también se puede esperar
de los cambios pasados ​en las concentraciones de As. que desempeñar un papel significativo cuando está presente en cantidad
(Hingston et al, 1971;. Manning y Goldberg, 1997b). La experiencia de
La importancia de óxidos en el control de la concentración de As en tratamiento del agua sugiere que por debajo de pH 7,5, Al hidróxidos son tan e
aguas naturales se ha apreciado durante mucho tiempo (Livesey y Huang, ff reflexivo como hidróxidos de Fe (sobre una base molar) para la adsorción de
1981;. Matiso ff et al, As (V) pero que las sales de Fe son más ciente e fi a pH más alto y para la
1982) y se ha producido una amplia gama de estudios para medir las adsorción de As (III) (Edwards , 1994).
isotermas de adsorción en minerales de óxido natural y sintético y para
establecer los procesos de sorción a la escala molecular (Tabla 5). Aun así,
las incertidumbres importantes todavía permanecen en relación con las Las interacciones de Al igual que con los óxidos de Fe se han estudiado
interacciones de As (III) y As (V) en concentraciones ambientales y en la con bastante detalle en el laboratorio y, por tanto, proporcionar la mejor
presencia de otros iones que interactúan. Con frecuencia, el elemento que comprensión de la conducta probable de interacciones Como-minerales en
se correlaciona mejor con Como en los sedimentos es Fe. Esta es también los acuíferos. Sin embargo, la mayoría de estos estudios de laboratorio, en
la base para el uso de sales de Fe (así como sales de Al y Mn) en el particular los estudios anteriores, se han llevado a cabo en más bien alta
tratamiento de agua para la eliminación de Como y otros elementos (por Como concentraciones (Hingston et al., 1971) y hay una escasez de datos
ejemplo, Edwards, de adsorción fiables a la baja metro gl 1 nivel de relevancia a las aguas
naturales. Además, existe incertidumbre sobre el grado en que los óxidos de
1994). El contenido A partir de lodos residuales de tratamiento de agua Fe más comúnmente estudiados en el laboratorio re fl ejar los óxidos de Fe
puede estar en el intervalo 1000-10.000 mg kg 1 que se encuentran en el campo. Los datos de campo para As (V) de
(Forstner y Haase, 1998;. Driehaus et al, 1998). Las arcillas también pueden adsorción a óxidos naturales 'diagenéticas' Fe (capturado en un lago con
adsorber As (III) y As (V) (Manning y Goldberg, 1997b), pero su papel en los instalado verticalmente-fl Te en hojas) en paralelo de cerca los datos de
sedimentos en términos de Como unión no está claro en la actualidad. laboratorio de Pierce y Moore (1982), que se incluyó en el Dzombak
andMorel (1990) de base de datos (De Vitre et al., 1991). Sin embargo, era
Es di fi culto para estudiar las interacciones de agua mineral directamente en considerablemente mayor que el calculado utilizando Hingston et al. (1971)
los acuíferos. La mayoría de los estudios, incluyendo aquellos con un cojinete datos de As (V) de adsorción en goetita, destacando la alta un nidad FFI
onas en las aguas subterráneas, se han llevado a cabo ya sea en los suelos o en para As de óxidos amorfos '' Fe formados recién. Paige et al. (1997)
el lago o los sedimentos oceánicos y por lo general desde profundidades midieron las relaciones de As / Fe durante la disolución de ácido de un
bastante superficiales. Hay mucho que aprender de los estudios de suelos y ferrihidrita sintético que contiene sorbida As (V) y concluyó que la disolución
sedimentos ya que se espera que los mismos principios generales a aplicar. Una fue incongruente (es decir, Fe y As no fueron liberados en la misma
de las áreas más importantes donde puede ocurrir la fertilización cruzada de proporción que se encuentra en el mineral a granel) y que el inicial, como se
ideas es en la comprensión del comportamiento de los óxidos de Fe en la presenta fue probablemente absorbidos en la superficie de las partículas
reducción de los suelos y sedimentos y la influencia de esta sobre la liberación de muy pequeñas ferrihidrita. Lo mismo es probable que suceda durante la
Al igual que en. Matiso ff et al. (1982) relacionados con la disolución reductiva de disolución reductora. El Como adsorbido también se ralentizó la disolución
óxidos de Fe a la posible liberación de Como en el agua subterránea froman de ácido de la ferrihidrita.
acuífero aluvial en NE Ohio. Korte (1991) y Korte y Fernando (1991) también
especularon que la desorción de A partir de óxidos de Fe podría ocurrir en la
reducción,

4.2. asociaciones de arsénico en los sedimentos 4.3. Reduced sediments and the role of iron oxides

Los principales minerales como la unión (tanto como arseniato y A well-known sequence of reduction reactions occurs when lakes, fjords,
arsenito) en sedimentos son los óxidos metálicos, particularmente aquellos soils, sediments and aquifers become anaerobic (Berner, 1981; Stumm and
de Fe, Al y Mn (De Vitre et al, 1991;. Sullivan y Aller, 1996). Alrededor del Morgan, 1995; Langmuir, 1997). The processes causing changes in Fe
50% de la Fe en sedimentos de agua dulce es en forma de óxidos de Fe y redox chemistry are particularly important since they can directly affect the
aproximadamente 20% del Fe es 'reactiva' Fe. Arcillas también adsorber mobility of As. One of the principal causes of high As concentrations in
debido al carácter de óxido-como de sus bordes. El grado de As (V) de subsurface waters is the reductive dissolution of hydrous Fe oxides and/or
sorción a, y coprecipitación en, minerales de carbonato es desconocida, the release of adsorbed or combined As. This sequence begins with the
pero si se comporta como fosfato, es probable estar fuertemente retenido consumption of O 2 and an increase in dissolved CO 2 from the decomposition
por estos minerales y esto puede limitar en concentraciones en aguas of organic matter. Next, NO 3- decreases by reduction to
subterráneas de los acuíferos de piedra caliza (Millero et al ., 2001). De
estos
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 535

Table 5
Studies of As adsorption by metal oxides

Mineral Comment Reference

Aluminium oxides As(V) and As(III) adsorption on activated alumina: pH dependence, kinetics, column Ghosh and Yuan (1987)
breakthrough. Regeneration by desorbing with NaOH. Modelling with pH-dependent Langmuir
isotherm (for As) and surface complexation model (for protons)

‘Amorphous’ As(V) on precipitated Al(OH) 3 ( pH 3–10). ‘Adsorption’ exceeded 15 mol kg 1 at pH 5. Fitted data Anderson et al. (1976)
aluminium hydroxide to pH dependent Langmuir isotherm

HFO Kinetics and pH dependence of As(V) and As(III) adsorption on HFO (202 m 2 g 1). Found very high Raven et al. (1998)
As(V) and As(III) loadings (up to 4–5 mol As kg 1) at the highest concentrations. pH adsorption
envelopes at various As T loadings

HFO Adsorption isotherms for arsenite and arsenate over free concentration range from 10 7 to 10 3 M Pierce and Moore (1982)
(pH 4–10). Fitted to Langmuir isotherm at low concentrations and linear isotherm at higher
concentrations. Dzombak and Morel (1990) fitted this data to their diffuse double layer model

HFO Sorption of As(V) and As(III) on HFO at As concentrations of environmental significance (low Wilkie and Hering (1996)
micromolar range) and pH 4–9. Compared results with Dzombak and Morel (1990) model
predictions— generally reasonable agreement. SO 4 decreased adsorption of As(V) and As(III),
especially at low pH, while Ca increased As(V) adsorption at high pH. 1 mM bicarbonate did not
affect either As(V) or As(III) adsorption greatly

HFO A wide angle X-ray scattering (and EXAFS) study of two-line ferrihydrite coprecipitated with varying Waychunas et al. (1996)
amounts of As(V) suggested that the As reduced crystallite size because of the formation of
strongly bound inner sphere complex between As(V) and edge sharing Fe(O,OH) 6

octahedra. Saturation at As/Fe mol ratio of 0.68

HFO As(III) and As(V) adsorption and OH release/uptake on synthetic two-line ferrihydrite. As(V) at pH 9.2 Jain et al. (1999)
released up to 1 mol OH- per mol As sorbed whereas As(III) released <0.25 mol As per mol Fe. At pH
4.6, OH release was much less for As(V) adsorption and under these conditions there was a net
release of H+ by arsenite. These differences reflect the mechanism of As adsorption and influence the
pH dependence of adsorption

Granular ‘ferric hydroxide’ As(V) isotherms given in the sub- m M concentration range; SO 4 competition significant at mM Driehaus et al. (1998)
(akageneite) concentrations below pH 7 only; phosphate competition at ‘natural’ groundwater concentrations

Goethite An EXAFS and XANES study of As(III) adsorption to a synthetic goethite suggested bidentate inner Manning et al. (1998)
sphere binding. One plot of As(III) and As(V) pH adsorption envelopes. As(III) data fitted to Constant
Capacitance SCM

Goethite Batch adsorption of As(V) on synthetic goethite. Used Mo blue analysis for As. Shows pH edge at Matis et al. (1997)
about pH 9. Data fitted Langmuir isotherm presumably at constant pH (up to 60 mg l 1 As)

Goethite Successfully applied the CD-MUSIC surface complexation model to literature data for anion Hiemstra and van Riemsdijk
adsorption to goethite including As(V)-P competition. The CD-MUSIC is the most promising of (1999)
the SCMs for modelling complex natural systems

Goethite As(V) adsorption on synthetic goethite primarily for a study of impact on flocculation and Matis et al. (1999)
electrokinetics. No isotherms. Final pH varied but not defined

( continued on next page)

 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

Table 5 ( continued)

Mineral Comment Reference

Goethite EXAFS study of As(V) and Cr (VI) adsorption on goethite. Monodentate binding favoured at low surface Fendorf et al. (1997)
coverages of As(V), bidentate at high surface coverages

Manganese oxides As(III) and As(V) removal by MnO 2( s) is similar, up to say 5 mmol As mol 1 Mn at m M As Driehaus et al. (1995)
equilibrium solution concentrations. Freundlich isotherm obeyed. As(III) oxidised to As(V). Rapid
oxidation (minutes) and adsorption of As(III). Monitored Mn release and effect of pH, Ca,
phosphate and sulphate

Birnessite, cryptomelane and Studied adsorption of As(III) and As(V) and kinetics of As(III) oxidation in presence of various MnO 2. As(III) Oscarson et al. (1983)
pyrolusite adsorption (per unit weight of oxide): cryptomelane>birnessite>pyrolusite whereas for As(V):
cryptomelane
> pyrolusite>birnessite (not detectable). No isotherms given

Goethite, hematite and Batch adsorption of As(V), As(III), MMAA and DMAA on natural minerals (coarse-grained and very Bowell (1994)
lepidocrocite low He-Ar surface area). As adsorption: generally goethite>lepidocrocite>>hematite (pH 2–12,
maximum often pH 5–8). At pH 7 on goethite, As(III)>MMAA>DMAA>As(V) (?). FA (up to 50 mg l 1) tended
to reduce As adsorption. Gives K d values

Alumina, hematite, quartz As(V) adsorption on natural, low surface area alumina, hematite, quartz and kaolin (0.12–5 m 2 g 1) at Xu et al. (1988)
and kaolin pH 3–10. Adsorption decreases with pH; alumina=kaolin>hematite>>quartz. Gives K d values and
isotherms at low concentrations. Some SO 42 competition especially below pH 7. FA (>10 mg l 1) generally
reduced adsorption at pH 5–7 but not above pH 7 where FA is not adsorbed

Alumina On natural alumina, adsorption was As(V)>As(III)>MMAA=DMAA (pH>6). Maximum adsorption at Xu et al. (1991)
pH 5 for As(V) and pH 7 for As(III). As(V) but not As(III) adsorption decreased rapidly above pH 6.
Log K d
(l kg 1) at micromolar concentrations (pH 7) was 2.5–3.5 for As(V) and about 1.5 for As(III). FA
decreased adsorption

Notes: HFO=hydrous ferric oxide.

SCM=surface complexation model.
EXAFS=extended X-ray absorption fine structure. XANES=X-ray
absorption near-edge structure. MMAA=monomethylarsonic acid, CH 3 AsO(OH)
2.

DMAA=dimethylarsinic acid, (CH 3)2 AsO(OH)). FA=fulvic acid.

CD-MUSIC=charge distribution-multisite complexation model. 536

NO 2 and the gases N 2 O and N 2. Insoluble manganic oxides dissolve by transformations of the Fe oxides under reducing conditions. This is most
reduction to soluble Mn 2+ and hydrous ferric oxides are reduced to Fe 2+. These obviously reflected in a colour change from reddish/orange/brown/tan
processes are followed by SO 42 reduction to S 2 , then CH 4 colours to grey/green/ blue colours. Changes to the magnetic properties
have also been documented (Sohlenius, 1996). Direct analysis of the Fe(II)
production from fermentation and methanogenesis, and finally reduction of N 2 and Fe(III) contents of Fe oxides from reduced lake waters and sediments
to NH 4+. During SO 42 reduction, the consequent S 2 reacts with any available often indicates the presence of a mixed Fe(II)–Fe(III) oxide with an
Fe to produce FeS and ultimately pyrite, FeS 2. Iron is often more abundant approximate average charge on the Fe of 2.5 (Davison, 1993). The exact
than S so that there is ‘excess Fe’ beyond that which can be converted to fate of Fe during reduction is not well understood, in part because it is
pyrite (Widerlund and Ingri, probably very fine-grained and difficult to observe directly. Mo¨ ssbauer
spectroscopy is a useful technique for identifying the form of Fe oxides in
1995). Arsenic(V) reduction would normally be expected to occur after sediments, including anoxic sediments (Boughriet et al., 1997; Drodt et al.,
Fe(III) reduction but before SO 42 reduction. 1997).
In SO 42 - poor environments, Fe from free Fe oxides is solubilized as Fe 2+ under
reducing conditions. This gives rise to characteristically high-Fe waters.
Groundwaters in such conditions tend to have Fe concentrations of 0.1– 30
mg l 1. The reaction is microbially mediated (Lovley andChappelle, 1995). ‘Green rusts’ are one possible product of the transformations. These
There is also evidence for solid-state have occasionally been identified or suspected in anoxic soils and
sediments (Taylor, 1980;
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 537

Boughriet et al., 1997; Cummings et al., 1999). They consist of a range of and Naylor, 1994; McGeehan, 1996; Reynolds et al.,
green-coloured Fe(II)–Fe(III) hydroxide minerals with a layered structure and 1999). Similar evidence is available from laboratory and field studies of
a chargebalancing interlayer counterion, usually carbonate or sulphate. marine and lake sediments. Numerous studies have demonstrated the
Green rusts were originally referred to as ‘hydrated magnetite’ and given a release of both P (Mortimer, 1942; Farmer et al., 1994; Slomp et al., 1996)
composition ‘Fe 3( OH) 8 ’. Boughriet et al. (1997) suspected the presence of and As (Aggett and O’Brien, 1985; Moore et al., 1988; De Vitre et al., 1991;
either greenrust-like compounds, Fe(III)–Fe(II)–(CO 3)( OH) or Fe(II) x Ca 1 x CO 3 solid Azcue and Nriagu, 1995; Widerlund and Ingri,
solutions, in anoxic sediments from the Seine Estuary. They used 57 Fe Mo¨
ssbauer spectroscopy to characterize the Fe. Green rusts have also been 1995) below the redox boundary in sediments. This release has long been
identified in anaerobic soils and are thought to play an important role in associated with Fe oxide dissolution. Deuel and Swoboda (1972) found that
controlling soil solution Fe concentrations (Genin et al., 1998). reducing an untreated black clay soil led to the release of As and that the
amount released was related to the total As content of the soil and the redox
potential. They proposed that the release was primarily due to reduction
(and dissolution) of ‘ferric arsenates’ rather than to changes in the As
speciation. Arsenic release occurred in less than a week.
Authigenic magnetite (Fe 3 O 4), is another possible product which has been
identified in anaerobic sediments (Fredrickson et al., 1998), often with
extremely small particle sizes (Maher and Taylor, 1988; Canfield,
De Vitre et al. (1991) showed that there was a rapid increase in
1989). Magnetite is frequently found in sediments as a residual detrital porewater As concentrations (up to about 30
phase from rock weathering but very fine-grained magnetite is also formed m g l 1) with depth in a lake sediment and that this was mirrored by an increase
by so-called ‘magnetotactic’ bacteria. Magnetite formation has been in dissolved Fe. Upwardly diffusing Fe 2+ was oxidised near the
established under reducing conditions in the laboratory (Guerin and sediment-water interface and precipitated as an Fe oxide which then
Blakemore, 1992). However, under strongly reducing conditions magnetite is adsorbed the upwardly diffusing As. As noted in Section
unstable and in the presence of high concentrations of H 2 S, it slowly
converts to pyrite over a period of 100a or more (Canfield and Berner, 2.2.7, much larger As concentrations, up to a peak of 6430 m g l 1, have been
1987). At the sediment/water interface in oceans, partial oxidation of primary measured in porewaters from shallow, anoxic lake sediments in the
magnetite (Fe 3 O 4) geothermal region of New Zealand (Aggett and Kriegman, 1988). This
dissolved As, mostly As(III), diffused across the sediment-lake water
interface and accumulated along with dissolved Fe and Mn in the
can lead to a coating of maghemite, g- Fe 2 O 3. Further burial and reduction hypolimnion until turnover. On the other hand, recent studies of As profiles in
leads to the dissolution of the primary magnetite (Torii, 1997). Crowley Lake, California, a lake affected by large inputs of As in surface
water affected by geothermal sources, suggest that As is not released from
These studies of Fe oxides in reducing environments indicate a lack of the sediments. Rather it is taken up by the sediments, probably in solid
an as yet well-defined sequence of events taking place when Fe(III) oxides sulphide phases (Kneebone and Hering, 2000).
are subjected to strongly reducing conditions. The changes are evidently
substantial and can result in the partial dissolution of the oxides and their
transformation to completely new mineral phases. It is not yet clear what
impact these transformations have on the adsorbed As load of the original Guo et al. (1997) measured the rate of release of As (and other trace
Fe(III) oxides. Suffice it to say that even quite small changes in As binding elements) as a spiked sediment was progressively reduced. Arsenic was
could have a large impact on porewater As concentrations because of the rapidly released after the Fe and Mn had dissolved, suggesting that
large solid/solution ratio in sediments. Therefore, it is likely that dissolution rather than desorption was the dominant process, or at least that
understanding the changes to the nature of Fe oxide minerals in dissolution and desorption occurred simultaneously. Selective extractions
sedimentary environments is an important aspect in understanding the suggested that most of the As in the sediments was associated with Fe and
processes leading to As mobilisation in sedimentary environments. Mn oxides. Riedel et al. (1997) monitored the release of metals when a
column of estuarine sediment was subjected to reducing conditions for
several months. Both As and Mn were released following reduction.

4.4. Arsenic release from soils and sediments following reduction A few studies have attempted to differentiate between the oxidation
states of As sorbed by sediments. Masscheleyn et al. (1991) measured the
release of As and other metals following the flooding and reduction of an
There is considerable evidence from laboratory studies that As is As-contaminated soil and found that the release of some As occurred before
released from soils following flooding and the development of anaerobic Fe dissolution but that the amount of As released rapidly increased as the
conditions (Deuel and Swoboda, 1972; Hess and Blanchar, 1977; amount of Fe-
McGeehan
538 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

oxide dissolution increased. Both As(V) and As(III) were released. Rochette highly-contaminated sediments from the Wells G&H Superfund site in the
et al. (1998) demonstrated with XANES spectroscopy that reducing Aberjona catchment was found to be in the (ii)–(iv) fractions described
conditions can lead to the conversion of As(V) to As(III) in the solid phase of above.
As minerals. Preliminary results based on XANES also indicate a change in Brannon and Patrick (1987) studied the kinetics of As release and
solid-state speciation of the As in Bangladesh sediments in going from speciation [As(V), As(III), organic] from freshwater sediments when
oxidising to reducing conditions (Foster et al., 2000). incubated under both oxidising and reducing conditions. This included
sediments with and without added As(V). Most of the native and added As
was found in the ‘moderately reducible’ (oxalate-extractable) fraction. During
There is now considerable evidence that high-As groundwaters can be incubation, a steady release of As was observed over a 3-month period, with
associated with reducing conditions, particularly in alluvial and deltaic As(V) occurring under oxidising conditions and As(III) under reducing
environments. The Bengal Basin is the most notable example. While the conditions. There was no concomitant release of Fe (or Al or Mn), indicating
precise mechanisms responsible for this remain uncertain, it is possible that that reductive dissolution of Fe oxides was not responsible for the As
both reductive desorption and reductive dissolution of As from oxides and release. Brannon and Patrick (1987) speculated that a change in the
clays play a role. At the near-neutral pH of many groundwaters, As(III) is structure of the Fe oxides may have been important. McGeehan (1996) was
expected to be less strongly sorbed than As(V) and so some desorption of not sure whether the As(V) reduction that occurs in flooded soils occurs in
As may occur as a result of the onset of strongly reducing conditions the soil solution or on the soil particles.
following sediment burial (DPHE/BGS/MML, 1999, Vol. S4). Recent
experiments with synthetic Fe and Al oxides have demonstrated the
desorption of As following reduction of As(V) to As(III) (Zobrist et al., 2000).
Dissolution of the oxides was not necessary for As release.
Manning and Goldberg (1997a) measured As(V) and As(III) adsorption
by 3 Californian soils and found that the soils with the highest
citrate-dithionite-bicarbonate extractable Fe and percent clay had the
greatest affinity for bothAs(III) and As(V). Arsenic(V) sorbed to a greater
extent than As(III) at the micromolar As concentrations used, suggesting that
4.5. Speciation of elements in sediments and the role of selective As would be released under reducing conditions when As(V) is reduced to
extraction techniques As(III). Cummings et al. (1999) found that As(V) was released from hydrous
ferric oxide (HFO) under reducing conditions without any pre-reduction of
The As concentration in sediments is normally too low and/or the As(V) to As(III). Scorodite, a ferric arsenate mineral (Table 2), was also in
particles too small for direct investigation of solid phase As speciation using part transformed to various ferrous arsenates. Therefore, the reduction of
techniques such as XAFS and PIXE and so selective dissolution has been As(V) to As(III) may follow the initial release of As into solution rather than
most widely used. A number of chemical extraction ‘schemes’ have been initiate it.
devised which attempt to allocate elements to particular solid phases but few
of these are specifically designed for speciating solid phase As. Go´
mez-Ariza et al. (1998) developed a method to speciate solid-phase As
based on selective extraction of sediments with hydroxylamine Aggett and Roberts (1986) found a good correlation between the release
hydrochloride, an acidic and reducing extractant that is rather selective for of both As and phosphate from New Zealand lake sediments with that of
extracting Mn oxides but that also extracts small amounts of Fe oxides. EDTAextractable Fe. They concluded that the As was primarily associated
Hydroxylamine hydrochloride did not reduce the As(V) during the extraction. with amorphous Fe oxides and they suggested that because of the relative
constancy of the Fe/As ratio during dissolution, the As had probably been
coprecipitated with the Fe oxide rather than being adsorbed to it.

Keon et al. (2001) have described a more comprehensive 8-step

sequential extraction scheme that attempts to partition sediment As into Acid ammonium oxalate has been widely used for extracting ‘amorphous
various forms. The scheme uses: (i) 1 M MgCl 2 ( for ionically-bound As); (ii) 1 Fe oxides’ and has been extensively used on sediments from Bangladesh
M NaH 2 PO 4 ( strongly adsorbed); (iii) 1 M HCl (acid volatile sulphides, (BGS and DPHE, 2001). There was a good overall correlation between
carbonates, Mn oxides and very amorphous Fe oxyhydroxides); (iv) 0.2 M extractable As and Fe but many other elements were also correlated with
oxalate/oxalic acid (amorphous Fe oxyhydroxides); (v) 0.05 M Ti(III)– the extractable Fe since this tended to be most abundant in the fine-grained
citrate-EDTA-bicarbonate (crystalline Fe oxyhydroxides); (vi) 10 M HF sediments. Nevertheless, the amount of oxalate-extractable Fe and As of
(arsenic oxides and silicates); (vii) 16 MHNO 3 ( pyrite and amorphous As 2 S 3) and the aquifer sediments appeared to separate low-As groundwater areas from
(viii) hot 16 M HNO 3+ 30% H 2 O 2 ( orpiment and other recalcitrant minerals). high-As areas. Acid ammonium oxalate is less selective with reducing
About 90% of the As in a selection of sediments compared with oxidising sediments since mixed
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 539

valence Fe minerals such as magnetite are also dissolved to a considerable have different adsorption isotherms, should travel through an aquifer with
extent. It also can dissolve appreciable amounts of clays, as reflected by the different velocities. This will lead to their increased separation along a flow
extensive release of Mg, Al and Si. path. This was demonstrated by Gulens et al. (1979) using breakthrough
experiments with columns of sand (containing 0.6% Fe and 0.01% Mn) and
All of these studies demonstrate the ability of soils and sediments to various groundwaters pumped continuously from piezometers. They studied
release As when subjected to reducing conditions but there is no clear As(III) and As(V) mobility with groundwaters having a range of Eh and pH
consensus on the precise mechanisms involved, particularly with respect to values using radioactive
the roles played by reductive desorption, reductive dissolution and/or
diagenetic changes to the mineral structure.
74 As (half-life=17.7 days) and 76 As (half-life=26.4 h) to monitor the

Alkaline extractants, particularly bicarbonate solutions at various pH breakthrough of As. They showed that: (i) As(III) moved 5–6 times faster

values (e.g. 7.6, 8.5 and 10), have been widely used to assess the plant than As(V) under oxidising conditions (pH 5.7); (ii) with a ‘neutral’

availability of soil phosphate. These have not yet been applied to the groundwater (pH 6.9), As(V) moved much faster than under condition (i) but

extraction of As, specifically As(V), although Gustafsson and Jacks (1995) was still slower than As(III); (iii) with reducing groundwater at pH 8.3, both

used 0.5 M NaOH. This usually extracted some 1/2 to 2/3 of the ‘total’ As(V) As(III) and As(V) moved rapidly through the column; (iv) when the amount of

from the mineral horizons of some Swedish forest soils. As injected was substantially reduced, the mobility of the As(III) and As(V)
was greatly reduced. This chromatographic effect may account in part for
the highly variable As(III)/As(V) ratios found in many reducing aquifers. Such
Unfortunately, none of the selective extraction schemes is perfect or a separation is used to advantage in analytical chemistry to speciate As with
universally applicable and there is little consensus on the best techniques to various columns. Chromatographic separation during transport will also tend
use. There are no recognised procedures for solid phase As speciation, to uncorrelate any correlations found at the source, for example in the As
although a number of traditional approaches have been used on an ad hoc versus Fe relationship, thus further complicating a simple interpretation of
basis and new approaches are the subject of current research (Keon et al., well water analyses.
2001). The interpretation of results for many of these extractions is difficult
for minor and trace constituents which may be released by dissolution,
codissolution and desorption processes. Nonetheless, these extractants can
probe the solid phase in a useful way that reflects to a varying extent the
nature of an element in the solid phase, and therefore its potential behaviour
or availability. In particular, such techniques are useful for characterising A number of experimental investigations of As adsorption reported in the
very-fine grained minerals or organic phases that are presently poorly literature, most commonly for pure Fe and Al oxides, allow K d values to be
characterised by direct examination but which nevertheless play an estimated for a range of adsorbents (Table 6). The K d s thus derived, here
important role in the behaviour of many trace elements in the natural mostly calculated for pH 7, have a large range, spanning around 6 orders of
environment. magnitude. All other things being equal, K d s tend to decrease with
increasing As concentration reflecting some nonlinearity in the sorption
isotherm. As expected, under similar conditions, K d s are often greater for
As(V) than for As(III) but this is not always the case. Values are highest for
HFO which in part reflects the large adsorption capacity of HFO. High K d values
are also found for Mn oxides (birnessite). Experiments with Mn oxides by
4.6. Transport of arsenic Driehaus et al. (1995) suggest that values are high for both As(V) and
As(III), although in practice, much of the As(III) was probably oxidised to
The transport of chemicals and adsorption are closely related in that As(V) during the experiment by the Mn(IV) oxide (Oscarson et al., 1981;
adsorption slows down the transport of a chemical compared with the water 1983). There is a need for more high-quality data on the sorption of As(V)
flow (Appelo and Postma, 1994). In the simplest case of a linear adsorption and As(III) at low As concentrations (1–100 m g l 1) including experiments
isotherm, this relationship is straightforward and the partition coefficient, K d, defines carried out in the presence of competing anions and using aquifer solids
a constant retardation factor. With a non-linear adsorption isotherm, the rather than synthetic minerals.
value of K d varies with concentration and is related to the shape of the
isotherm. Normally, the K d decreases with increasing concentration, leading
to less retardation at high concentrations and ultimately to self-sharpening
fronts and diffuse tails during transport. This means that it is difficult to flush
As completely from an aquifer.

A few field-based investigations have been carried out on natural and

contaminated systems which allow K d
Since the transport of a solute is closely related to the extent of values for As sorption to be determined directly. Kuhlmeier (1997a,b)
adsorption and the nature of the adsorption isotherm, it follows that arsenate studied the transport of As in highlycontaminated clayey and sandy soils
and arsenite, which from around an
540 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

Table 6
Solid-solution partition coefficients ( K d s) calculated from experimental data at or near pH 7 for a range of oxides and clays

Material Components K d ( l kg 1) pH Comments Reference

a c= 37 m g l 1,
Alumina ( a- Al 2 O 3) As(III) 42 7 Xu et al. (1991), Fig. 2
I= 0.1 M
Alumina ( a- Al 2 O 3) As(V) 760 7 c= 3.8 m g l 1, Xu et al. (1988), Fig. 3
I= 0.1 M
Alumina ( a- Al 2 O 3) As(V) 520 7 c= 1200 m g l 1, Anderson et al. (1976), Fig. 2
I= 0.01 M
Amorphous aluminium As(III) 230 7 c= 4 m g l 1 Manning and Goldberg (1997a), Fig. 1
hydroxide
Gibbsite As(V) 133 7 c= 16 mg l 1 Hingston et al. (1971), Fig. 3a
Gibbsite As(V) 32 7 c= 16 mg/l+ Hingston et al. (1971), Fig. 3c+b
5.5 mg l 1 P
Goethite As(V) 192 7 c= 4.9 mg l 1, Hingston et al. (1971), Fig. 2
I= 0.1 M
Goethite As(V)+P 54 7 c= 66 mg l 1, Hingston et al. (1971), Fig. 4
+ 74 mg l 1 P,
I= 0.1 M
Goethite (natural) As(III) 32 7 c= 40 m g l 1 Bowell (1994), Fig. 2
Goethite (natural) As(V) 1800 7 c= 1.5 m g l 1 Bowell (1994), Fig. 2
Haematite As(V) 34 7 c= 48 m g l 1, Xu et al. (1988), Fig. 3
I= 0.1 M
Haematite (natural) As(III) 21 7 c= 48 m g l 1 Bowell (1994), Fig. 2
Haematite (natural) As(V) 25 7 c= 45 m g l 1 Bowell (1994), Fig. 2
HFO As 7000 c= 50 m g l 1 Thirunavukukkarasu et al. (2001), Fig. 3
HFO As(III) 120,000 7 c= 310 m g l 1, Swedlund and Webster (1999), Fig. 1a
I= 0.1 M
HFO As(III) 670,000 7 c= 27 m g l 1, Pierce and Moore (1982), Fig. 1
I= 0.01 M
HFO As(III) 7340 7 c= 18900 m g l 1, Pierce and Moore (1982), Fig. 3
I= 0.01 M
HFO As(III) 520,000 7 c= 30 m g l 1, Wilkie and Hering (1996), Fig. 1
I= 0.01 M; possibly partial
oxidation during experiment

HFO As(III)+Si 13,000 7 c= 1690 m g l 1, Swedlund and Webster (1998), Fig. 1a

Si T= 62 mg l 1,
I= 0.1 M
HFO As(V) > 1,000,000 7 c< 50 m g l 1, Swedlund and Webster (1998), Fig. 1b
I= 0.1 M
HFO As(V) 460,000 7 c= 32 m g l 1 Pierce and Moore (1982), Fig. 5
I= 0.01 M
HFO As(V) 120,000 7 c= 160 m g l 1 Pierce and Moore (1982), Fig. 5
I= 0.01 M
HFO As(V) 37,000 7 c= 850 m g l 1 Pierce and Moore (1982), Fig. 5
I= 0.01 M
HFO As(V) 66,000 7 c= 19500 m g l 1 Pierce and Moore (1982), Fig. 7
I= 0.01 M
HFO As(V)+Si 8,100 7 c= 2130 m g l 1, Swedlund and Webster (1998), Fig. 1b
Si T= 62 mg l 1,
I= 0.1 M
HFO (granular) As(V) 2,100,000 6 50 m g l 1 Driehaus et al. (1998), Fig. 1
Iron-oxide-coated sand Oxidn state 600 ? c= 50 m g l 1 Thirunavukukkarasu et al. (2001), Fig. 2
uncertain
Lepidocrocite (natural) As(III) 35 7 c= 39 m g l 1 Bowell (1994), Fig. 2
Lepidocrocite (natural) As(V) 1000 7 c= 2.7 m g l 1 Bowell (1994), Fig. 2

( continued on next page)

 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 541

Table 6 ( continued)

Material Components K d ( l kg 1) pH Comments Reference

Birnessite ( d- MnO 2) ‘‘As(III)’’ 46,000 7 c= 75 m g l 1, Driehaus et al. (1995), Fig. 1

I= 0.01 M; As(III) probably all
oxidised during experiment

Birnessite ( d- MnO 2) As(V) 57,500 7 c= 75 m g l 1, Driehaus et al. (1995), Fig. 1

I= 0.01 M
Quartz As(V) 2 7 c= 71 m g l 1, Xu et al. (1988), Fig. 3
I= 0.1 M
Illite As(III) 98 7 c= 9 m g l 1 Manning and Goldberg (1997a), Fig. 1
Kaolinite As(III) 19 7 c= 20 m g l 1 Manning and Goldberg (1997a), Fig. 1
Kaolinite As(V) 760 7 c= 3.8 m g l 1, Xu et al. (1988), Fig. 3
I= 0.1 M
Wyoming Bentonite As(III) 30 7 c= 17 m g l 1 Manning and Goldberg (1997a), Fig. 1

a c=final dissolved As concentration; I= ionic strength.

old As herbicide plant in Houston, Texas. He used column experiments to tion, pH and concentration of competitors such as phosphate
estimate ‘apparent’ K d values. These were time- and implicitly (DPHE/BGS/MML, 1999, Vol. S3 and S4). Inferred K d s from these
concentration-dependent and for the sandy soils ranged from 0.26 l kg 1 calculations for Bangladesh sediments range from about 1 l kg 1 for As(V)
under ‘high P-low Fe’ conditions to more than 200 l kg 1

after one void volume to 3.3 l kg 1 after 6 void volumes. They were not too
different for the clayey materials. However, the overall As concentrations under ‘low P-high Fe’ conditions. Broadly similar values are inferred for
were very high: the groundwater was heavily contaminated with As As(III) sorption under comparable conditions—the presence of high
(408–464 mg l 1), mostly as MMAA. The sediment contained only a few mg kg 1 phosphate concentrations is calculated to severely reduce As(V) sorption
of inorganic As. but not As(III) sorption. Coupled studies of sediment and groundwater
chemistry in piezometers (10–50 m depth) in 3 high-As groundwater
Baes and Sharp (1983) gave K d values of 1.0–8.3 l kg 1 ( median 3.3) for locations in Bangladesh (BGS and DPHE, 2001) suggest that the K d s for As
As(III) binding by soils and 1.9– are low, approximately 2–6 l kg 1. These values have been derived by
18.0 l kg 1 ( median 6.7) for As(V). The authors have estimated K d s for 3 assuming that the sorbed As can be equated to the oxalate-extractable As
Californian soils (pH 5.7–7.1) at an equilibrium concentration of 50 m g l 1 to and so are likely to represent an upper estimate.
range from 5– 52 l kg 1 for As(III) and 10–80 for As(V) (Manning and
Goldberg, 1997a, Fig. 4).

Data from Sullivan and Aller (1996) indicate that K d Values obtained for K d from these field studies in areas having high-As
values calculated for sediment profiles from the Amazon Shelf are in the groundwaters generally suggest that it is, for whatever reason, the low K d values
approximate range 11–5000 l kg 1. that are responsible for the high dissolved As concentrations, rather than
High-As porewaters were mostly from the zones with low K d values (typically high absolute concentrations of As in the sediment. The K d values given in
<100 l kg 1). The concentrations of reactive solid As derived from an acid Table 6 are in many cases much higher than found in natural sediments,
leach were in the approximate range 1–13 mg kg 1 and the authors gave an even after allowing for the relatively minor concentration (a few percent) of
average total sediment As concentration of 12 mg kg 1. Smedley et al. (2000) Fe oxides inmost sediments. There is some evidence that use of the surface
also estimated complexation model and database of Dzombak and Morel (1990) can lead to
an overestimation of sorption when applied to natural sediments (Kent et al.,
K d for loess sediments bearing high-As groundwaters from La Pampa, 1995). This may reflect a difference between the natural Fe oxides found in
Argentina. They estimated a low value, close to 1 l kg 1, using coupled sediments and synthetic HFO used for most laboratory studies or other
porewater and oxalateextract data. Arsenic concentrations of the analysed factors such as the presence of competing ions in the natural sediments.
sediments were in the range 3–18 mg kg 1. Certainly it would be difficult to infer the location of high-As groundwaters
from an analysis of total sediment As concentrations alone.
Calculated sorption and retardation factors, based on the Dzombak and
Morel (1990) diffuse double layer model and database for HFO, indicate
highly variable
K d s depending on: the HFO (and other active oxide) content of the sediment,
As speciation, As concentra-
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

5. Groundwater environments with high arsenic concentrations guidelines for As has prompted a reassessment of the situation in many
countries. The recent discovery of As enrichment on a large scale in
Bangladesh has highlighted the need for a rapid assessment of the situation
5.1. World distribution of groundwater arsenic problems in alluvial aquifers worldwide. As described above, As problems also occur
in some areas where sulphidemining activity is prevalent, the As being
A number of large aquifers in various parts of the world have been released from sulphide minerals as they are oxidised as a result of mining
identified with problems from As occurring at concentrations above 50 m g l 1, often operations. In mining areas, As problems can be severe with concentrations
significantly so. The most noteworthy occurrences are in parts of Argentina, in affected waters sometimes being in the mg l 1 range. However, unlike As
Bangladesh, Chile, China, Hungary, India (West Bengal), Mexico, Romania, occurrences in major aquifers, the problems in these areas are typically
Taiwan, Vietnam and many parts of the USA, particularly the SW (Fig. 3). localised, rather than of widespread occurrence. Miningrelated As problems
Some of the better documented cases are summarised in Table 7. These in water have been identified in many parts of the world, including Ghana,
include natural sources of enrichment as well as mining-related sources. Greece, Thailand and the USA (Fig. 3).
Recent reconnaissance surveys of groundwater quality in other areas such
as parts of Nepal, Myanmar and Cambodia have also revealed
concentrations of As in some sources exceeding 50 m g l 1,

While high-As groundwaters (with As above drinking-water standards)

are not uncommon, they are by no means typical of most aquifers and only
although documentation of the affected aquifers is so far limited. Arsenic exist under special circumstances. These relate to both the geochemical
associated with geothermal waters has also been reported in several areas, environment and to the past and present hydrogeology. Paradoxically,
including hot springs from parts of Argentina, Japan, New Zealand, Chile, high-As groundwaters are not necessarily related to areas of high As
Kamchatka, Iceland, France, Dominica and the USA. concentrations in the source rocks. Distinctive groundwater As problems
occur under both reducing and oxidising groundwater conditions; also under
Localised groundwater As problems are now being reported from an both humid/temperate and arid climates. Below, the authors discuss the
increasing number of countries and many new cases are likely to be characteristics of the As problems worldwide through a series of type
discovered. Until recently, As was not traditionally on the list of elements examples. These have been ordered according to the environment under
routinely tested
Areas in blue by water-quality
are lakes. 542 testing laboratories and so many high-As which they are developed.
water sources may have been missed. Revision of drinking-water
regulations and

Fig. 3. Distribution of documented world problems with As in groundwater in major aquifers as well as water and environmental problems related to mining and geothermal sources.
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 543

Fig. 4. Smoothed map showing the distribution of As in groundwater from shallow (<150 m) tubewells in Bangladesh.

5.2. Reducing environments internal As-related health problems is also not known but could be
appreciable.
5.2.1. Bangladesh and India (West Bengal) West Bengal and Bangladesh rely heavily on groundwater for public
In terms of the population exposed, As problems in groundwater from the drinking-water supply. Groundwater development has been actively
alluvial and deltaic aquifers of Bangladesh and West Bengal represent the encouraged in the region over the last few decades by government and
most serious occurrences other agencies as a means of providing an alternative to polluted surface
identified globally. Concentrations in water and thereby reducing the incidence of water-borne diseases. There
groundwaters from the affected areas have a very large range from <0.5 to has also been a rapid increase in the number of private tubewells and now
ca. 3200 m g l 1 ( DPHE/BGS/MML, 1999; CGWB, 1999; BGS and DPHE, the number of these exceeds the number of public tubewells. In this sense,
2001). Some 27% of shallow (<150 m deep) wells in Bangladesh contain the increase in use of groundwater has been very successful. The
more than 50 m g l 1 As (BGS and DPHE, 2001). The worst-affected area is in identification of chronic health problems related to As was unforeseen and
the SE of Bangladesh (Fig. 4) where in some districts more than 90% of has taken a number of years to become apparent.
wells are affected. Resultant health problems were first identified in West
Bengal in the 1980s but the first diagnosis in Bangladesh was not made until
1993. Up to around 30– 35 million people in Bangladesh are estimated to be
exposed to As in drinking water at concentrations above 50 m g l 1 ( BGS and The affected aquifers are generally shallow (less than 100–150 m deep),
DPHE, 2001) and up to 6 million in West Bengal (Table 7). Skin disorders of Holocene age and comprise micaceous sands, silts and clays deposited
including hyper/ hypopigmentation changes and keratosis are the most by the Ganges, Brahmaputra and Meghna river systems and their
common external manifestations, although skin cancer has also been precursors. The sediments are derived from the upland Himalayan
identified. Around 5000 patients have been identified with As-related health catchments and from basement complexes of the northern and western
problems in West Bengal (including skin pigmentation changes) although parts of West Bengal. In most affected areas, the aquifer sediments are
some estimates put the number of patients with arsenicosis at more than capped by a layer of clay or silt (of variable thickness) which effectively
200,000 (Smith et al., 2000). The number in Bangladesh is not known but restricts entry of air to the aquifers. This, together with the presence of
must be many times greater than in West Bengal. The instance of recent solid organic matter deposited with the sediments, has resulted in the
development of highly reducing conditions which favour the mobilisation of
As. The mobilisation has probably occurred by a complex combination of
redox changes
 10 6

10 6 10 6 10 6
10 7
exposed a
diagnosed

upto1300 100–1000 < 1–5300 < 2–176 1–3050 40–750 < 1–2400 10–1820 < 10–3200 < 0.5–2500 Concentration

(7500insome

Argentina(Chaco-
porewaters) ranges( m gl
1
)
Alluvialbasins,some ?Quaternaryvolcanogenic Holocenealluvialplain
Holocenealluvial/deltaic
Quaternaryalluvialplain
Holoceneandearlierloess Alluvialplain Sediments,including
Holocenealluvialand AsBangladesh Holocenealluvial/deltaic
Aquifertype

sediment
BasinandRange,
evaporites RedRiverdelta,
sediments
blackshale [Link]
UNICEF(1999)
Hungary,Romania
BGSandDPHE(2001)
(1999);SanchaandCastro(2001)

lacustrinesediments solidorganicmatter

withrhyoliticvolcanicash

Gurzau(2001)
(mainlyAs(V))correlatespositively
Oxidising,[Link] [Link]
concentrationsinsomeriverwaters
V,M Reducinggroundwater,some
Oxidising,neutraltohighpH, ?ReducingReducing,deepwells(upto660m) Stronglyreducingconditions,
highalkalinity
Reducing,highFe,M AsBangladesh Stronglyreducing,neutralpH,
Stronglyreducing,artesian Groundwaterconditions

neutralpH,highalkalinity. flow

withM o,[Link] rates

Deepgroundwatersoftenartesian,
o,Se,V,F
conditions,somegroundwaters
somehavehighconcentrations
[Link] areartesian
conditions,highsalinity,highB. ofhumicacid

containhumicacid
highalkalinity,slow
[Link] groundwater
n,NH

Alsohigh-Asriverwaters

4,

As(V),accompaniedbyhighB,
[Link]

Robertson(1989)
Smithetal.(1992)Ca´ Varsa´ Sunetal.(1999)
Bergetal.(2001)
Nicollietal.(1989),Sanchaand W CGW
Sunetal.(2001)
Luoetal.(1997),Zhaietal.
Kuo(1968),Tsengetal.(1968) DPHE/BGS/M Reference

ceresetal.(1992),Karcheretal. angandHuang(1994)

nyietal.(1991),Gurzauand B(1999);PHED/
(1998),M
aetal.(1999),Sunetal.
( continuedonnextpage)

M
L(1999);

(1999),Smedleyetal.(2001a)

Castro(2001),Smedleyetal.(2002)
 10 5
Fairbanks,
exposed a

< 10–150 0.5–580 upto2000 upto1400 50–3000 upto10,000 1to5000 8–620 upto2600 < 1–2600 Concentration

ranges( m gl
1
)
Sulphidemineralveinsin
Lakesediments
UpperTriassicKeuperSandstone M
Valley-filldeposits M DredgedQuaternaryalluvium
Schist,alluvium,minetailings Volcanicsediments
(someproblemsinlimestone),tailings Holocenemixedaeolian, Holoceneandolder
Aquifertype
1
(drinking-waterstandardofmostcountries). inetailings inetailings

ining
NorthernBavaria,
Coeurd’Alene,

BowenIsland,
alluvial,lacustrinesediments,

basin-fillsediments

volcaniccountryrocks

somethinvolcanicashbands

withmineralisation(uncharacterized)

O VariableSONeutraltohigh-pH
Arsenicinsedimentporewaters Goldmining,arsenopyite,
M
Oremining(Au,haematite,
Riverwaterandgroundwater Oxidationofdisseminated Somesalinegroundwaters,with
P,M
Oxidising,neutraltohighpH, Largelyreducing,somehighpH. Groundwaterconditions
Internally-drainedbasin.M
2 concentrations
from arsenopyriteduetoformertin
mining,subsequentgroundwater highU n,DOC
AuminingintheBlackHills
rebound

usuallylow
NO 4 concentrations,
(Fetoalesserextent)
3, low Somewithhighsalinitydueto
possiblyscorodite
magnetite,Pb,Co)
AsmainlyasAs(V)
groundwaters
dissolved

affectedbyPb-Zn-Agmining ixed
redoxconditionsProportionof
As(III)increaseswithwelldepth.
Highsalinityinsomeshallow
[Link],U,B,M
[Link],
(upto8.9),AscorrelatedwithB,F o

Boyleetal.(1998)
HeinrichsandUdluft(1999) WW
FicklinandCallender(1989) WW
AzcueandNriagu(1995) WW W
DelRazoetal.(1990) W Reference
FujiiandSwain(1995)
ai(1990)
elchetal.(1988),M ilsonandHawkins(1978);
elchetal.(1988) illiams(1997)
illiamsetal.(1996), elchandLico(1998) elchandLico(1998)

okand
546 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

brought on by rapid burial of the alluvial and deltaic sediments, including 2001), presumably in part because of great variation in sedimentary
reduction of the solid-phase As to As(III), desorption of As from Fe oxides, characteristics and variations in abstraction depth. Estimates of the
reductive dissolution of the oxides themselves and likely changes in proportions of tubewells affected in West Bengal are not well-documented
Fe-oxide structure and surface properties following the onset of reducing and difficult to assess. However, the indications are that the degree of
conditions (BGS and DPHE, 2001). Deep wells, tapping depths greater than enrichment is not as severe in West Bengal as in the worst-affected (SE)
150–200 m, almost invariably have low As concentrations: less than 5 m g l 1 and districts of Bangladesh (e.g. Dhar et al. 1997). Certainly, the overall areal
usually less than 0.5 m g l 1 ( BGS and DPHE, 2001). Also wells from the older extent of enrichment in West Bengal is less than in Bangladesh.
Plio-Pleistocene sediments of the Barind and Madhupur Tracts have low As
concentrations (Fig. 4). It is a fortunate fact that both Calcutta and Dhaka
draw their water from older sediments and do not have an As problem. The As-affected groundwaters in the Bengal Basin are associated with
Dhaka is sited at the southern tip of the Madhupur Tract (Fig. 4). Dug wells sediments having total As concentrations in the range <2–20 mg kg 1, i.e. not
also generally have low As concentrations, typically <10 m g l 1 ( BGS and exceptional by world-average values. This is not surprising given the scale
DPHE, 2001). of the problem. These sediments are derived from the drainage systems of 3
major rivers (Ganges, Brahmaputra and Meghna) which are themselves
sourced from a wide area of the Himalaya. Therefore, while it could be
argued that the source of much of the As in the Bengal Basin sediments is
derived from specific mineralised areas in the source region, these are likely
The characteristic chemical features of the high-As groundwaters of the to be so widespread as to be academic and of little practical relevance.
Bengal Basin are high Fe (>0.2 mg l 1), Mn (>0.5 mg l 1), HCO 3 (> 500 mg l 1) and
often P (>0.5 mg l 1) concentrations, and low Cl
(<60 mg
l 1), SO 42 (< 1 mg l 1), NO 3 and F (<1 mg l 1) concentrations, with pH values close to
or greater than 7. Measured redox potentials are typically less than 100 mV Isotopic evidence suggests that some groundwater from the Bengal
(PHED, 1991; CGWB, 1999; DPHE/BGS/MML, 1999; BGS and DPHE, Basin has had a long residence time in the aquifers. In Bangladesh, BGS
2001). However, the correlations between dissolved elements are usually far and DPHE (2001) found that 3 H, an indicator of modern groundwater, was
from perfect and where good correlations with As are found, these are only usually detectable at a few TU in the shallowest groundwaters but deeper
applicable locally and are of limited value for quantitative prediction of As groundwaters usually had lower concentrations, typically <0.4 TU. Such low
concentrations, even at a village scale. For example, some workers have concentrations are indicative of older groundwater, with a large proportion
found a positive correlation between As and Fe in village studies (e.g. Nag having been recharged prior to the 1960s. Radiocarbon data also suggest
et al., 1996), but this is not true of Bangladesh and West Bengal as a whole. the presence of old groundwater at some sites. Groundwater from 10– 40 m
One commonly observed relationship in the groundwaters is a general depth in groundwaters from a study area in western Bangladesh was
negative correlation between As and SO 4 concentrations (BGS and DPHE, ‘modern’ since it contained 83% modern C (pmc) or greater, indicating an
2001). This association suggests that As mobilisation is effected under the age of the order of decades. Shallow groundwaters collected from
most strongly reducing conditions, coincident with SO 42- reduction. Some of south-central Bangladesh were also modern (78 pmc or greater), although
the groundwaters of Bangladesh are sufficiently reducing for CH 4 generation groundwater from 150 m was notably older (51 pmc) with a model age of
to have taken place. about 2 ka. Deep groundwaters analysed from southern Bangladesh were
even older with 14 C activities of 28 pmc or less, suggesting the presence of
palaeowaters with ages of the order of 2–12 ka.

Arsenic speciation studies have revealed a large range in the relative

proportions of dissolved arsenate and arsenite present in the groundwaters
(e.g. Das et al., 1995; Acharyya, 1997). The modal proportion of arsenite
appears to be between 50 and 60% of the total As (BGS and DPHE, 2001). The reasons for the distinction between groundwater As concentrations
This may reflect lack of redox equilibrium in the aquifer or a mixed in the shallow and deep aquifers of the Bengal Basin are not yet
groundwater from a strongly stratified aquifer. Low As concentrations are well-understood. Differences between the sediments at depth may occur in
most common in groundwaters from northern Bangladesh and the aquifers terms of absolute As concentrations and in the oxidation states and binding
in Plio-Pleistocene sediments of the uplifted Barind and Madhupur Tracts of properties of the As to the sediments. However, it is also possible that the
north-central Bangladesh. history of groundwater movement and aquifer flushing in the Bengal Basin
has been important in generating the differences in dissolved As
concentrations between the shallow and deep aquifers. Older, deeper
sediments have been subject to longer periods of groundwater flow,
The regional distribution of the high-As waters in West Bengal and
Bangladesh is known to be extremely patchy (PHED, 1991; CSME, 1997;
BGS and DPHE,
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 547

aided by greater hydraulic heads during the Pleistocene period when glacial 5.2.3. Northern China
sea levels around the Bangladesh landmass were up to 130 m lower than Arsenic has been found at high concentrations (in excess of the Chinese
today (e.g. Umitsu, 1993). Flushing of the deeper older aquifers with national standard of 50 m g l 1) in groundwaters from Inner Mongolia as well as
groundwater is therefore likely to have been much more extensive than in Xinjiang and Shanxi Provinces (Fig. 2; Wang, 1984; Wang and Huang,
the Holocene sediments deposited during the last 5–10 ka. Hence, much of 1994; Niu et al., 1997; Smedley et al., 2001a). The first cases of As
the As in the deep sediments may have previously been flushed away. poisoning were recognised in Xinjiang Province in the early 1980s. Wang
Salinity becomes a problem in the near-coastal parts of the aquifers in (1984) found As concentrations up to 1200 m g l 1 in groundwaters from the
southern Bangladesh as a result of saline intrusion (BGS and DPHE, 2001). province. Wang and Huang (1994) reported As concentrations of between
This affects the usability of the shallow aquifer in parts of Bangladesh and 40 and 750 m g l 1 in deep artesian groundwater from the Dzungaria Basin on
means that deep wells, often more than 200 m deep, may need to be the north side of the Tianshan Mountains (from Aibi Lake in the west to
constructed to obtain fresh water. As mentioned above, these almost always Mamas River in the east, a stretch of ca. 250 km). Arsenic concentrations in
have low As concentrations. Other potential sources of low-As water in the artesian groundwater from deep boreholes (up to 660 m) were found to
region are surface water (rivers and ponds), rainwater and dug-well water. increase with depth. Shallow (non-artesian) groundwaters had observed As
concentrations between <10 m g l 1 ( the detection limit) and 68 m g l 1. The
concentration of As in the saline Aibi Lake was reported as 175

5.2.2. Taiwan
Arsenic problems in groundwaters in Taiwan were first recognised during m g l 1, while local rivers had concentrations of between 10 and 30 m g l 1. Artesian
the 1960s (e.g. Tseng et al., 1968) and chronic As-related health problems groundwater has been used for drinking in the region since the 1960s and
have been welldocumented by several workers since then (e.g. Chen et al., chronic health problems have been identified as a result (Wang and Huang,
1985). Taiwan is the classic area for the identification of blackfoot disease 1994).
but a number of other typical health problems, including internal cancers,
have been described. High As concentrations in groundwater have been In Inner Mongolia, concentrations of As in excess of 50 m g l 1 have been
recognised in both the SW (Tseng et al., 1968) and NE (Hsu et al., 1997) of identified in groundwaters from aquifers in the Ba Men region and the Tumet
the island. Plain, which includes the Huhhot Basin (e.g. Luo et al., 1997; Ma et al.,
1999). These areas include the towns of Boutou and Togto. In the Huhhot
Basin, the problem is found in groundwaters from Holocene alluvial and
Kuo (1968) observed As concentrations in groundwater samples from lacustrine aquifers under highly reducing conditions and is worst in the
SW Taiwan ranging between 10 and 1800 m g l 1 ( mean 500 m g l 1, n= 126) and lowest-lying parts of the basin (Smedley et al., 2001a). Concentrations up to
found that half the samples analysed had concentrations between 400 and 1500 m g l 1 have been found in the groundwaters, with a significant
700 m g l 1. A large study carried out by the Taiwan Provincial Institute of proportion (60–90%) of the As being present as As(III). Some shallow dug
Environmental Sanitation established that 119 townships in the affected area wells also have groundwater with relatively high As concentrations (up to
had As concentrations in groundwater of >50 m g l 1 556 m g l 1;

and 58 townships had >350 m g l 1 ( Lo et al., 1977). In north-eastern Taiwan,

Hsu et al. (1997) found As concentrations in some groundwaters exceeding Smedley et al., 2001a). Shallow groundwaters in parts of the region are
600 m g l 1, saline as a result of evaporative concentration exacerbated by irrigation and
with an average of 135 m g l 1 ( 377 samples). many have high F concentrations, although the F does not generally
In the SW, the high As concentrations are found in groundwaters from correlate with As. In the affected region, As-related disease has been
deep artesian wells (mostly 100–280 identified by Luo et al. (1997). Recognised health effects include lung, skin
m) abstracted from sediments which include fine sands, muds and black and bladder cancer as well as prevalent keratosis and skin-pigmentation
shale (Tseng et al., 1968). Groundwaters abstracted from the NE of Taiwan problems.
are also artesian, but of shallower depth (typically in the range 16– 40 m;
Hsu et al., 1997). In each area, the groundwaters are likely to be strongly
reducing, a hypothesis supported by the observation that the As is present 5.2.4. Vietnam
largely as As(III) (Chen et al., 1994). However, both the geochemistry of the The aquifers of the large deltas of the Mekong and Red Rivers are now
groundwaters and the mineral sources in Taiwan are poorly defined at widely exploited for drinking water. The total number of tubewells in Vietnam
present. Groundwater samples taken from shallow open dug wells are is unknown but could be of the order of one million, with perhaps
observed to have low As concentrations (Guo et al., 1994).
150,000 in the Red River delta region. The majority of these are private
tubewells. The capital city, Hanoi, is now largely dependent on groundwater
for its public
548 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

water supply. The aquifers exploited are of both Holocene and Pleistocene lowest parts of the basin, where the sediment is finegrained. Gurzau and
age. In parts of the Red River delta region, Holocene sediments form the Gurzau (2001) reported As concentrations up to 176 m g l 1 in the associated
shallow aquifer which may be only 10–15 m deep. Where absent, older aquifers of neighbouring Romania (Table 7).
Pleistocene sediments are exposed at the surface. Unlike Bangladesh, even
when the Holocene sediments are present, there is not always a layer of fine
silt-clay at the surface. Normally the Holocene sediments are separated 5.3. Arid oxidising environments
from the underlying Pleistocene sediments by a clay layer several metres
thick, although ‘windows’ in this clay layer exist where there is hydraulic 5.3.1. Mexico
continuity between the Holocene and Pleistocene aquifers. The total The Lagunera Region of north central Mexico has a well-documented As
thickness of sediments is typically 100–200 m. problem in groundwater with significant resulting chronic health problems.
The region is arid and groundwater is an important resource for potable
supply. Groundwaters are predominantly oxidising with neutral to high pH.
Del Razo et al. (1990) quoted pH values for groundwaters in the range 6.3
The groundwaters in the delta regions are usually strongly reducing with to
high concentrations of Fe, Mn and NH 4. Much of the shallow aquifer in the
Vietnamese part of the Mekong delta region is affected by salinity and 8.9. They found As concentrations in the range 8 to 624
cannot be used for drinking water. Little was known about the As m g l 1 ( average 100 m g l 1, n= 128), with half the samples having concentrations
concentrations in groundwater in Vietnam until recently. UNICEF and greater than 50 m g l 1. They also noted that most (>90%) of the groundwater
EAWAG/CEC (Hanoi National University) have been carrying out extensive samples investigated had As present predominantly as As(V). Del Razo et
investigations to assess the scale of the problem. Results from Hanoi al. (1994) determined the average concentration of As in drinking water from
(Wegelin et al., 2000; Berg et al., 2001) indicate that there is a significant As Santa Ana town in the region as 404 m g l 1. The estimated population
problem in shallow tubewells in the city, particularly in the south. exposed to As in drinking water with >50 m g l 1 is around 400,000 in
Concentrations in the range 1–3050 m g l 1 ( average 159 Lagunera Region (Del Razo et al.,

1990). Groundwaters from the region also have high concentrations of F-

m g l 1) were reported by Berg et al. (2001). There appears to be a large (up to 3.7 mg l 1; Cebria´ n et al.,
seasonal variation with significantly lower concentrations having been found 1994).
at most investigated sites during sampling in May (early rainy season). This High As concentrations have also been identified in groundwaters from
could be related to the local hydrology since there are significant interactions the state of Sonora in NW Mexico. Wyatt et al. (1998) found concentrations
between the aquifer and the adjacent Red River. Little is known about the in the range 2– 305 m g l 1 ( 76 samples) with highest concentrations in
As concentrations in groundwater from the middle and upper parts of the groundwaters from the towns of Hermosillo, Etchojoa, Magdalena and
Mekong delta (and into adjacent Cambodia and Laos) and other smaller Caborca. The As concentrations were also positively correlated with F. The
alluvial aquifers in Vietnam but investigations are presently taking place. highest observed F concentration in the area was 7.4 mg l 1. The reasons for
the correlation in this case are uncertain. It is also believed that high-As
groundwaters have been found in other parts of northern Mexico.

5.2.5. Hungary and Romania

Concentrations of As above 50 m g l 1 have been identified in 5.3.2. Chile
groundwaters from alluvial sediments in the southern part of the Great Health problems related to As in drinking water were first recognised in
Hungarian Plain (Fig. 3) of Hungary and neighbouring parts of Romania. northern Chile in 1962. Typical symptoms included skin-pigmentation
Concentrations up to 150 m g l 1 ( average 32 m g l 1, 85 samples) have been changes, keratosis, squamous-cell carcinoma (skin cancer), cardiovascular
found by Varsa´ nyi et al. (1991). The Plain, some 110,000 km 2 in area, problems and respiratory disease (Zaldivar,
consists of a thick sequence of subsiding Quaternary sediments.
Groundwaters vary from Ca–Mg–HCO 3- type in the recharge areas of the 1974). More recently, As ingestion has been linked to lung and bladder
basin margins to Na–HCO 3- type in the lowlying discharge regions. cancer. It has been estimated that around 7% of all deaths occurring in
Groundwaters in deep parts of the basin (80–560 m depth) with high As Antofagasta between 1989 and 1993 were due to past exposure to As in
concentrations are reducing with high concentrations of Fe and NH 4 drinking water at concentrations of the order of 500

m g l 1 ( Smith et al., 1998). Since exposure was chiefly in the period

1955–1970, this pointed to a long latency period of cancer mortality. Other
and many have reported high concentrations of humic acid (up to 20 mg l 1; Varsa´ reported symptoms include impaired resistance to viral infection and lip
nyi et al., 1991). The groundwaters have highest As concentrations in the herpes (Karcher et al., 1999).
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 549

High As concentrations have been reported in surface waters and l 1 ( median 255 m g l 1). Nicolli and Merino (2002) in a study of the Carcaran˜ a´
groundwaters from Administrative Region II (incorporating the cities of River Basin (Co´ rdoba and Santa Fe Provinces) found concentrations in the
Antofagasta, Calama and Tocopilla) of northern Chile (Ca´ ceres et al., range <10– 720 m g l 1 ( mean 201 m g l 1). Smedley et al. (1998,
1992). The region is arid (Atacama Desert) and water resources are limited.
High As concentrations are accompanied by high salinity and high B 2002) found concentrations for groundwaters in La Pampa Province in the
concentrations. This in part relates to evaporation but is also thought to be range <4–5280 m g l 1 ( median 145 m g l 1). Nicolli et al. (2001) found
significantly affected by geothermal inputs from the El Tatio geothermal field. concentrations in groundwaters from Tucuma´ n Province of 12–1660 m g l 1 ( median
Arsenic concentrations below 100 m g l 1 in surface waters and groundwaters 46 m g l 1). The groundwaters often have high salinity and the As
are apparently quite rare, and concentrations up to 21,000 concentrations are generally well-correlated with other anion and oxyanion
elements (F, V, HCO 3, B, Mo). They are also predominantly oxidising with
low dissolved Fe and Mn concentrations. Under the arid conditions, silicate
and carbonate weathering reactions are pronounced and the groundwaters
m g l 1 have been found. Karcher et al. (1999) quoted ranges of 100 m g l 1 to often have high pH values. Smedley et al. (2002) found pH values typically
1000 m g l 1 in raw waters (average 440 m g l 1). The affected waters of Chile of 7.0–8.7; Nicolli et al. (2001) found pH values of 6.3–9.2. Arsenic is
are taken to be predominantly oxidising (with dissolved O 2 present), largely dominantly present as As(V) (Smedley et al., 2002). Metal oxides in the
because the As is reported to be present in the waters as arsenate sediments (especially Fe and Mn oxides and hydroxides) are thought to be
(Thornton and Farago, 1997 and references cited therein). However, the the main source of dissolved As, caused by desorption under high-pH
geochemistry of the aquifers of Chile is as yet poorly understood. The conditions (Smedley et al., 1998, 2002), although the direct dissolution of
aquifers are composed of volcanic rocks and sediments, but the As sources volcanic glass has also been cited as a potential source (Nicolli et al., 1989).
are not well-characterised. In Antofagasta, concentrations of As in the
sediments are ca. 3.2 mg kg 1 ( Ca´ ceres et al., 1992). Additional As
exposure from smelting of Cu ore has also been noted in northern Chile
(Ca´ ceres et al., 1992).

Arsenic treatment plants were installed in the towns of Antofagasta and 5.4. Mixed oxidising and reducing environments
Calama in 1969 to mitigate the problems. Today, the urban populations of
the major towns are supplied with treated water from the Rivers Toconce 5.4.1. South-western USA
and Loa (Karcher et al., 1999) which is transported from the foot of the Many areas have been identified in the USA with As problems in
Andes mountains to the treatment works. However, rural communities still groundwater. Most of the worst-affected and best-documented cases occur
largely rely on untreated water supplies which contain As. in the south-western states (Nevada, California, Arizona). However, within
the last decade, aquifers inMaine, Michigan, Minnesota, South Dakota,
Oklahoma and Wisconsin have been found with concentrations of As
exceeding 10 m g l 1 and smaller areas of high As groundwaters have been
5.3.3. Argentina found in many other States. Much water analysis and research has been
The Chaco-Pampean Plain of central Argentina constitutes perhaps one carried out in the USA, particularly in view of the long-proposed reduction in
of the largest regions of high-As groundwaters known, covering around 1 10 6 the US-EPA drinkingwater maximum contaminant level and public concern
km 2. over the possible long-term health effects. Occurrences in groundwater are
High concentrations of As have been documented from Co´ rdoba, La therefore noted to be widespread, although of those reported, relatively few
Pampa, Santa Fe, Buenos Aires and Tucuma´ n Provinces in particular. have significant numbers of sources with concentrations greater than 50 m g
Symptoms typical of chronic As poisoning, including skin lesions and some l 1. A recent review of the analyses of some
internal cancers, have been recorded in these areas (e.g. Hopenhayn-Rich
et al., 1996). The climate is temperate with increasing aridity towards the
west. The high-As groundwaters are from Quaternary deposits of loess
(mainly silt) with intermixed rhyolitic or dacitic volcanic ash (Nicolli et al.,
1989; Smedley et al., 1998, 2002). The sediments display abundant 17,000 water analyses from the USA concluded that around 40% exceeded
evidence of post-depositional diagenetic changes under semi-arid 1 m g l 1 and about 5% exceeded 20 m g l 1 ( percentage above 50 m g l 1 unknown;
conditions, with common occurrences of calcrete in the form of cements, Welch et al., 1999). The As is thought to be derived from various sources,
nodules and discrete layers, sometimes many centimetres thick. including natural dissolution/desorption reactions, geothermal water and
mining activity. The natural occurrences of As in groundwater occur under
both reducing and oxidising conditions in different areas. Concentration by
evaporation is thought to be an important process in the more arid areas.

Nicolli et al. (1989) found As concentrations in groundwaters from Co´

rdoba in the range 6–11500 m g
550 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

In Nevada, at least 1000 private wells have been found to contain As New Zealand, Chile, Iceland, Kamchatka, France and Dominica (e.g. White
concentrations in excess of 50 m g l 1 ( Fontaine, 1994). The city of Fallon, et al., 1963; Welch et al., 1988; Criaud and Fouillac, 1989). Parts of Salta
Nevada (population 8000) is served by a groundwater supply with an As and Jujuy Provinces in NW Argentina also have thermal springs with high As
concentration of 100 m g l 1 which for many years has been supplied without concentrations. In the USA, occurrences of As linked to geothermal sources
treatment other than chlorination. Welch and Lico (1998) reported high As have been summarised by Welch et al. (1988, 2000). Reported occurrences
concentrations, often exceeding 100 m g l 1 but with extremes up to 2600 m g l 1, include Honey Lake Basin, California (As up to 2600 m g l 1), Coso Hot
in shallow groundwaters from the southern Carson Desert. These are largely Springs, California (up to 7500 m g l 1),
present under reducing conditions, having low dissolved-O 2 concentrations
and high concentrations of dissolved organic C, Mn and Fe. The
groundwaters also have associated high pH (>8) and high concentrations of Imperial Valley, California (up to 15,000 m g l 1), Long Valley, California (up to
P (locally >4 mg l 1) and U (>100 m g l 1; Welch and Lico, 1998). The high As 2500 m g l 1) and Steamboat Springs, Nevada (up to 2700 m g l 1). Geothermal
and U concentrations were thought to be due to evaporative concentration waters in Yellowstone National Park also contain high concentrations of As.
of groundwater, combined with the influence of redox and desorption Thompson and Demonge (1996) reported concentrations of <1–7800 m g l 1 in
processes involving metal oxides. geysers and hot springs; values up to 2830 m g l 1 were reported by Ball et al.
(1998). These geothermal sources have given rise to high concentrations of
As (up to 370 m g l 1) in waters of the Madison River (Nimick et al., 1998).
Geothermal waters at Lassen Volcanic National Park, California have As
concentrations ranging up to 27,000 m g l 1 ( Thompson et al., 1985). An As
concentration of 3800 m g l 1 has also been reported from Geyser Bight,
In groundwaters from the Tulare Basin of the San Joaquin Valley, Umnak Island, Alaska (White et al., 1963). Geothermal inputs from Long
California, a large range of groundwater As concentrations from <1 m g l 1 to Valley, California are believed to be responsible for relatively high
2600 m g l 1 concentrations (20 m g l 1)
have been found (Fujii and Swain, 1995). Redox conditions in the aquifers
appear to be highly variable and high As concentrations are found in both
oxidising and reducing conditions. The proportion of As present as As(III)
increases in the groundwaters with increasing well depth. The groundwaters
from the Basin are often strongly affected by evaporative concentration with of As in the Los Angeles Aqueduct which provides the water supply for the
resulting high TDS values. Many also have high concentrations of Se (up to city of Los Angeles (Wilkie and Hering, 1998). Geothermal inputs also
1000 m g l 1), U (up to 5400 m g l 1), B ( up to 73,000 m g l 1) and Mo (up to 15,000 m contribute significantly to the high dissolved As concentrations (up to 20 mg l 1)
g l 1; Fujii and Swain, 1995).
in Mono Lake, California (Maest et al., 1992).
Welch et al. (1988) noted a general relationship between As and salinity
in geothermal waters from the USA. Despite a lack of good positive
Robertson (1989) also noted the occurrence of high As concentrations in correlation between As and Cl, geothermal waters with As greater than ca.
groundwaters under oxidising conditions in alluvial aquifers in the Basin and 1000 m g l 1 mostly had Cl concentrations of 800 mg l 1 or more. Wilkie and
Range Province in Arizona. Dissolved O 2 values of the groundwaters were in Hering (1998) noted the high alkalinity and pH values (average pH 8.3) as
the range 3–7 mg l 1. Arsenic in the groundwater was found from a limited well as high Cl and B concentrations of As-rich geothermal waters in Long
number of samples to be present predominantly as As(V). The dissolved As Valley. Of 26 geothermal water samples analysed from 5 geothermal fields
correlated well with Mo, Se, V, F and pH, the latter being in the range in Kyushu, Japan, As concentrations have been reported in the range 500–
6.9–9.3. Of the 467 samples analysed, 7% had As concentrations greater 4600 m g l 1. The waters are typically of Na–Cl type and the As is present in all
than 50 m g l 1. Arsenic concentrations in the sediments ranged between 2 but one sample overwhelmingly as As(III) (Yokoyama et al., 1993).
and 88 mg kg 1. Oxidising conditions (with dissolved O 2 present) were found to
persist in the aquifers down to significant depths (600 m) despite significant
groundwater age (up to 10 ka old). The high As (and other oxyanion)
concentrations are a feature of the closed basins of the province.
Robinson et al. (1995) found an As concentration in waste geothermal
brine from the main drain at the Wairakei geothermal field in New Zealand of
3800 m g l 1. River and lake waters receiving inputs of geothermal water from
the Wairakei, Broadlands, Orakei Korako and Atiamuri geothermal fields
have As concentrations up to 121 m g l 1, although concentrations are reported
to diminish significantly downstream away from the geothermal input areas.
5.5. Geothermal sources

As noted above, As associated with geothermal waters has been

reported in several parts of the world, including hot springs from parts of the High As concentrations have been found in geothermal waters from the
USA, Japan, El Tatio system in the Antofagasta
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 551

region of Chile. The geothermal area lies in a basin (altitude 4250 m) with a median concentration in tubewell waters of just 2
between the volcanoes of the Andes and the Serrania de Tucle. The m g l 1. Some higher concentrations were observed (up to 64 m g l 1) but these
geothermal waters are highly saline (Na–Cl solutions with Na concentrations were not generally in the vicinity of the mines or related directly tomining
in the range 2000–5000 mg l 1). Arsenic concentrations of the waters are activity. Rather, the higher concentrations were found to be present in
reported to be in the range 45,000–50,000 m g l 1 ( Ellis and Mahon, 1977). relatively reducing groundwaters (Eh 220–250 mV). Oxidising groundwaters,
White et al. (1963) also reported As concentrations in the range 50–120 m g l 1 especially from shallow hand-dug wells, had low As concentrations. This
for thermal waters from Iceland and in the range 100–5900 m g l 1 was taken to be due retardation of As by adsorption onto hydrous ferric
oxides under the ambient low pH condition of the groundwaters (median pH
5.4 in dug wells; 5.8 in tubewells; Smedley, 1996; Smedley et al., 1996).
for thermal waters from Kamchatka.

5.6. Sulphide mineralisation and mining-related arsenic problems

5.6.3. United States

5.6.1. Thailand Arsenic contamination from mining activities has been identified in
Probably the worst case of As poisoning related to mining activity known numerous areas of the USA, many of which have been summarised by
is that of Ron Phibun District in Nakhon Si Thammarat Province of southern Welch et al. (1988;
Thailand. Health problems were first recognised in the area in 1999). Groundwater from some areas has been reported to have very high
As concentrations locally (up to 48,000
1987. By the late 1990s, around 1000 people had been diagnosed with m g l 1). Well-documented cases of As contamination include the Fairbanks
As-related skin disorders, particularly in and close to Ron Phibun town Au-mining district of Alaska (Wilson and Hawkins, 1978; Welch et al., 1988),
(Williams, 1997; Choprapawon and Rodcline, 1997). The affected area lies the Coeur d’Alene Pb–Zn–Ag mining area of Idaho, (Mok and Wai, 1990),
within the SE Asian Tin Belt. Arsenic concentrations up to 5000 m g l 1 have Leviathan Mine, California (Webster et al., 1994), Kelly Creek Valley,
been found in shallow groundwaters from Quaternary alluvial sediment that Nevada (Grimes et al.,
has been extensively dredged during Sn-mining operations. Deeper
groundwaters from an older limestone aquifer have been found to be less 1995), Clark Fork river, Montana (Welch et al., 2000) and Lake Oahe in
contaminated (Williams et al., 1996) although a few high As concentrations South Dakota (Ficklin and Callender,
occur, presumably also as a result of contamination from the mine workings. 1989). Some mining areas of the USA have significant problems with acid
The mobilisation of As is believed to be caused by oxidation of arsenopyrite, mine drainage resulting from extensive oxidation of Fe sulphide minerals. In
exacerbated by the former Sn-mining activities. The recent appearance in these, pH values can be extremely low and Fe oxides, produced from the
groundwater has occurred during post-mining groundwater rebound oxidation reaction, dissolve and release bound As. Iron Mountain has some
(Williams, 1997). extremely acidic minedrainage waters with negative pH values and As
concentrations in the mg l 1 range (Nordstrom et al., 2000).

In Wisconsin, As and other trace-element problems in groundwater have

arisen as a result of the oxidation of sulphide minerals (pyrite and marcasite)
5.6.2. Ghana present as a discrete secondary cement horizon in the regional Ordovician
Ghana is an important Au-mining country and mining has been active sandstone aquifer. Concentrations of As up to 12,000 m g l 1 have been
since the late 19th century. Today, Ghana produces about one third of the reported in the well waters (Schreiber et al., 2000). The oxidation appears to
world’s Au. The most important mining area is the Ashanti Region of central have been promoted by groundwater abstraction which has led to the
Ghana. As with Ron PhibunDistrict in Thailand, the Au is associated with lowering of the piezometric surface at a rate of around 0.6 m a 1 since the
sulphide mineralisation, particularly arsenopyrite. Arsenic mobilises in the 1950s with partial dewatering of the aquifer. The high As concentrations are
local environment as a result of arsenopyrite oxidation, induced (or observed where the piezometric surface intersects, or lies close to, the
exacerbated) by the mining activity. Around the town of Obuasi, high As sulphide cement horizon (Schreiber et al., 2000).
concentrations have been noted in soils close to the mines and treatment
works (Amasa, 1975; Bowell, 1992; 1993). Some high concentrations have
also been reported in river waters close to the mining activity (Smedley et
al., 1996).
5.6.4. Other areas
Many other areas have increased concentrations of As in water, soils,
sediments and vegetation as a result of local mineralisation, exacerbated by
Despite the presence of high As concentrations in the contaminated soils mining activity. Documented cases include the Lavrion region of Greece,
and in bedrocks close to the mines, Smedley et al. (1996) found that many associated with Pb and Ag mining (Komnitsas et al., 1995), the Zimapa´ n
of the groundwaters of the Obuasi area had low As concentrations, Valley of Mexico (Armienta
552 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

et al., 1997), parts of SW England (Thornton and Farago, 1997), South since in this case mobilisation of As is not an issue: As is already present in
Africa and Zimbabwe (Jonnalagadda and Nenzou, 1996). Although severe solution and the size of geothermal reservoirs can be large. Perhaps more
contamination of the environment has often been documented in these puzzling is the way in which exceptionally high concentrations of As, up to
areas, the impact on groundwaters used for potable supply is usually minor. several mg l 1, are found in groundwaters from areas with apparently
near-average source rocks. In aquifers with extensive high-As groundwater,
this appears to be the rule rather than the exception. Most of these cases
Increased concentrations of dissolved As have also been found in parts arise in aquifers derived from relatively young aquifer materials, often
of the world with local mineralisation which has not been mined. Boyle et al. consisting of alluvium or loess where the total As concentrations in the
(1998) recorded concentrations up to 580 m g l 1 in groundwaters from an sediments are usually in the range 1–20 mg kg 1. Recognition of this fact is a
area of sulphide mineralisation in Bowen Island, British Colombia. Heinrichs recent development and its late appreciation has delayed the discovery of
and Udluft (1999) found often high concentrations in groundwater from the many high-As groundwater provinces.
Upper Triassic Keuper Sandstone in northern Bavaria. Out of 500 wells, 160
had As concentrations in the range 10–150 m g l 1. The nature of the
mineralisation in this aquifer was not clearly identified. As yet unidentified
areas of mineralisation could be quite widespread, although these are likely
to be on a local scale. A critical point is that the drinking-water limit for As is very low in relation
to the overall abundance of As in the natural environment. Fortunately, most
of this As is normally immobilised by various minerals, particularly Fe oxides,
and so is not available for abstraction. However, it only takes a small
percentage of this ‘solid’ As to dissolve or desorb to give rise to a serious
groundwater problem. This can provide an explanation for both the oxidising
6. Common features of groundwater arsenic problem areas and reducing high-As environments. An abundant source of Fe oxides with
its surface-bound and coprecipitated As provides a ready source of As that
may be released given an appropriate change in geochemical conditions.
6.1. A hydrogeochemical perspective

Historically, as new sources of high As groundwaters have been found,

treatment plants have been built and the problem has receded from public
attention. Although much recent research has been carried out in the USA,
there have been few detailed hydrogeochemical and hydrogeological studies 6.3. Arsenic mobilisation—the necessary geochemical trigger
in the As-affected aquifers from many other parts of the world. Despite this,
sufficient is already known that it is useful to attempt to bring together some
of the common features and to speculate about the critical factors that can There appear to be two key factors involved in the formation of high-As
lead to high-As groundwaters. This will help to focus future scientific studies groundwaters on a regional scale: firstly, there must be some form of
and should provide some guidance to water providers who have to geochemical trigger which releases As from the aquifer solid phase into the
undertake a rapid assessment of water supplies for As. It is helpful to groundwater. Secondly, the released As must remain in the groundwater
consider the formation of high-As groundwaters in terms of the 3 major and not be flushed away. There are a number of possible geochemical
factors involved, namely, the source of the As, triggers. In mining and mineralised areas, oxidation of sulphide ores may be
triggered by influxes of O 2 or other oxidising agents. However, in most
As-affected aquifers, the most important trigger appears to be the
desorption/dissolution of As from oxide minerals, particularly Fe oxides. An
its important feature of this process is that the initial adjustment is probably
mobilisation, and its subsequent transport (or lack of it). quite rapid since it involves a shift from one point on the adsorption isotherm
to another and adsorption reactions, being surface reactions, are usually
6.2. The source of arsenic rapid. The rate-limiting factors are probably those controlling the major
changes in pH, Eh and associated water quality parameters of the aquifer.
In the cases where affected groundwaters are found close to obvious These are in part related to physical factors such as the rate of diffusion of
geological or industrial sources rich in As (geothermal springs, drainage gases through the sediment and the rate of sedimentation, in part due to the
from mineralised and mining areas, specific contaminant sources), it is clear extent of microbiological activity and in part related to the rates of chemical
that the anomalously high As concentrations in the source region are reactions. However, many of these factors
responsible. The extent of this contamination is usually highly localised
because the geochemical conditions within most aquifers do not favour As
mobilisation on a regional scale. Areas affected by geothermal activity are
potentially more widespread
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 553

are likely to be rapid on a geological time scale (tens of thousands of years at pH 7 with a river water containing 1 m g l 1 of As and
and longer). Dissolution reactions are slower but even oxide dissolution is 0.05 mol l 1 NaCl, then according to the DLM, HFO has an As loading of
rapid on a geological time scale and can be observed in a matter of weeks almost 15,000 mg kg 1. This is equivalent to 23 mg As kg 1 sediment. If the pH
or even days in flooded soils (Ponnamperuma et al., 1967; Masscheleyn et is then raised while maintaining a constant total As concentration in the
al., 1991). sediment plus porewater, equivalent to evolution within a ‘closed’ system,
then desorption of As occurs (Fig. 5). There is a sharp increase in porewater
A qualification is that if diagenetic changes to the oxide mineral structure As concentration above pH 8.5. Above pH 9, the As(V) concentration can
are important (see below) or if burial of sediment is important, then there exceed 1000 m g l 1. An ionic strength of 0.05 M is greater than found in most
could be a slow release of As over a much longer time scale. Details of the river waters but is useful for maintaining a constant ionic strength in the
rate of release of As and how this varies with time are not yet clear. It is calculations. Normally the effects of changes in ionic strength are relatively
likely that the rate will diminish with time with the greatest changes occurring small. This system assumes no competing anions in solution.
in the early stages. Natural groundwater flushing means that very slow
releases of As are likely to be of little consequence since the As released
will not tend to accumulate to a significant extent. A corollary of this
hypothesis is that once the diagenetic readjustment has taken place and the
sediments have equilibrated with their new environment, there should be More realistically, other anions (e.g. phosphate, bicarbonate and silicate)
little further release of As. This contrasts with some mineral-weathering in the river water will compete for sorption sites on the HFO and thereby
reactions which occur in ‘open’ systems and can continue for millions of reduce the initial As loading. If we assume for example that the river water
years until all of the mineral has dissolved. Seen in this context, the also contains 10 m g l 1 phosphate-P, then the initial As loading is reduced to
desorption/dissolution of As from metal oxides in young aquifers is 5600 mg kg 1 HFO. However, while this reduces the As release at high pH to
essentially a step change responding to a new set of conditions. As some extent, the pH effect is still strong (Fig. 5). Phosphate (and other
discussed above, the type of reactions that may occur can be seen today adsorbed anions) are also released along with As at high pH. At pH 9, the
most clearly where they occur at a small spatial scale and over a short time calculated total P concentration in the above example is 13 mg l 1.
scale, for example, across a redox boundary in a lake sediment. The
geochemical triggers involved could arise for a number of possible reasons.
Below the authors speculate what these might be. Some model calculations
of their possible impact are given in BGS and DPHE (2001). There are several reasons why the pH might increase but the most
important in the present context is the uptake of protons by mineral
weathering and ionexchange reactions, combined with the effect of
evaporation in arid and semi-arid regions. This pH increase is commonly
associated with the development of salinity and the salinisation of soils.
Inputs of high-pH geothermal waters may be important in maintaining high
As

6.3.1. Desorption at high pH under oxidising conditions

Under the aerobic and acidic to near-neutral conditions typical of many
natural environments, As is very strongly adsorbed by oxide minerals as the
arsenate ion. The highly non-linear nature of the adsorption isotherm for
arsenate ensures that the amount of As adsorbed is relatively large, even
when dissolved concentrations of As are low. Adsorption protects many
natural environments from widespread As toxicity problems. As pH
increases, especially above pH 8.5, As desorbs from the oxide surfaces,
thereby increasing the concentration of As in solution. The impact of this is
magnified by the high solid/solution ratios typical of aquifers (3–10 kg l 1).

It is possible to demonstrate this effect with some model calculations.

The Dzombak and Morel (1990) diffuse double layer model (DLM) for
hydrous ferric oxide (HFO), and its accompanying thermodynamic database,
provides a simple means of calculating the amount of As adsorbed under
various conditions. If we assume that a sandy sediment with 25%porosity
contains 1 g Fe kg 1 as HFO and that it is initially in equilibrium Fig. 5. Calculated increase in As concentration when the pH of a sediment containing 1
g kg 1 Fe as HFO is increased from its initial value of pH 7 under closed-system
conditions.
554 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

concentrations in some alkaline lakes. Desorption at high pH is the most concentrations. Other high-pH environments (up to pH
likely mechanism for the development of groundwater-As problems under 8.3), particularly open-system calcareous environments, are likely to be too
the oxidising conditions and would account for the observed positive well flushed to allow any released As to have accumulated. Since calcium
correlation of As concentrations with increasing pH (e.g. Robertson, 1989; arsenate is highly insoluble, it is also likely that arsenate will be strongly
Smedley et al., 2002). sorbed by calcium carbonate minerals, although this has not been
demonstrated.
As such a pH increase induces the desorption of a wide variety of
oxyanions, other oxyanions such as phosphate, vanadate, uranyl and The pH dependence of adsorption is critical but has not yet been
molybdate will also tend to accumulate. There is evidence that this is indeed measured in detail for any aquifer materials, especially in the presence of
the case (Smedley et al., 2002). These specificallyadsorbed anions all typical groundwater compositions. The pH dependence is likely to depend to
interact with the adsorption sites on the oxides in a competitive way and so some extent on the heterogeneity of the aquifer material. Other specifically
influence, in a complex way, the extent of binding of each other. This is not adsorbed anions, particularly phosphate and perhaps HCO 3, may also
well understood in a quantitative sense. Phosphate in particular may play an significantly affect the pH dependence of As(V) and As(III) binding. High pH
important role in As binding since it is invariably more abundant than As, values cannot explain the development of high As concentrations in
often by a factor of 50 or more (in molar terms), and is also strongly bound reducing environments such as Bangladesh since groundwaters in reducing
to oxide surfaces. At pH 7, arsenate is as strongly sorbed as phosphate environments normally have a near-neutral pH.
(Hingston et al., 1971). The role of HCO 3 , often the major anion in
As-affected groundwaters, in promoting the desorption of arsenate is unclear
at present. Wilkie and Hering (1996) did not find any large effects of 1 mM
HCO 3 on As(V) or As(III) sorption by HFO at pH 6 and 9 (but greatest for
As(III) at pH 9). Recent studies have shown that a high 6.3.2. Arsenic desorption and dissolution due to a change to reducing
conditions
The onset of strongly reducing conditions, sufficient to enable Fe(III) and
probably SO 4 reduction to take place, appears to be another trigger for the
release of As. The most common cause of this is the rapid accumulation and
burial of sediments. This occurs in river valleys, especially in broad valleys
p CO and implicitly HCO 3 concentration) significantly reduces the binding of
2( with wide meandering river channels carrying heavy sediment loads. Large,
chromate, another strongly sorbed anion, by goethite (Villalobos et al., rapidly advancing deltas are an extreme case. The organic C content of the
2001). Bicarbonate concentrations in high-As groundwaters usually exceed buried sediment will largely determine the rate at which reducing conditions
300 mg l 1 ( 5 mM) (Smedley et al., 1998; 2001a BGS and DPHE, 2001) and are created. Freshly-produced soil organic matter readily decomposes and it
can exceed 1000 mg l 1 ( 16 does not take much of this to use up all of the dissolved O 2, NO 3 and SO 4. Reducing
conditions can only be maintained if the diffusion and convection of
mM). Hence, experiments need to be extended to these high concentrations dissolved O 2 and other oxidants from the surface is less rapid than their
to verify the role of HCO 3 in sorption processes. consumption. This is helped if there is a confining layer of fine-grained
material close to the surface. This often occurs in large deltas where
The role of dissolved organic C (fulvic and humic acids) is also uncertain, finegrained overbank deposits overlie coarser-grained alluvial deposits.
at least from a quantitative point of view. Humic substances have been
shown to reduce As(III) and As(V) sorption by Fe oxides under some
conditions (Xu et al., 1991; Bowell, 1994) and high-As groundwaters are
associated with high humicacid concentrations in some aquifers (Smedley et
al., 2001a). However, direct evidence for a causal link between dissolved
organic C and As desorption does not yet exist.
While the detailed reactions (in surface chemical terms) that occur when
reduction takes place are not well understood, the change from normally
strongly adsorbed As(V) to normally less strongly adsorbed As(III) may be
Some cations, because of their positive charge, may promote the one of the first reactions to take place, although not all the evidence
adsorption of negatively charged arsenate (Wilkie and Hering, 1996). supports this (e.g. De Vitre et al., 1991). A change in the redox state of the
Calcium and Mg are likely to be the most important cations in this respect adsorbed ions could have wider-ranging repercussions since it will also
because of their abundance in most natural waters and their +2 charge. affect the extent to which other anions can compete for adsorption sites.
Divalent Fe may be important in reduced waters and Al in acidic waters. Phosphate-arsenite competition, for example, is likely to be less important
Silica also exerts a control on the sorption of As (Swedlund and Webster, than phosphatearsenate competition. There is also the potential for
1998). arsenite-arsenate competition. Model calculations suggest that adsorbed
phosphate can reverse the relative
The aridity described above enables the high pH values to be maintained
and minimises the flushing of the As. It also allows the build-up of high Cl
and F
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 555

affinity of As(III) and As(V) at near-neutral pH values (BGS and DPHE,

2001). These complexities are poorly understood at present but are
important if reliable quantitative predictions of As concentrations under
reducing conditions are to be made.

In the absence of other specifically adsorbed anions, As(III) adsorption

by Fe oxides is practically independent of pH. This contrasts sharply with
that of As(V) as described above. In the ‘real world’, some pH dependence
in As(III) adsorption will be induced by secondary interactions arising from
the pH dependence of other specifically adsorbed and competing ions such
as phosphate and even As(V).

6.3.3. Reduction in surface area of oxide minerals

Disordered and fine-grained Fe oxides, which may include HFO,
lepidocrocite, schwertmannite and magnetite, are commonly formed in the
early stages of weathering. Freshly-precipitated HFO is extremely
finegrained with cluster sizes of about 5 nm diameter and a specific surface
area of 600 m 2 g 1 or greater. HFO gradually transforms (crystallises) to more
ordered forms such as goethite or hematite with correspondingly large
crystal sizes and reduced surface areas. This ‘ageing’ reaction can take
place rapidly in the laboratory but the rate in nature is likely to be somewhat
inhibited by the presence of other ions, particularly by strongly adsorbed loading, and are therefore sensitive to all the interactions that control the
ions such as Al, PO 4, SO 4, AsO 4, HCO 3 and silicate (Cornell and Schwertmann, isotherm. For example, for As(III) which has a close-to-linear isotherm at
1996). typical groundwater concentrations, the effect of a reduction in surface area
is less dramatic and is closer to a linear function of the surface-area
reduction.

One consequence of this reduction in surface area is that the amount of

of 600 m 2 g 1 under closed-system conditions.
As(V) adsorption may decrease on a weight for weight basis. If the site 6.3.4. Reduction in binding strength between arsenic and mineral surfaces
density (site nm 2)
and binding affinities of the adsorbed ions remain constant, then as the While the calculations outlined above are useful in the sense that they
specific surface area of an oxide mineral is reduced, some of the adsorbed give some indication of possible surface area effects, they make important
ions will be desorbed. The specific surface area of HFO on which the DLM and
HFOunverified assumptions,
in a sediment and
containing 1 gare
kg almost certainly
1 Fe as HFO an oversimplification
is reduced from its initial valueof
was calibrated by Dzombak and Morel (1990) was taken as 600 m 2 g 1. Aged reality. For example, some of the desorbed ions are likely to be incorporated
products, such as goethite typically have specific surface areas of 150 m 2 g 1 into the evolving oxide structure as a solid solution. This will reduce the
amount of As released. Also, if the surface structure changes, then it is likely
that the binding affinity of arsenate ions and protons will also change since
Calculated increase in As concentration when the specific surface area of
or less and even less for hematite (Cornell and Schwertmann, 1996). the binding affinity is closely related to surface structure. For example,
Kinniburgh et al. (1977) found that while aged HFO gels had a significantly
Assuming that the site density remains unchanged during ageing and the reduced proton buffer capacity, and by implication a reduced specific
binding affinity of As(V) and protons also remains unchanged, it is possible surface area, the binding of trace Zn 2+ increased on ageing, implying that the
to calculate the effect that a reduction in surface area might have. If we binding affinity
Specifically for of
FeZn increased
oxides, somewith increasing
of the surface crystallisation of the gel
Fe could be reduced and
Fig. 6.
assume similar initial conditions to the pH example given above, i.e. HFO in that this more than compensated for the reduction in specific surface area,
equilibrium with a solution containing 1 m g As(V) l 1 and a sediment with 25% i.e. the isotherm changed from a low-affinity isotherm to a high-affinity
porosity and a HFO concentration equivalent to 1g Fe kg 1, then these isotherm.
calculations show that there is a marked increase in As concentration in
could operate which may lead to a reduction in the overall adsorption of As.
solution when the surface area is reduced to below 300 m 2 g 1 ( Fig. 6).

Assuming that the HFO was also initially in equilibrium with 10 m g l 1 phosphate-P Under strongly reducing conditions, it appears that additional processes
increases the effect somewhat. These calculations are strongly dependent
on the shape of the adsorption isotherm and the initial As
556 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

from Fe(III) to Fe(II) to produce a mixed-valence oxide perhaps akin to that occurs during the reductive dissolution of Fe(III) oxides containing adsorbed
of a magnetite or a green rust. This would tend to reduce the net positive and coprecipitated As is complex and has not been studied in detail. It is
charge of the surface (or increase its net negative charge) and would even more complex than for phosphate release because of the variable
thereby reduce the electrostatic interaction between the surface and anions. oxidation state of As. The reduction of both the Fe(III) oxide and the As(V)
This could result in the desorption of As and a corresponding large increase are microbially catalysed and the relative rates depend on the viability and
in the concentration of As in solution (BGS and DPHE, 2001). nutrient supply of the specific microbial strains involved (Ehrlich, 1996).
Reductive dissolution cannot of course explain the occurrence of high-As
oxidising groundwaters.
On balance, laboratory and field evidence suggests that at micromolar As
concentrations, freshly-formed HFO binds more As than goethite on a mole
of Fe basis (De Vitre et al., 1991) and so a reduction in affinity appears to be Manganese oxides also undergo reductive desorption and dissolution
more probable. In Bangladesh, areas with high-As groundwaters tended to and so could contribute to the As load of groundwaters in the same way as
correspond with those areas in which the sediments contain a relatively high Fe. Certainly many of the reducing groundwaters of Bangladesh contain
concentration of oxalate-extractable Fe (BGS and DPHE, 2001). This high concentrations of Mn (DPHE/BGS/MML, 1999; BGS and DPHE, 2001).
provides indirect support for the importance of Fe oxides. Some early work The Mn oxide surfaces also readily catalyse the oxidation of As(III)
(Khalid et al., 1977) also showed that the sorption of phosphate by reduced (Oscarson et al.,
soils was less than that for their oxidised equivalents but that this was only
true at low (near natural) phosphate loadings. It can be speculated that the 1981). It is not known whether or not the dissolution of carbonate minerals
soils and sediments most sensitive to arsenic release on reduction and (calcite, dolomite, siderite), which are common minerals in aquifers,
ageing are those in which Fe oxides are abundant, in which HFO is a major contribute significantly to the release of As to groundwater, or its uptake
fraction of the Fe oxides present, and in which other As-sorbing minerals are from groundwater.
relatively scarce. While the existing evidence is somewhat contradictory, it
tends to suggest that a change from aerobic to anaerobic conditions often Sulphide oxidation, particularly pyrite oxidation, can also be an important
results in a net release of As. source of As especially where these minerals are freshly exposed as a result
of a lowering of the water table. This can occur locally in and around mines
and on a more regional scale in aquifers. In extreme cases, this can lead to
highly acidic groundwaters rich in SO 4, Fe and trace metals. As the dissolved
Fe is neutralised, it tends to precipitate as a hydrous ferric oxide (sometimes
schwertmannite) with a resultant adsorption and coprecipitation of dissolved
As(V). In this sense, pyrite oxidation is not a very efficient mechanism for
releasing As to surface and groundwaters.
6.3.5. Mineral dissolution
Mineral dissolution reactions tend to be most rapid under extremes of pH
and Eh. Iron oxides dissolve under strongly acidic conditions and under
strongly reducing conditions. Minor elements, including As, present either as
adsorbed (labile) As or as irreversiblybound (non-labile) As will also tend to 6.4. Transport—historical groundwater flows
be released during this dissolution. This can explain, in part at least, the
presence of high As concentrations in acid mine drainage and in strongly The geochemical triggers described above may release As into
reducing groundwaters. The reductive dissolution of Fe(III) oxides has been groundwater but are not alone sufficient to account for the distribution of
extensively discussed in the context of estuarine, lake and river particles high-As groundwaters observed. The additional factor is that the released As
and sediments (Davison, 1993; Lovley and Chapelle, 1995). It accounts for must not have been flushed away or diluted by normal groundwater flow.
the high Fe(II) content of anaerobic waters, and the ubiquity of Fe in the This also places a time dimension on the problem since the rate of release
environment means that waters with near-neutral pH and high Fe are must be set against the accumulated flushing of the aquifer that has taken
invariably anaerobic waters. While this process undoubtedly accounts for place during the period of release. The rocks of most aquifers used for
some of the As found in reducing groundwaters, it does not appear to be drinking water are several hundred million years old and yet contain
sufficient to account for all, or even most, of the As released. Congruent groundwater that may be only a few thousand years old or younger. This
dissolution of a typical Fe oxide without any precipitation of secondary Fe implies that many pore volumes of fresh water have passed through the
phases would only release a few, or a few tens, of m g As l 1 which is far less aquifer over its history. The oldest fresh groundwaters are found in the Great
that that found in many As-rich reducing groundwaters. The precise Artesian Basin of Australia, being up to about 400 ka (Collon et al., 2000).
sequence of events that The water moves slowly through this aquifer and over its 2.5 Ga history,
there have been many pore volumes of fresh water flushed through the
system. Any
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 557

desorbed As will have long since disappeared. The same is true of most usually non-linear, which means that the K d varies with concentration. This
young aquifers with actively flowing groundwater. On the other hand, many leads to more complex transport behaviour but the same general principles
deltaic and alluvial aquifers are characterised by relatively young sediments apply. In aquifers with high-As groundwater, the K d will be less than under
and often relatively old groundwater. The relative ages of the aquifer rocks ‘normal’ oxidised conditions since a reduced
and of the groundwater are important. It is only when the geochemical
trigger to mobilise As and the hydrogeological regime to preserve it are both K d is precisely the reason for the development of As problems in aquifers.
operating that we see high groundwater As concentrations on a regional There have so far been no reliable studies of K d values applicable to
scale. As-affected aquifers. The greater the quantity of As involved, the more
strongly it is adsorbed and the slower the rate of groundwater movement,
the longer that high-As groundwaters will persist.
It is also necessary to consider historical groundwater flows which may
have been very different from the present-day flows. One of the more
significant ‘recent’ events is the global change in sea levels that has As described above, the number of pore volumes that have passed
occurred over the last 130 ka (Pirazzoli, 1996). Sea levels reflect global through the aquifer is a function of the groundwater flow velocity integrated
climate patterns. Between about 120 ka ago and 18 ka ago, the sea level over the time since sediment burial. In Bangladesh, the age of sediment vs
steadily declined (with a few fluctuations) as glaciers expanded. The last depth relationship is particularly important since this has a direct bearing on
glaciation was at a maximum some 21–13.5 ka ago with sea levels being up the extent of flushing. Many of the shallow sediments in southern
to 130 m below present mean sea level. This was a worldwide phenomenon Bangladesh are less than 13 ka old, even less than 5 ka old, and so will not
and would have affected all then existing coastal aquifers. Continental and have experienced the extensive flushing of the last glacial period. These
closed basin aquifers on the other hand would have been unaffected. The sediments are from where the majority of the tubewells abstract water.
hydraulic gradient in coastal aquifers would therefore have been much Certainly at present, flushing is slow because of the extremely small
greater than at present which would have resulted in correspondingly large hydraulic gradients especially in southern Bangladesh. However, deeper
groundwater flows and extensive flushing. The As in these older aquifers and older sediments, which may exceed 13 ka old, will have been subjected
would therefore tend to have been flushed away. The deep unsaturated to more extensive flushing. This may account for the ‘As-free’ groundwaters
zone would also have led to more extensive oxidation of the shallower found in the deep aquifers of Bangladesh. Geochemical factors may also
horizons with possible increased sorption of As to Fe(III) oxides. Relics of play a role since the evidence is that while the deep groundwaters are
these high flows are seen in the extensive fissure formation in some of the currently reducing, they are less strongly reducing than the shallow aquifers.
world’s older carbonate aquifers. Between some 13.5–7 ka ago, warming Certainly, the aquifers in the Pleistocene uplifted alluvial sediments of the
occurred and sea levels rapidly rose to their existing levels. Therefore Barind and Madhupur Tracts (Fig. 4) will have been well flushed since they
aquifers that are younger than some 7 ka old will not have been subjected to are at least 25–125 ka old. These sediments invariably yield low-As
this increased flushing that occurred during the most recent glaciation. groundwaters, typically containing less than 0.5 m g l 1 As. A complication is
that the Bengal Basin is locally rapidly subsiding and filling in with
sediments. This adds to the high degree of local and regional variation.

The time taken to flush an aquifer depends on many factors (Appelo and
Postma, 1994). A critical factor is the number of pore volumes of ‘fresh’ Regional flow patterns are not the only important factors. At a local scale,
water that have passed through the aquifer since the initial release of As has small variations in relief or in drainage patterns may dictate local flow
taken place. The other important factor is the partitioning of As between the patterns and hence the distribution of As-rich groundwater. For example,
aquifer solid phase and the groundwater. This determines the ease with there is evidence from Argentina that the highest groundwater As
which As is flushed out and is related to the slope of the adsorption isotherm concentrations are found in the slightly lower areas where seasonal
(Appelo and Postma, 1994). In simple cases, this can be expressed by the discharge occurs (Smedley et al., 2002). The same is true in Inner Mongolia
partition coefficient, K d. (Smedley et al., 2001a) and may also be true in Bangladesh. In any case, it
is a characteristic of groundwater As problem areas that there is a high
degree of local-scale variation. This reflects the poor mixing and low rate of
The greater the K d, the greater the capacity of the sediment to withstand flushing, characteristic of the affected aquifers.
changes and the slower the As will tend to be flushed from the aquifer. The K
d depends on many factors both relating to the aquifer material itself and to
the chemistry of the groundwater, i.e. its pH, As concentration and
speciation, phosphate concentration and so on. In practice, the adsorption
isotherms are It is clear that flat low-lying areas, particularly large plains and delta
regions, are particularly prone to
558 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

potentially high-As groundwaters since they combine many of the risk of the sediment. Secondly, these field studies need to be backed up by new
factors identified above. The process of delta development also favours the theoretical advances in modelling the relevant surface chemical reactions of
separation of minerals based on particle size and produces the the oxides and sediments, particularly in reducing environments. This will
characteristic upwardly fining sequences of sand–silt–clay. These lead to involve both modelling and laboratory work.
confining or semi-confining layers which aid the development of strongly
reducing conditions. The youngest, distal part of the deltas will tend to Calculations of the rate of movement of As through an aquifer depend on
contain the greatest concentration of fine-grained material and this provides knowing the appropriate solidsolution partition coefficient ( K d), or more
an abundant source of As in the form of colloidal-sized oxide materials. particularly, on knowing the nature of the adsorption isotherm and in being
Flocculation of colloidal material, including Fe oxides, at the freshwatersea able to predict how the partitioning changes with changes in groundwater
water interface will tend to lead to relatively large concentrations of these chemistry. Therefore, there is a need for laboratory studies of the interaction
colloids in the lower parts of a delta. The larger the delta, and the more rapid of arsenate, and if appropriate of arsenite also, with the affected aquifer
the infilling, the lower the hydraulic gradient and the less flushing that is materials. These will need to be carried out under conditions as close as
likely to have occurred. However, some deltas, even large deltas, may be so possible to those found in the field including reducing conditions if
old and well-flushed that even the existing low hydraulic gradients will have appropriate. This can be difficult. These studies need to be backed up by
been sufficient to flush away any desorbed or dissolved As. laboratory investigations of the interaction of As with model oxide materials
to establish better models for competitive adsorption of both arsenate and
arsenite with other common anions and cations. It is likely that this will lead
to the development of new models, or at least to a refinement of existing
ones. Any new adsorption models need to be incorporated into a
groundwater solute transport package.

6.5. Future developments in arsenic research

It is necessary to know how As moves in an aquifer to predict how

concentrations might change in the future. Arsenic, like any other solute, Reductive dissolution of oxides with adsorbed As is poorly understood
moves in response to the flow of groundwater and its interaction with the and needs careful experimental investigations to establish the sequence of
aquifer solid phase. Adsorption or precipitation reactions will tend to retard events in terms of changes in As and Fe speciation, changes in mineral
movement relative to that of the groundwater whereas the co-transport of surface chemistry and the kinetics and stoichiometry of Fe and As release.
chemicals, including phosphate from fertilisers, that enhance the release of
As could lead to its more rapid movement through the aquifer, albeit limited
by the rate of flow of the groundwater. Establishing the basic groundwater
flow patterns within an aquifer is a prerequisite to understanding the 6.6. Identification of ‘at risk’ aquifers
movement of As. The concentration profile of a nonreactive solute such as
Cl can help to establish this. Agerelated tracers such as 3 H, 14 C and CFCs This review has outlined some of the factors that are likely to be
can also help, as well as basic hydrogeological investigations of the aquifer. responsible for the development and persistence of As-rich groundwaters.
These can be summarised in the form of various ‘risk’ factors that can help
to identify groundwater provinces which deserve the highest priority for As
testing (Fig. 7). These factors relate to the nature of the environment,
particularly in relation to the source of As and the hydrogeology of the
aquifer, as well as to the possible processes that can lead to the mobilisation
Aside from the basic hydrogeology of the aquifer, it is also important to of As. The best option is obviously to test the groundwater directly for As
understand quantitatively the solidsolution interactions that take place. This enrichment but where this is not possible, other water-quality data may
refers principally to the nature of the adsorption–desorption isotherms and provide some indication of the likelihood of arsenic enrichment. No single
the mechanisms of reductive dissolution of Fe and Mn oxides. It is likely that factor is sufficient to identify a problem area but if collectively many of the
what is conveniently called ‘reductive dissolution’ is in fact a mixture of environmental characteristics and water-quality indicators point towards this,
desorption, dissolution and structural rearrangement of the oxides then some kind of testing should be undertaken as a matter of priority. A
themselves. A two-stranded approach is required: firstly, a detailed stratified random survey is the best approach with the stratification going
characterisation of sediments and associated porewaters is needed from a across geological or landform types. Fig. 7 can only be used to identify
variety of aquifers, both affected and not affected, akin to that undertaken by susceptible provinces, not individual wells.
limnologists and oceanographers when studying their sedimentary
environments. In reduced aquifers, special care should be taken to avoid
oxidation
 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568 559

Fig. 7. Classification of groundwater environments prone to As problems from natural sources. Not all the indicators of low rates of flushing necessarily apply to all environments.

7. Concluding remarks and elsewhere. This review has attempted to characterise the distribution of
As in the environment, and to describe the main geochemical controls on its
Much research has been carried out on As, particularly in the last few speciation and mobilisation. The documented As-rich areas are also
years, as a response to the growing evidence of the element’s detrimental summarised and the main types of environment under which As
health effects, to reductions in regulatory limits for As, and to the recognition concentrations in waters are expected to be problematic are highlighted.
of the scale of arsenic enrichment in Bangladesh Doubtless there are
560 P.L. Smedley, D.G. Kinniburgh / Applied Geochemistry 17 (2002) 517–568

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