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A review on sources, toxicity and remediation

technologies for removing arsenic from drinking water

Ankita Basu • Debabrata Saha • Rumpa Saha •

Tuhin Ghosh • Bidyut Saha

Received: 7 August 2012 / Accepted: 23 December 2012 / Published online: 9 January 2013 Springer Science+Business Media Dordrecht 2013

Abstract Arsenic is a natural element found in the environment in organic and

inorganic forms. The inorganic form is much more toxic and is found in ground water,

surface water and many foods. This form is responsible for many adverse health

effects like cancer (skin, lung, liver, kidney and bladder mainly), and cardiovascular

and neurological effects. The estimated number of people in Bangladesh in 1998

exposed to arsenic concentrations above 0.05 mg/l is 28–35 million, and the number

of those exposed to more than 0.01 mg/l is 46–57 million. The estimated number of people in West Bengal, India (the border province to Bangladesh), in 1997 actually

using arsenic-rich water is more than 1 million for concentrations above 0.05 mg/l

and is 1.3 million for concentrations above 0.01 mg/l. The United States Environ-

mental Protection Agency (USEPA) has estimated that 13 million of the US popu-

lation are exposed to arsenic in drinking water at 0.01 mg/l. The situation has

prevailed for more than 10 years and is more severe now. The USEPA lowered the

maximum contaminant level (MCL) for drinking water arsenic from 50 to 10 lg/l in

2001 based on international data analysis and research. This recommendation is now

on hold. The level of 10 ppb become standard in the European Union (EU) in 2001.Arsenic may be found in water flowing through arsenic-rich rocks. The source is

diverse. These include the earth’s crust, introduced into water through the dissociation

of minerals and ores, industrial effluents to water, combustion of fossil fuels and

seafoods. Arsenic-removal methods are coagulation (ferric sulfate, ferrous sulfate,

A. Basu R. Saha B. Saha (&)

Department of Chemistry, The University of Burdwan, Golapbag, Burdwan 713104,

West Bengal, India

e-mail: [email protected]

D. Saha

Department of Chemistry, Suri Vidyasagar College, Suri, Birbhum 731101, West Bengal, India

T. Ghosh

Department of Chemistry, A.B.N. Seal College, Cooch Behar 736101, West Bengal, India

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Res Chem Intermed (2014) 40:447–485

DOI 10.1007/s11164-012-1000-4

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ferric chloride, aluminum sulfate, copper sulfate, and calcium hydroxide as coagu-

lants), adsorption (activated carbon, activated alumina, activated bauxite) ion

exchange, bio-sorption, etc.

Keywords Arsenic Toxicity Source Removal techniques

Introduction

Sources of drinking water are of three different types. These sources are surface

water (river water, lake water and pond water), rain water and ground water. Surface

water needs processing while rain water needs proper storage, which may not besufficient. On the other hand, ground water does not require processing and storage.

In addition, agriculture is the main source of income for highly populated Asian

countries. During the dry season, surface water is not sufficient for irrigation.

Ground water is the only solution. Dangerous arsenic levels in natural waters are

now a universal problem and often referred to as a twentieth–twenty-first century

calamity. Arsenic contamination of ground water is now regarded as one of the

worst public health crises [1–3]. Arsenic also enters into the human body system via

the food chain. The presence of arsenic in ground water has been reported from

many parts of the world, such as Argentina [4–9], Australia [10, 11] Bangladesh

[12–22], Cambodia [23–27], Canada [28, 29], Chile [30, 31], China [32–37], Ghana

[38–40], Germany [41–43], Hungary [44, 45], India [46–69], Japan [70–74], Laos

[75], Mexico [76–82], Nepal [83–86], Pakistan [87–90], Poland [91, 92], Romania

[93], Taiwan [94–100], Thailand [101], UK [102], USA [103, 104], and Vietnam

[105–111].

With increasing population and with the change in climate, ground water

represents one of the most important and stable sources of drinking water. There is

an immediate, critical need to supply arsenic-free drinking water to society, and this

need will continue to grow. The magnitude of the problem of poisoning was so great

that the World Health Organization, having recognized the enormous health

implications, lowered the provisional guideline value for arsenic in drinking water

from 50 to 10 lg/l. One of the main uses of arsenic in the past was as pesticides in

agriculture, e.g. MSMA (monosodium methylarsonate, NaMeHAsO3), DSMA

(disodium salt, Na2MeAsO3) [112], and wood preservation with CCA (chromated

copper arsenate) [113]. Arsenic had its uses in medicine, too, against syphilis and

African trypanosomiasis, though in recent years these uses have become obsolete

[113]. Arsenic from the natural environment and anthropogenic sources can enter

the human body through food, water, soil, and air. Inhalation of airborne arsenic or

arsenic-contaminated dust is a common health problem in many ore mines. As theparticular species in the environment is not normally determined in routine

procedures, so the level and nature of arsenic exposure may not be known. Here,

Table 1 summarizes the documented cases of naturally occurring arsenic poisoning

throughout ground water in the whole world [78].

448 A. Basu et al.

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Arsenic chemistry

The element arsenic (valence configuration 3d10 4s2 4p3) is known to exist in four

major oxidation states, ?5, ?3, 0, and -3. It is found as a commonly distributed

element in the atmosphere, rocks, minerals, soil, water, and in the biosphere. In

Table 1 Naturally occurring poisoning throughout ground water in the whole world

Sl.

no.

Country/

religion

Potential

exposed

population

Concentration

(lg/l)

Environmental conditions Reference

1 Bangladesh 30,000,000 \1–2,500 Natural; alluvial/deltaic sediments

with high phosphate, organics

[78]

2 West

Bengal

6,000,000 \10–3,200 Similar to Bangladesh

3 Vietnam [1,000,000 1–3,050 Natural; alluvial sediments

4 Thailand 15,000 1–[5,000 Anthropogenic; mining and

dredged alluvium

5 Taiwan 100,000–200,000 10–1,820 Natural; coastal zones, black

shales

6 InnerMongolia 100,000–600,000 \

1–2,400 Natural; alluvial and lakesediments; high alkalinity

7 Xinjiang,

Shanxi

[500 40–750 Natural; alluvial sediments

8 Argentina 2,000,000 \1–9,900 Natural; loess and volcanic rocks,

thermal springs; high alkalinity

9 Chile 400,000 100–1,000 Natural and anthropogenic;

volcanogenic sediments; closed

basin lakes, thermal springs,

mining

10 Bolivia 50,000 – Natural; similar to Chile and parts

of Argentina

11 Brazil – 0.4–350 Gold mining

12 Mexico 400,000 8–620 Natural and anthropogenic;

volcanic sediments, mining

13 Germany – \10–150 Natural: mineralized sandstone

14 Hungary,

Romania

400,000 \2–176 Natural; alluvial sediments;

organics

15 Spain [50,000 \1–100 Natural; alluvial sediments

16 Greece 150,000 – Natural and anthropogenic;

thermal springs and mining

17 United

Kingdom

– \1–80 Mining; southwest England

18 Ghana \100,000 \1–175 Anthropogenic and natural; gold

mining

19 USA,

Canada

– \1–[100,000 Natural and anthropogenic;

mining, pesticides, As2O3stockpiles, thermal springs,

alluvial, closed basin lakes,

various rocks

A review on sources, toxicity and remediation technologies 449

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these minerals are relatively rare in the natural environment. Several other, less

common minerals contain arsenic, including orpiment, realgar, and enargite, which

are arsenic sulfides. Arsenic commonly accompanies deposits of copper, silver,

gold, zinc, cadmium, mercury, uranium, tin, lead, phosphorus, antimony, bismuth,

sulfur, selenium, tellurium, molybdenum, tungsten, iron, nickel, cobalt, and

platinum, particularly those containing sulfides and sulfosalts. The commonly

identified arsenic-bearing minerals are realgar (AsS), orpiment (As2O3), arsenopy-

rite (FeAsS), claudetite (As2O3), arsenolite (As2O3), pentoxide (As2O5), and

scorodite (FeAsO42H2O). Within this group of minerals, arsenopyrite is probably

the most common and abundant mineral [119–121]. In the weathering of sulfides,

arsenic can be oxidized to arsenite and arsenate. Arsenic oxide is also formed as a

by-product of copper, lead, and nickel smelting. In fact, environmental laws require

that arsenic be removed from ores, so that it does not enter the environment in

effluent gases, fluids, or solids. The greatest concentrations of these minerals occur

in mineralized areas. It is generally accepted that arsenopyrite, together with the

other dominant As-sulfide minerals, realgar and orpiment, are only formed underhigh temperature conditions in the earth’s crust. However, authigenic arsenopyrite

has also been reported in sediments [122]. Although often present in ore deposits,

arsenopyrite is much less abundant than arsenian (‘-rich’) pyrite (Fe(S, As) 2), which

is probably the most important source of arsenic.

Me2As O(OH)V

Me2AsH

Me3As Me3As OV

Me2As O(OH)V

MeAs O(OH)2V

As O(OH)III

As O2(OH)V

FeAsO4AsH3 As2S3 MeAsH2

Oxidation

Oxidation

Bacterial

Reduction

Reduction

ReductionReduction

Reduction

Biomethylation

Biomethylation

Biomethylation

(Bacteria)

(Sediment) (Sediment)

Scheme 1 Species distribution of in the environment


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T a b l e 2

M a j o r a r s e n i c m i n e r a l s o c c u r r i n g i n n a t u r

e

M i n e r a l

C o m p o s i t i o n

O c c u r r e n c e

R e f e r e n c e

N a t i v e

A s

H y d r o t h e r m a l v e i n s

[ 1 2 2 – 1 2 4 ]

N i c c o l i t e / N i c k e l i n

e

N i A s

V e i n d e p o s i t s a n d

n o r i t e s

R e a l g a r

A s S / A s 4 S 4

L o w - t e m p e r a t u r e

h y d r o t h e r m a l v e i n m i n e r a l a s s o c i a t e d

w i t h o t h e r a n d a n t i m o n y m i n e r a l s , c l a y s a n d

l i m e s t o n e s ; a l s o

o c c u r s a s v o l c a n i c s u b l i m a t i o n ,

d e p o s i t s f r o m h

o t s p r i n g s . V e i n d e p o s i t s , o f t e n

a s s o c i a t e d w i t h

o r p i m e n t , c l a y s a n d l i m e s t o n e s , a l s

o

d e p o s i t s f r o m h

o t s p r i n g s

O r p i m e n t

A s 2 S 3

H y d r o t h e r m a l v i e

n s , h o t s p r i n g s a n d o c c u r s a s

s u b l i m a t i o n p r o

d u c t i n v o l c a n i c f u m a r o l e s

C o b a l t i t e

C o A s S

H i g h - t e m p e r a t u r e

d e p o s i t s , m e t a m o r p h i c r o c k s

A r s e n o p y r i t e

F e A s S

H i g h t e m p e r a t u r e

h y d r o t h e r m a l v e i n s , i n p e g m a t i t e

s ,

a n d i n a r e a s o f

c o n t a c t m e t a m o r p h i s m o r

m e t a s o m a t i s m

T e n n a n t i t e

C u 1 2 A s 4 S 1 3

H y d r o t h e r m a l v e i n s a n d c o n t a c t m e t a m o r p h i c d e p o

s i t s

i n a s s o c i a t i o n w

i t h o t h e r C u – P b – Z n – A g s u l fi d e s

a n d

s u l f o s a l t s

E n a r g i t e

C u 3 A s S 4

S e c o n d a r y m i n e r a l i n t h e o x i d e z o n e o f C o – N i – A s -

b e a r i n g m i n e r a l d e p o s i t s

O l i v e n i t e

( C u 2 A s O 4 O H )

H y d r a t e d c o p p e r a r s e n a t e m i n e r a l , f o u n d i n c o p p e r

d e p o s i t s

M i m e t i t e

P b 5 ( A s O 4 ) 3 C l

S e c o n d a r y m i n e r a l i n l e a d o r e s

E r y t h r i t e

C o 3 ( A s O 4 ) 2

8 H 2

O

S e c o n d a r y m i n e r a l i n c o b a l t - b e a r i n g d e p o s i t s

P r o u s t i t e

A g 3 A s S 3

L a t e - f o r m i n g m i n

e r a l i n h y d r o t h e r m a l d e p o s i t s ; i n

t h e

o x i d i z e d a n d e n

r i c h e d z o n e , a s s o c i a t e d w i t h o t h e r

s i l v e r m i n e r a l s a n d s u l fi d e s

A r s e n o l i t e

A s 2 O 3

S e c o n d a r y m i n e r a

l f o r m e d b y o x i d a t i o n o f a r s e n o p y

r i t e ,

n a t i v e a n d o t h e r A s m i n e r a l s

452 A. Basu et al.

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T a b l e 2

c o n t i n u e

d

M i n e r a l


O c c u r r e n c e

R e f e r e n c e

C l a u d e t i t e

A s 2 O 3

S e c o n d a r y m i n e r a l f o r m e d b y o x i d a t i o n o f r e a l g a r ,

a r s e n o p y r i t e a n d o t h e r A s m i n e r a l s

S c o r o d i t e

F e A s O 4

2 H 2 O

H y d r o t h e r m a l d e p o s i t s a n d a s a s e c o n d a r y m i n

e r a l i n

g o s s a n s w o r l d w i d e

A n n a b e r g i t e

N i 3 ( A s O 4 ) 2

8 H 2 O

S e c o n d a r y m i n e r a l

H o e r n e s i t e

M g 3 ( A s O 4 ) 2

8 H 2 O

S e c o n d a r y m i n e r a l , s m e l t e r w a s t e s

H a e m a t o l i t e

( M n , M g ) 4 A l ( A s O 4 ) ( O H

) 8

W e a t h e r i n g p

r o d u c t , s e c o n d a r y m i n e r a l

C o n i c h a l c i t e

C a C u ( A s O 4 ) ( O H )

S e c o n d a r y m i n e r a l

P h a r m a c o s i d e r i t e

K F e 4 ( A s O 4 ) 3 ( O H ) 4

6 - 7 H 2 O

O x i d a t i o n p r o d u c t o f a r s e n o p y r i t e a n d o t h e r A s

m i n e r a l s

A k t a s h i t e

C u 6 H g 3 A s 4 S 1 2

H y d r o t h e r m a l v e i n s , A k t a s h s k o y e S b – H g d e p o s i t s

A l a c r a n i t e

A s 8 S 9

H y d r o t h e r m a l A s – S v e i n s , i n t h e c o n d e n s a t i o n z

o n e o f a

h y d r o t h e r m a l H g – S b – A s s y s t e m , a r e a o f b a s a l t i c

s h i e l d v o l c a n o w i t h l a c u s t r i n e s e d i m e n t s ,

h y d r o t h e r m a l fl u i d s f r o m h o t s p r i n g s

A b e r n a t h y i t e

K 2 ( U O 2 ) 2 ( A s O 4 ) 2

6 H 2 O

U r a n i u m d e p o s i t , a s a s e c o n d a r y f r a c t u r e - fi l l i n g

m i n e r a l

A d a m i t e

Z n 2 A s O 4 O H

O c c u r s a s a s

e c o n d a r y m i n e r a l i n t h e o x i d i z e d

z o n e o f

z i n c a n d - b e a r i n g h y d r o t h e r m a l m i n e r a l d e p o

s i t s

A d e l i t e

C a M g A s O 4 O H

A r a r e m i n e r a

l i n a m e t a m o r p h o s e d F e – M n o r e b o d y ; o n

w i l l e m i t e – f r a n k l i n i t e o r e f r o m a m e t a m o r p h o

s e d

s t r a t i f o r m z

i n c o r e b o d y

A e r u g i t e

N i 9 ( A s O 4 ) 2 A s O 8

A s a n e n c r u s t a t i o n o n f u r n a c e w a l l s i n w h i c h o r e s a r e

r o a s t e d

A k r o c h o r d i t e

( M n , M g ) 5 ( A s O 4 ) 2 ( O H ) 4

4 H 2 O

A r a r e m i n e r a l i n h a u s m a n n i t e o r e f r o m a

m e t a m o r p h o s e d F e – M n o r e b o d y ; i n a

m e t a m o r p h o s e d s t r a t i f o r m z i n c o r e b o d y

A g a r d i t e

( L a / C e ) C u 6 [ ( O H ) 6 ( A s O

4 ) 3 ] 3 H 2 O

B a r i t e – fl u o r i t e v e i n s i n c l u d i n g c o p p e r , s i l v e r a n d l e a d

m i n e r a l s , h o s t e d b y g n e i s s e s a n d t r i a s s i c s a n d s t o n e s


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T a b l e 2

c o n t i n u e

d

M i n e r a l


O c c u r r e n c e

R e f e r e n c e

A l l a c t i t e

M n 7 ( A s O 4 ) 2 ( O H ) 8

M e t a m

o r p h o s e d M n – F e o r e b o d i e s

A n d y r o b e r t s i t e

K C d C u 5 [ H 2 A s O 4 ( A s O 4 ) 4 ] 2 H 2 O

L o w - t e m p e r a t u r e s e c o n d a r y p a r a g e n e s e s

A n n a b e r g i t e

N i 3 ( A s O 4 ) 2

8 H 2 O

A n u n c o m m o n o x i d a t i o n z o n e m i n e r a l i n N i – C o – A s

d e p o

s i t s

A l g o d o n i t e

C u 6 A s

I n h y d

r o t h e r m a l d e p o s i t s

A u s t i n i t e

C a Z n A s O 4 ( O H )

A r a r e

m i n e r a l i n t h e o x i d i z e d z o n e o f s e c o n d a r y

m i n e

r a l s o f c o p p e r , - b e a r i n g b a s e m e t a l d e p o s i t s

B a u m h a u e r i t e

P b 3 A s 4 S 9

M e t a m

o r p h o s e d s u l f o s a l t / s u l fi d e d e p o s i t

i n s u g a r y

d o l o m i t e

B e l l i t e

P b C r O 4 , A s O 4 , S i O 2

_

B e u d a n t i t e

P b F e 3 ( O H ) 6 S O 4 A s O 4

S e c o n d a r y m i n e r a l o c c u r r i n g i n t h e o x i d

i z e d z o n e s o f

p o l y m e t a l l i c d e p o s i t s

B r a s s i t e

M g ( A s O 3 O H ) 4 ( H 2 O )

R i c h v

e i n - t y p e A g – C o – N i – B i – U d e p o s i t

B u k o v s k y i t e

F e 2 ( A s O 4 ) ( S O 4 ) ( O H ) 7 ( H 2 O )

A p o s t - m i n i n g s u p e r fi c i a l w e a t h e r i n g p r o d u c t o f F e – A s

s u l fi d e s

C e r v a n d o n i t e

( C e , N d , L a ) ( F e ?

3 , F e ?

2 , T i , A l ) 3 O 2

( S i 2 O 7 ) ( A s ?

3 O 3 ) ( O H ) )

_

C a b a l z a r i t e

( C a ( M g , A l , F e 3 ? ) 2 [ A s O 4 ] 2

2 0 ( H 2

O , O H )

_

C a h n i t e

C a 2 [ A s O 4 ] [ B ( O H ) 4 ]

_

C h a l c o p h y l l i t e

C u 2 A l ( A s O 4 ) ( O H ) 4

4 ( H 2 O )

S e c o n d a r y c o p p e r a r s e n a t e m i n e r a l o c c u

r r i n g i n t h e

o x i d i z e d z o n e s o f s o m e - b e a r i n g c o p p

e r

C l i n o c l a s e

C u 3 A s O 4 ( O H ) 3

S e c o n d a r y c o p p e r m i n e r a l a n d f o r m s a c i c u l a r c r y s t a l s i n

t h e f

r a c t u r e d w e a t h e r e d z o n e a b o v e c o

p p e r s u l fi d e

d e p o

s i t s

C o r n u b i t e

C u 5 ( A s O 4 ) 2 ( O H ) 4

R a r e s

e c o n d a r y c o p p e r a r s e n a t e m i n e r a l

D u f t i t e

P b C u A s O 4 ( O H )

U n c o m

m o n m i n e r a l , o c c u r s i n t h e o x i d i

z e d z o n e o f

s o m e s u l fi d e d e p o s i t s

454 A. Basu et al.

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T a b l e 2

c o n t i n u e

d

M i n e r a l


O c c u r r e n c e

R e f e r e n c e

D o m e y k i t e

C u 3 A s

F o u n d i n v e i n

a n d r e p l a c e m e n t d e p o s i t s f o r m e d

a t

m o d e r a t e t e m p e r a t u r e s

R a m m e l s b e r g i t e

N i A s 2

C o m m o n l y i n

m e s o t h e r m a l v e i n d e p o s i t s

L o l l i n g i t e

F e A s 2

F o u n d i n m e s o t h e r m a l v e i n d e p o s i t s

S e l i g m a n n i t e

P b C u A s S 3

O c c u r s i n t h e

h y d r o t h e r m a l v e i n s

S m a l t i t e

C o A s 2

_

E u c h r o i t e

C u 2 A s O 4 O H

3 H 2 O

_

F r e i b e r g i t e

( A g , C u , F e ) 1 2 ( S b , A s ) 4 S 1 3

O c c u r s i n s i l v e r m i n e s , h y d r o t h e r m a l d e p o s i t s

F o r n a c i t e

P b 2 C u ( C r O 4 ) ( A s O 4 ) ( O H

)

_

G a l k h a i t e

( C s , T l ) ( H g , C u , Z n ) 6 ( A s , S b ) 4 S 1 2

O c c u r s i n C a r l i n - t y p e h y d r o t h e r m a l d e p o s i t s

G e o c r o n i t e

P b 1 4 ( S b , A s ) 6 S 2 3

F o u n d i n h y d r

o t h e r m a l v e i n s u s u a l l y a s s o c i a t e d

w i t h

o t h e r s i m i l a r m i n e r a l s , p a r t i c u l a r l y t h e s u l fi d e s

o f i r o n

a n d c o p p e r

G e r s d o r f fi t e

N i A s S

O c c u r s a s a h y

d r o t h e r m a l v e i n m i n e r a l a l o n g w i t h o t h e r

n i c k e l s u l fi d

e s

G l a u c o d o t

( C o , F e ) A s S

O c c u r s i n h i g h t e m p e r a t u r e h y d r o t h e r m a l d e p o s i t s w i t h

p y r r h o t i t e a n

d c h a l c o p y r i t e

G r a t o n i t e

P b 9 A s 4 S 1 5

H y d r o t h e r m a l

c o p p e r d e p o s i t s

G e i g e r i t e

M n 5 ( A s O 3 O H ) 2 ( A s O 4 ) 2

1 0 H 2 O

O c c u r s a s a s e

c o n d a r y m i n e r a l i n t h e o x i d i z e d z o n e o f

m a n g a n e s e

H u t c h i n s o n i t e

( T l , P b ) 2 A s 5 S 9

R a r e h y d r o t h e

r m a l m i n e r a l

H a i d i n g e r i t e

C a ( A s O 3 O H ) H 2 O

O c c u r s a s a d e h y d r a t i o n p r o d u c t o f p h a r m a c o l i t e i n t h e

G e t c h e l l M i n e

K a a t i a l a i t e

F e ( H 2 A s O 4 ) 3

5 H 2 O

S e c o n d a r y F e – a r s e n a t e m i n e r a l s

K a n k i t e

F e A s O 4

3 5 H 2 O

O c c u r s a s p h a

s e a l p h a - A s S , t r i m o r p h o f r e a l g a r

a n d

p a r a r e a l g a r


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T a b l e 2

c o n t i n u e

d

M i n e r a l


O c c u r r e n c e

R e f e r e n c e

K r u t o v i t e

N i A s 2

O c c u r s i n t h e G e s h i b e r v e i n , S v o r n o s t s h a f t i n t

e r g r o w t h

w i t h n i c k e l s k u t t e r u d i t e a n d s o m e t i m e s w i t h

t e n n a n t i t e

L o r a n d i t e

T l A s S 2

O c c u r s i n l o w - t e m p e r a t u r e h y d r o t h e r m a l a s s o c i a t i o n s

a n d i n g o l d a n d m e r c u r y o r e d e p o s i t s

L a v e n d u l a n

N a C a C u 5 ( A s O 4 ) 4 C l 5 H

2 O

U n c o m m o n c o p p e r a r s e n a t e m i n e r a l , a s s o c i a t e

d w i t h

e r y t h r i t e , c

u p r i t e , m a l a c h i t e a n d c o b a l t i a n w a d

L e g r a n d i t e

Z n 2 ( A s O 4 ) ( O H ) ( H 2 O )

U n c o m m o n s e c o n d a r y m i n e r a l i n t h e o x i d i z e d

z o n e o f

z i n c – - b e a r i n g d e p o s i t s a n d o c c u r s r a r e l y i n g r a n i t e

p e g m a t i t e

L i r o c o n i t e

C u 2 A l A s O 4 ( O H ) 4

4 H 2

O

F o u n d a s a s

e c o n d a r y m i n e r a l s i n t h e o x i d i z e d

z o n e o f

p r i m a r y c o

p p e r o r e s

L a f fi t t i t e

A g H g A s S 3

I n a h y d r o t h e r m a l d e p o s i t w i t h o t h e r s u l fi d e s

M i x i t e

B i C u 6 ( A s O 4 ) 3 ( O H ) 6 3 ( H 2 O )

O c c u r s a s a s e c o n d a r y m i n e r a l i n t h e o x i d i z e d

z o n e s o f

c o p p e r d e p

o s i t s , a s r a d i a t i n g a c i c u l a r p r i s m s

a n d

m a s s i v e e n

c r u s t a t i o n s

M a u c h e r i t e

N i 1 1 A s 8

O c c u r s i n h y

d r o t h e r m a l v e i n s a l o n g s i d e o t h e r

n i c k e l

a r s e n i d e a n d s u l fi d e m i n e r a l s

O r e g o n i t e

N i 2 F e A s 2

S e c o n d a r y m

i n e r a l s , a s s o c i a t e d w i t h h y d r o t h e r m a l

n i c k e l m i n e r a l s i n a m e t a m o r p h o s e d u l t r a m a

fi c ,

w i t h i n s e r p

e n t i n i t e - h o s t e d c h r o m i t e d e p o s i t s

P a r a r e a l g a r

b - A s S / A s 4 S 4

F o u n d i n n a t

u r e a s a s e c o n d a r y m i n e r a l a n d c a n a l s o b e

f o r m e d b y

e x p o s i n g r e a l g a r t o l i g h t a t w a v e l e n g t h s

b e t w e e n a p p r o x i m a t e l y 5 0 0 a n d 6 7 0 n m

P o l y b a s i t e

( A g C u ) 1 6 ( S b A s ) 2 S 1 1

F o u n d w o r l d

w i d e a n d i s a n o r e o f s i l v e r . T h e

n a m e

c o m e s f r o m

t h e n u m b e r o f b a s e m e t a l s i n t h e m i n e r a l

P i c r o p h a r m a c o l i t e

C a 4 M g ( A s O 3 O H ) 2 ( A s O

4 ) 2

1 1 H 2 O

F o r m e d a s a n o x i d a t i o n p r o d u c t o f - b e a r i n g s u

l fi d e s i n

r e a c t i o n w i t h s u r r o u n d i n g c a l c i u m - b e a r i n g r o c k s

456 A. Basu et al.

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T a b l e 2

c o n t i n u e

d

M i n e r a l


O c c u r r e n c e

R e f e r e n c e

R e i n e r i t e

Z n 3 ( A s O 3 ) 2

E x t r e m e l y r a r e i n a d e e p o x i d a t i o n z o n e i n a d o l o s t o n e -

h o s t e d h y d r o

t h e r m a l p o l y m e t a l l i c o r e d e p o s i t

R o u t h i e r i t e

T l ( C u , A g ) ( H g , Z n ) 2 ( A s , S b )

2 S 6

I n h y d r o t h e r m

a l d e p o s i t s i n d o l o s t o n e

S k u t t e r u d i t e

( C o , N i , F e ) A s 3

H y d r o t h e r m a l

o r e m i n e r a l f o u n d i n m o d e r a t e t o

h i g h

t e m p e r a t u r e

v e i n s w i t h o t h e r N i – C o m i n e r a l s

S p e r r y l i t e

P t A s 2

O c c u r s i n t h e

l a y e r e d i g n e o u s c o m p l e x , i n t h e

O k t y a b r ’ s k o y e c o p p e r – n i c k e l d e p o s i t a n d i n t h e

n i c k e l o r e d e p o s i t o f S u d b u r y B a s i n

T e r u g g i t e

C a 4 M g A s 2 B 1 2 O 2 2 ( O H ) 1 2 1

2 ( H 2 O )

_

T y r o l i t e

C a C u 5 ( A s O 4 ) 2 C O 3 ( O H ) 4 6

H 2 O

S e c o n d a r y m i n e r a l f o r m e d b y t h e w e a t h e r i n g o f

a s s o c i a t e d c o p p e r a n d m i n e r a l s

Z i m b a b w e i t e

( N a , K ) 2 P b A s 4 ( N b , T a , T i ) 4 O

1 8

H y d r o t h e r m a l l y k a o l i n i z e d z o n e i n a n F - e n r i c h e

d

g r a n i t i c p e g m a t i t e i n t r u d e d i n P r e c a m b r i a n s t a

u r o l i t e

s c h i s t s

Z e u n e r i t e

C u ( U O 2 ) 2 ( A s O 4 ) 2

1 0 - 1 6 ( H

2 O )

O c c u r s a s a s e

c o n d a r y m i n e r a l i n t h e o x i d i z e d

w e a t h e r i n g z

o n e o f h y d r o t h e r m a l u r a n i u m o r e

d e p o s i t s w h i c h c o n t a i n


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In the case of the presence of arsenopyrite in sulfide ores having association with

sediment-hosted gold deposits, it is likely to be the earliest-formed minerals which are

obtained from hydrothermal solutions and formed around 100 C. It is responsible for

the native arsenic first and then arsenian pyrite, and even later, these are converted into

realgar and orpiment. This paragenetic sequence is often reflected by zonation withinsulfide minerals, with arsenopyrite cores zoning out to arsenian pyrite and realgar–

orpiment rims. Oxides and sulfates are formed at the latest stages of ore mineralization

[123, 124].

Rock-forming minerals

Arsenic is often present in varying concentrations in other common rock-forming

minerals, not as a major component. As far as the crustal abundance of arsenic is

concerned, it is 1.5 mg/kg. The element is strongly chalocophile. Almost 60 % of natural minerals are arsenates, 20 % sulfides and sulfosalts, and the remaining 20 %

are arsenides, arsenites, oxides, alloys, and polymorphs of elemental arsenic. As the

chemistry of arsenic closely follows that of sulfur, the greatest concentrations of the

element tend to occur in sulfide minerals, of which pyrite is the most abundant.

Arsenic concentrations of more than 105 mg/kg have been reported in sulfide minerals

and up to 7.6 9 104 mg/kg in iron oxides [125, 126]. However, concentrations are

typically much lower. Incorporation of arsenic into primary rock-forming minerals is

restricted in extent, for example by the substitution of As3? for Fe3? or Al3?.

Therefore, arsenic concentrations in silicate minerals are typically*

1 mg/kg or less[79]. Many igneous and metamorphic rocks have average arsenic concentrations of

1–10 mg/kg. Innumerable carbonate minerals and carbonate rocks contain similar

concentrations [127]. Concentrations in pyrite, chalcopyrite, and galena may change,

even within a given grain, but in some cases reach up to 10 % by weight (Table 3).

Arsenic may be found in the crystal structure of many sulfide minerals as a substitute

for sulfur. Apart from being a significant constituent of ore bodies, pyrite is also

formed in low-temperature sedimentary environments under reducing conditions

(authigenic pyrite). Authigenic pyrite plays a very important role in present-day

geochemical cycles. As for the natural formation of arsenic, the rich sources include

the sediments of a number of rivers, lakes and the oceans, as well as many aquifers.

Pyrite commonly forms preferentially in zones of intense reduction, such as around

buried plant roots or other nuclei of decomposing organic matter. It is sometimes

present in a characteristic form as framboidal pyrite. As and when this pyrite gets

formed, some of the soluble arsenic is liable to be imbibed. Pyrite is not stable in

aerobic systems and oxidizes to iron oxides with the release of large amounts of

sulfate, acidity, and associated trace constituents including arsenic. The presence of

pyrite as a minor constituent in sulfide-rich coals is ultimately responsible for the

production of ‘acid rain’ and acid mine drainage (AMD), and for the presence of

problems around coal mines and areas of intensive coal burning. High arsenic

concentrations are also found in many oxide minerals and hydrous metal oxides either

as part of the mineral structure or as sorbed species. Concentrations in Fe oxides can

also reach percent by weight values (Table 3), particularly where they form as the

oxidation products of primary iron sulfide minerals which have an abundant supply of

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arsenic . Adsorption of arsenate to hydrous iron oxides is particularly strong, and

sorbed loadings can be appreciable even at very low arsenic concentrations in solution

[128–130]. Adsorption by hydrous aluminium and manganese oxides may also be

important if these oxides are present in quantity [131–133]. Arsenic may also be

sorbed to the edges of clays and on the surface of calcite, a common mineral in manytypes of sediment [134, 135]. However, these loadings are much smaller on a weight

basis than for the iron oxides. It is adsorption reactions that are at the basis of the

relatively low (and non-toxic) concentrations of arsenic found in most natural waters.

Although arsenic concentrations in phosphate minerals indubitably vary, they can also

reach high values, for example up to 1,000 mg/kg in apatite (Table 3). However,

phosphate minerals are much less abundant than oxide minerals and so make a

correspondingly small contribution to the load of most sediments. Arsenic can also

substitute for Si4?, Al3?, Fe3?, and Ti4? in many mineral structures, and is therefore

present in many other rock-forming minerals, albeit at much lower concentrations.Most common silicate minerals contain around 1 mg/kg or less. Carbonate minerals

usually contain less than 10 mg/kg (Table 3).

Rocks, sediments and soils

Earth’s crust

A little discussion is required pertaining to the concentration of arsenic in the earth’scrust. Thus, the concentration is generally taken to be low. Onishi and Sandell gave

the average concentration of the lithosphere as about 2 mg/kg. A major source of

aqueous arsenic is derived mainly from concentration in all three types of rocks—

igneous, sedimentary and metamorphic—as has been stated in Table 4. An obvious

difference in arsenic concentration does not exist among the various types of

igneous rocks. Arsenic does, however, concentrate in some minerals. For instance,

arsenic readily substitutes for silicon, ferric iron, and aluminium in crystal lattices of

silicate minerals [136, 137]. As a result, concentrations tend to be relatively high in

volcanic glass, aluminosilicate minerals, and igneous rocks containing iron oxide.

Because the content of metamorphic rocks is dependent primarily on source-rock

composition, arsenic concentrations are highly variable in this rock type.

Sedimentary rocks generally contain higher arsenic concentrations than igneous

and metamorphic rocks. It was found that, in general, arsenic in non-marine shales/

clays has been adsorbed by clay minerals, whereas the arsenic associated with

marine shales/clays is present in pyrite and organic matter [138, 139].

Igneous rocks

Similarity may be found between concentrations of arsenic in igneous rocks and

those occurring in the crust. Ure and Berrow in 1982 [140] quoted an average value

of 1.5 mg/kg for all rock types (undistinguished). Averages for different types

distinguished by silica content (Table 4) are slightly higher than this value but


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generally less than 5 mg/kg. Volcanic glasses are only slightly higher with an

average of around 5.9 mg/kg (Table 4). Overall, there is relatively little difference

between the different igneous rock types. Despite not having exceptional

concentrations of arsenic, volcanic rocks, especially ashes, are often implicated in

the generation of high-arsenic waters. This may relate to the reactive nature of

recent acidic volcanic material, especially fine-grained ash and its tendency to give

rise to sodium-rich high-pH groundwaters [140].

Table 3 Typical concentrations

in common rock-forming

minerals

Mineral As concentration

range (mg/kg)

References

Sulfide minerals [76–82]

Pyrite 100–77,000Pyrrhotite 5–100

Marcasite 20–126,000

Galena 5–10,000

Sphalerite 5–17,000

Chalcopyrite 10–5,000

Oxide minerals

Haematite Up to 160

Fe-oxide(undifferentiated) Up to 2,000

Fe(III) oxyhydroxide Up to 76,000Magnetite 2.7–41

Ilmenite \1

Silicate minerals

Quartz 0.4–1.3

Feldspar \0.1–2.1

Biotite 1.4

Amphibole 1.1–2.3

Olivine 0.08–0.17

Pyroxene 0.05–0.8Carbonate minerals

Calcite 1–8

Dolomite \3

Siderite \3

Sulfate minerals

Gypsum/anhydrite \1–6

Barite \1–12

Jarosite 34–1,000

Other mineralsApatite \1–1,000

Halite \3–30

Fluorite \2

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Table 4 Typical arsenic concentrations in rocks, sediments, soils and other surficial deposits

Rock/sediment type As concentration

average and/or

range(mg/kg)

No. of

analyses

References

Igneous rocks [140–143]

Ultrabasic rocks (peridotite, dunite

kimberlite, etc.)

1.5 (0.03–15.8) 40

Basic rocks (basalt) 2.3 (0.18–113) 78

Basic rocks (gabbro, dolerite) 1.5 (0.06–28) 112

Intermediate (andesite, trachyte, latite) 2.7 (0.5–5.8) 30

Intermediate(diorite, granodiorite, syenite) 1.0 (0.09–13.4) 39

Acidic rocks (rhyolite) 4.3 (3.2–5.4) 2

Acidic rocks (granite, aplite) 1.3 (0.2–15) 116

Acidic rocks (pitchstone) 1.7 (0.5–3.3) –

Volcanic glasses 5.9 (2.2–12.2) 12

Metamorphic rocks

Quartzite 5.5 (2.2–7.6) 4

Hornfels 5.5 (0.7–11) 2

Phyllite/slate 18 (0.5–143) 75

Schist/gneiss 1.1 (\0.1–18.5) 16

Amphibolite and greenstone 6.3 (0.4–45) 45

Sedimentary rocks

Marine shale/mudstone 3–15 (up to 490)

Shale (Mid-Atlantic Ridge) 174 (48–361)

Non-marine shale/mudstone 3.0–12

Sandstone 4.1 (0.6–120) 15

Limestone/dolomite 2.6 (0.1–20.1) 40

Phosphorite 21 (0.4–188) 205

Iron formations and and Fe-rich sediment 1-2,900 45

Evaporites (gypsum/anhydrite) 3.5 (0.1–10) 5

Coals 0.3–35,000

Bituminous shale (Kupferschiefer, Germany) 100–900

Unconsolidated sediments

Various 3 (0.6–50)

Alluvial sand (Bangladesh) 2.9 (1.0–6.2) 13

Alluvial mud/clay (Bangladesh) 6.5 (2.7–14.7) 23

River bed sediments (Bangladesh) 1.2–5.9

Lake sediments, Lake Superior 2.0 (0.5–8.0)

Lake sediments, British Colombia 5.5 (0.9–44) 119

Glacial till, British Colombia 9.2 (1.9–170)

World average river sediments 5

Stream and lake silt (Canada) 6 (\1–72) 310


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Metamorphic rocks

Arsenic concentrations in the other two counterparts also have a direct bearing on

that in metamorphic rocks. Most contain around 5 mg/kg or less. Pelitic rocks

(slates, phyllites) typically have the highest concentrations, with on average ca.

18 mg/kg (Table 4).

Sedimentary rocks

The concentration of arsenic in sedimentary rocks is typically in the range 5–10 mg/

kg, i.e. slightly above average terrestrial abundance [141, 142]. Sedimentary rocks are

equally enriched in arsenic if a comparison is drawn with igneous rocks. Whereas

minerals such as quartz and feldspars predominantly abound in arsenic , sands and

sandstone are its relatively inferior containers. Average sandstone arsenic concen-

trations are around 4 mg/kg (Table 4), although Ure and Berrow gave a lower average

figure of 1 mg/kg. Argillaceous deposits have a broader range and higher average

arsenic concentrations than sandstones, typically an average of around 13 mg/kg

[140]. The higher values reflect the larger proportion of sulfide minerals, oxides,

organic matter, and clays. Arsenic concentration occurs in black shales mostly at thehigh end of the range primarily owing to their enhanced pyrite content. Data given in

Table 4 suggest that marine argillaceous deposits have higher concentrations than

non-marine deposits. This may also be a reflection of the grain-size distributions, with

potential for a higher proportion of fine material in offshore pelagic sediments as well

Table 4 continued

Rock/sediment type As concentration

average and/or

range(mg/kg)

No. of

analyses

References

Loess silts, Argentina 5.4–18

Continental margin sediments (argillaceous, some anoxic) 2.3–8.2

Soils

Various 7.2 (0.1–55) 327

Peaty and bog soils 13 (2–36) 14

Acid sulfate soils (Vietnam) 6–41 25

Acid sulfate soils (Canada) 1.5–45 18

Soils near sulfide deposits 126 (2–8,000) 193

Contaminated surficial depositsMining-contaminated lake sediment, British Colombia 342 (80–1,104)

Mining-contaminated reservoir sediment, Montana 100–800

Mine tailings, British Colombia 903 (396–2,000)

Soils and tailings-contaminated soil, UK 120–52,600 86

Tailings-contaminated soil, Montana Up to 1,100

Industrially polluted inter-tidal sediments, USA 0.38–1,260

Soils below chemicals factory, USA 1.3–4,770

Sewage sludge 9.8 (2.4–39.6)

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as systematic differences in sulfur and pyrite contents. Marine shales tend to contain

higher sulfur concentrations. Sediment provenance is also a likely important factor.

Particularly high arsenic concentrations have been determined for shales from mid-

ocean settings (mid-Atlantic ridge, average 174 mg/kg; Table 4). Atlantic Ridge

gases may in this case be a high-arsenic source. Concentrations in coals andbituminous deposits are variable but often high. Samples of organic-rich shale

(Kupferschiefer) from Germany have arsenic concentrations of 100–900 mg/kg

(Table 4). Some coal samples have been found with extremely high concentrations of

up to 35,000 mg/kg [143]. Carbonate rocks typically have low concentrations,

reflecting the low concentrations of the constituent minerals (ca. 3 mg/kg; Table 4).

Ironstones and Fe-rich rocks are the sources having the highest observed arsenic

concentrations, mostly several thousand mg/kg. Phosphorites are also relatively

enriched in arsenic (values up to ca. 400 mg/kg having been measured).

Unconsolidated sediments

Arsenic is the case with indurated equivalents such as muds and clays which have

usually higher concentration than sands and carbonates; in unconsolidated sediments,

concentrations are also of note. Values are typically 3–10 mg/kg, depending on

texture and mineralogy (Table 4). When concentrations are higher, they are likely to

reflect the amounts of pyrite or Fe oxides present. Higher values are also typically

found in mineralized areas. Placer deposits in streams can have very high

concentrations as a result of the abundance of sulfide minerals. Average arsenicconcentrations for stream sediments in England and Wales are in the range 5–8 mg/kg

[144]. Similar concentrations have also been found in river sediments where ground

water arsenic concentrations are high [145, 146]. It has been found that concentrations

in sediments from the River Ganges average 2.0 mg/kg (range 1.2–2.6 mg/kg), from

the Brahmaputra River they average 2.8 mg/kg (range 1.4–5.9 mg/kg), and from the

Meghna River they average 3.5 mg/kg (range 1.3–5.6 mg/kg). Cook et al. found that

the concentrations in lake sediments ranged between 0.9 and 44 mg/kg (median

5.5 mg/kg), but noted that the highest concentrations were present up to a few

kilometers down-slope of mineralized areas. The upper baseline concentration for

these sediments is likely to be around 13 mg/kg (90th percentile). They also found

concentrations in glacial till of 1.9–170 mg/kg (median 9.2 mg/kg; Table 4) and

noted the highest concentrations down-ice of mineralized areas (upper baseline, 90th

percentile, 22 mg/kg) [147, 148]. Relative arsenic enrichments have been observed in

reduci

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