Removal of arsenic from ground water

INTRODUCTION :

Sources of arsenics in water : Elevated arsenic levels are

found in groundwater due to antropogenic activities and natural
processes. Antropogenic activities include mining, use of
arsenical pesticides, herbicides and crop desiccants, release of
industrial effluents, and disposal of chemical wastes. The release
of arsenic from natural processes can be caused by the reduction
of iron hydroxide and the oxidation of pyrite minerals including
orpiment ( As2S3) and realgar (As2S2). Naturally occurring arsenic
in drinking water supplies may affect more than 100 million
people worldwide, including countries like India, Bangladesh,
China, Chile, Argentina, Mexico, Hungary, Taiwan, Vietnam, Japan,
New Zealand, Germany and the United States.

Side effects of arsenic in water : Arsenic can be

concentrated in lever, kidney, lung, and skin tissues by ingestion
of arsenic in drinking water. In order to minimize the health risk,
the United States Environmental Protection Agency (USEPA)
adopted a new maximum contaminant level ( MCL) for arsenic of
0.01 mg/L on January 22, 2001.

DIFFERENT METHODS ADOPTED FOR REMOVAL :

Arsenic exists in groundwater predominantly as inorganic
arsenite, As (III) ( H3AsO3 , H2AsO31- , HasO32- ) and arsenate, As(V)
( H3As04 , H2AsO41- , HAsO42- ). Greater attention is required for the
removal of As (III) from groundwater due to its higher toxicity and
mobility which mainly arise from its neutral state (HAsO30 ) in
groundwater as compared to the charged As (V) species which
predominates near pH 6-9.
Many methods are currently in use for the removal of As from
drinking water supplies including anion exchange, reverse
osmosis, lime softening , microbial transformation, chemical
precipitation and adsorption.

1. Removal of Arsenic (III) from Groundwater by

Nanoscale Zero Valency Iron:

( Environ.Sci.Technol.2005,39,1291-1298) Sushil Raj
Kanel,Bruce Manning

Introduction : The As (III) removal mechanism is mainly

due to spontaneous adsorption and coprecipitation of As (III)
with iron (II) and iron (III) oxides/ hydroxides, which form in
situ during Zero Valency Iron oxidation ( corrosion). The
oxidation of ZVI by water and oxygen produces ferrous iron.
Fe0 + 2 H2O 2 Fe2+ + H2 + 2OHFe0 + O2 + 2 H2O 2 Fe2+ + 4OH6 Fe2+ + O2 + 6 H2O 2 Fe3O4 (s)
Fe3O4 (s) + O2 + 18 H2O 12 Fe(OH)3 (s)

(1)
(2)
(3)
(4)

Heterogeneous reactions at the corroding ZVI surface are

complex and result in a variety of potential adsorption
surfaces for As (III) and As(V). Despite this complexity
studies using X ray absorption spectroscopy showed that
the products after reaction of As (III) and As (V) with ZVI
were inner sphere As (III) and As (V) surface complexes on
iron (III) oxides/ hydroxides corrosion products. Due to small
size and capacity to remain in suspension, NZVI can be
transported effectively by groundwater and can be injected
as subcolloidal metal particles into contaminated soils,
sediments and aquifers.

Materials and Chemicals :

1. Chemical Reagents used are NaAsO3 , HCl , NaOH,
NaH2PO4 , KI , NaBH4
2. Groundwater with total alkalinity, dissolved organic
carbon (DOC), iron (Fe2+) , sulphate (SO42-) and phosphate
(H2PO42-)with predetermined levels.
3. Polypropylene flasks
4. Concentrated HNO3
5. Disposable syringes
6. Hydride Generation Atomic Absorption spectrophotometry

Procedure :
1. NZVI material was synthesized by dropwise addition of
1.6M NaBH4 aquous solution to Ne- purged 1M
FeCl3.6H2O aquous solution at 23oC with stirring.
Fe(H2O)63+ + 3BH4- + 3H2O = Fe0 + 3B(OH)3 + 10.5H2

2. Stock solutions of 1000 mgL-1 As(III) and As(V) were

prepared by dissolving NaAsO2 and NaHAsO4.7H2O
respectively in deionized (DI) water.
3. Batch adsorption of As(III) was studied in 40 ml
polypropylene copolymer centrifuge tube containing 20
mg of NZVI in 20 ml of As(III) reaction solution in 0.01 M
NaCl.
4. Adsorption isotherms were produced by varying the
As(III) starting concentration, and the adsorption
envelopes were generated with a fixed As(III)
concentration (1 mg L-1) and varying pH.
5. Reaction proceeded for 12 h at 250C in a shaken water
bath(185 rpm) kept in dark.
6. After 12 hr the supernatant solution was filtered through
a 0.45-m membrane filter (Millipore) with a disposable
syringe and analysed by Hydride Generation atomic
absorption spectrophotometry with a detection limit of 1
gl-1.
7. As(III) was the initial form in all experiments and total
As( AsT) was measured by HGAAS after reaction with
NZVI.

Advantages of this method :

1. NZVI has applicability in ex-citu as well as in-situ
remediation of pollutants including arsenic.
2. NZVI can be used to remediate pollutants already present in
soil and groundwater.
3. NZVI promotes anaerobic microbial growth in the subsurface
by increasing pH, decreasing redox potential, producing
hydrogen gas and releasing ferrous iron.
4. The result of studies shows that NVZI is an efficient material
for the treatment of As(III) and may be used as a permeable
reactive barrier as well as for ex-citu groundwater
treatment.

Conclusion :
This work was supported by a grant (B10) from Sustainable
Water Resources Research Centre (SWRRC) of 21st Century
Frontier R&D Program through the Water Reuse Technology
Center (WRTC) at Gwangju Institute of Science and
Technology.

References :
Environ.Sci.Technol. 2005, 39 , 1291 1298

Sushil Raj Kanel , Bruce Manning , Laurent Charlet ,

Heechul Choi
Department of Environmental Science And Engineering
Gwangju Institute of Science and Technology.

2. Arsenic Removal with Composite Iron Matrix Filters

in Bangladesh
( Article Environmental Science & Technology) Anke
Neumann, Ralf Kaegi

Introduction :

The arsenic crisis in Bangladesh, due to widespread use of

groundwater contaminated with geogenic As, has been
described in various studies and reports. For rural and lowincome population who does not have access to safe water,
inexpensive, reliable, and low maintainance As- removal
filters are promising approach. The SONO filter, developed
and produced in Bangladesh from local materials, fulfils the
requirements and was approved for use.
SONO filters consists of two plastic buckets. The top bucket
contains a layer of zerovalent iron (ZVI) filings and turnings
of various sizes obtained from local foundry or machine
shop. The ZVI is thoroughly washed with water, treated with
food grade acids to enhance hydrous ferric oxide (HFO)
formation in the proprietary process, and dried. A loose
layer of this material forms the so-called composite iron
matrix (CIM). Water poured into the top bucket filters
through the sand and the CIM, resulting in corrosion of ZVI
and formation of Fe-phases that can remove arsenic from
the water. In the bottom bucket, more sand retains residual
Fe leached from the first bucket and wood charcoal
functions to sorb organic contaminants.

Materials & Chemicals :

1.
2.
3.
4.
5.

Acrylic glass tube column

Sand, CIM
Groundwater
H4SiO4 , phosphate, air-saturated water
Inductively coupled plasma mass spectrometry

Significance And Implications :

1. All studied SONO filters efficiently removes As, Mn, and Fe
from tubewell water.

2. Over 95% of the As passing the top sand layer was

removed in the CIM by sorption, coprecipitation, and
incorporation into solids formed during the corrosion of
ZVI.
3. The continued presence of dissolved Fe(II) in the CIM
appears to be important for the long term operation of
the filters.
4. Because As is removed predominantly in the CIM, the
other filter components such as sand, brick chips, and the
plastic components can be disposed without special care.

Conclusion :
This work was supported by the Swiss Agency for
Development and Cooperation (SDC) , discretionary funds of
EAWAG, and funds from the Alliance for Global Sustainability
Arsenic Mitigation Project in South East Asia.

Comparison of Arsenic Removal Technologies

Remarkable technological developments in arsenic removal from
rural water supply based on conventional arsenic removal
processes have taken place during the last five years. The
relative advantages and disadvantages of different arsenic
removal processes are compared .
Technology
Oxidation and
Sedimentation : air
oxidation, chemical
oxidation

Advantages

Relative simple, low

cost,but slow
process(air)
Relatively simple
and rapid process
(chemical)
Oxidises other
impurities and kills
microbes

Disadvantages

Process
removes only
some of arsenic.
Used as
pretreatment
for other
proesses

Coagulation and
filtration : alum
coagulation, iron
coagulation

Relatively low
capital cost
Relatively simple in
operation
Common chemicals
available

Sorption techniques :
activated alumina, iron
coated sand, ion
exchange resins,other
sorbents

Relatively well
known and
commercially
available
Well defined
technique

Membrane techniques :
nanofiltration, reverse
osmosis

Well-defined and
high removal
efficiency
No toxic solid waste
produced
Capable of removal
of other
contaminants.

Not ideal for

anion rich water
treatment ( eg.
Containing
phosphates)
Produces toxic
sludge
Low removal of
As(III)
Preoxidation is
required
Not ideal for
anion rich water
treatment ( eg
containing
Phosphates)
Produces
arsenic rich
liquid & solid
wastes
High cost
High capital and
running cost.
High-tech
operation and
maintainance
Arsenic rich
rejected water
is produced.

Comparison of Arsenic Removal Mechanisms and their

Costs in Bangladesh
Type of unit

Removal Mechanism

Bucket
Treatment
Type

Oxidation&
Coagulationsedimentation

Operation &
maintainance
cost/family/ye
ar($)
25

Capital
cost/
Unit ($)
6-8

filtration
SAFI Filter

Adsorption

Arsenic removal
unit for urban
water supply

Aeration,
Sedimentation and
Rapid filtration

Iron-arsenic
removal plant

Aeration,sedimentati
on,rapid filtration

Sidko

Adsorption by
granular
Fe(OH)3

40

1-1.5

240,000

200

10

4250

Comparison of Costs of different Arsenic Treatment

technologies in India
Technology

Treatment
Process

Type

Capacity

Cost ( US $)

AMAL(Oxide
India
Catalyst Pvt.
Ltd, W.B.)

Adsorption by
activated
alumina

Househol
d
Commun
ity

7,000-8,000
L
1,500000L/cy
cle

50
1,250;
400/charge

All India
Institute of
Hygiene &
Public
Health

Oxidation
followed by
coprecipitationfiltration

Househol 30 L/d
d
12,000 L/d
Commun
ity

5
1,000

Public
Health
Engineering
Department,
India

Adsorption of red
hematite,sand
and activated
alumina

Commun
ity

600 1000
L/h

1,000

Ion
Exchange
(India)
Limited

Adsorption by ion
exchange basin

Commun
ity

30,000
L/cycle

2,000

Chemicon and
Associates

Adsorption by
ferric oxide

Commun
ity

2,000,000
L/cycle

4,500;
400/charge

RPM
Marketing
Private
Limited

Activated
Alumina+ AAFS50(patented)

Commun
ity

200,000/
cycle

1,200 ;
500/charge

Pal Trockner
Limited, India

Adsorption by
ferric hydroxide

Househol 20 L/d
d
900,000
Commun L/cycle
ity

8
2000 ;
625/charge

Laboratory Methods :
A variety of analytical methods for laboratory determination of
arsenic has been described in has literature but many of them
essentially employ similar principles. The most common methods
prescribed for use after proper validation by international and
national standard methods include atomic absorption
spectrometry (AAS), inductively coupled plasma (ICP), anodic
stripping voltammetry (ASV), and silver diethyldithiocarbamate
(SDDC) spectrometric method. AAS is a sensitive single-element
technique with known and controllable interference. Both hydride
generation (HG) and graphite furnace (GF) AAS methods are
widely used for analysis of arsenic in water. ICP atomic emission
spectrometry (AES) and mass spectrometry (MS) are
multielement
techniques, also with known and controllable interference. ASV is
a useful technique for analysis of dissolved arsenic and arsenic
speciation but needs special precautions for accuracy. The SDDC
spectrometric method has been widely used for its simplicity and
low cost but suffers from interference and reproducibility. A
summary of laboratory analytical techniques, with important
features, is presented in table 4 (Rasmussen and Anderson 2002;
Khaliquzzaman and Khan 2003).

Field Test Kit :

Laboratory methods of arsenic measurement are costly and the
number of laboratories with arsenic measurement capabilities is
too few in the developing countries to meet present needs. Field
test kits have been developed for detection and measurement of
arsenic by different institutions and agencies in Bangladesh and
in other countries. The detection and
semiquantativemeasurement of arsenic by all field test kits is
based on the Gutzeit procedure, which involves the conversion of
all arsenic in water into As(III) by reduction, and then formation
of arsine gas by further reduction using nascent hydrogen in an

acid solution in a Gutzeit generator. The technique is also known

as the mercuric bromide stain method (APHA-AWWA-WEA 1985).
Presently available arsenic test kits have been developed
adopting various modifications of the method. The arsine, thus
liberated, produces a yellow to brown stain on a vertical paper
strip impregnated with mercuric bromide. The amount of arsenic
present in the water is directly related to the
intensity of the color. The color developed on mercuric bromidesoaked paper is compared either with a standard color chart or
measured by a photometer to determine the arsenic
concentration of the water sample. In some field test kits the
generated arsine is passed through a column containing a roll of
cotton moistened with lead acetate solution to absorb hydrogen
sulfide gas, if any is present in the gas stream.