Desalination 303 (2012) 1–11

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Desalination
journal homepage: www.elsevier.com/locate/desal

Removal of iron for safe drinking water

Shalini Chaturvedi, Pragnesh N. Dave ⁎
Department of Chemistry, Krantiguru Shyamji Krishna Verma Kachchh University, Mundra Road, Bhuj-370 001, Gujarat, India

H I G H L I G H T S

► Iron removal is among the problematic issues for making potable water.
► Its main issues involve taste, visual effects, and clogging
► Iron in the form of their hydroxide creates blockage in the pipe.
► Several removal methods summarized in here.
► Few methods are electro-coagulation: oxidation; ion-exchange; ultra-filtration, etc.

a r t i c l e i n f o a b s t r a c t

Article history: Universal access to safe drinking water is a challenge to the scientific community to which the responsibility
Received 19 April 2012 is incumbent on developing appropriate technologies. Safe drinking water must be globally available to all
Received in revised form 15 June 2012 communities worldwide. It can be roughly considered that water infrastructure is well developed in urban
Accepted 5 July 2012
areas as opposed to rural areas where the infrastructure is either poorly developed or non-existent. Accordingly,
Available online 26 July 2012
the population to be urgently deserved with safe drinking water is the rural one. In this review we are trying to
Keywords:
summarize all methods reported in the literature for the removal of iron from groundwater for water
Iron purification.
Water purification © 2012 Elsevier B.V. All rights reserved.
Filtration
Electro-coagulation
Oxidation
Ion-exchange

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Methods of removal of iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Electro-coagulation (EC) method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Mechanism of iron removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Oxidation/filtration method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3.1. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3.2. Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4. Ion exchange (IE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.5. Lime softening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.6. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.7. Activated carbon and other filtration materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.7.1. Granular activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.7.2. Activated carbon (AC) filtration process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.7.3. BIRM media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.7.4. Anthracite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.7.5. Greensand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.7.6. Pebbles and sand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.8. By Subsurface iron removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

⁎ Corresponding author. Tel.: +91 2832 235022.

E-mail address: pragnesh7@yahoo.com (P.N. Dave).

0011-9164/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.07.003
2 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11

2.9. Aerated granular filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

2.10. By ultrafiltration/microfiltration membrane process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.11. Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.12. Supercritical fluid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction
Iron is one of the most abundant metals of the Earth's crust. It
occurs naturally in water in soluble form as the ferrous iron (bivalent
iron in dissolved form Fe(II) or Fe(OH) +) or complexed form like the
ferric iron (trivalent iron: Fe(III) met in the precipity Fe(OH)3) or
bacterial form, too. The occurrence of iron in water can also have an
industrial origin; mining, iron and steel industry, metals corrosion,
etc. There are many industrial situations where iron or impurities
must be removed from solutions [1]. Iron in drinking water and
water supplies causes problems, such as giving reddish color and
odor [2].
Iron removal is among the problematic issues for making potable
water. Its main issues involve taste, visual effects, and clogging.
Excessive iron may be present in groundwater or can occur due to
the corrosion of iron pipes or residual of iron based coagulants. In
raw fresh water, iron concentration is usually 0–50 mg/L [3,4].
Groundwater contains iron due to the process of rain filtering
through soil, rocks, and minerals. Throughout its descent, the rainwater
collects iron from these sources and deposits them in the groundwater.
Water acidity and dissolved oxygen play an important role in the quan-
tity of iron collected. Greater acidity and higher levels of dissolved
oxygen lead to greater corrosion [4].
The objective of treating groundwater is to produce potable water
that seems natural. The presence of dissolved iron influences the taste
and aesthetic quality of the water. Depending on the type and amount
of iron, people may notice a metallic taste and red discoloration. Fur-
thermore, residual iron at levels above 0.3 mg/L may stain surfaces
and clothes. Certain bacteria thrive on elevated levels of iron, and
may cling to pipe surfaces as a suitable habitat. These bacteria may
become dense enough in population to clog pipes and reduce flow
rates. Unfortunately, once a colony is established it is difficult to erad-
icate. Furthermore, if the pipe is constructed of iron, degradation will
gradually occur and result in punctures and leakage. Clogging will
also occur if ferrous bicarbonate is present in the water. The chemical
reaction given below illustrates that ferrous bicarbonate in combina-
tion with water and oxygen will form iron hydroxide. This chemical
compound is insoluble and may collect to form a blockage in pipes
[4].
4FeðHCO3 Þ2 þ 2H2 O þ O2 →4FeðOHÞ3 þ 8CO2
Fortunately for us, iron intake has positive effects on our health in
moderate doses and is an essential nutrient. On average, we consume
approximately 2 L/day of water. Levels of iron in raw fresh water
typically do not exceed 50 mg/L and the recommended intake can
vary between 10 and 50 mg/L depending on age, sex, and physiological
status. As such, intake of untreated water would not be harmful to our
health. Removal of iron is a purely aesthetic issue [4].
There are several methods for removal of iron used in water puri-
fication processes. This is usually induced by the precipitation of iron
oxide/oxyhydroxides and often involves the co-removal of inorganic
and organic impurities because of the strong adsorptive capacity of
iron oxyhydroxides. Such processes are commercially significant. Iron
precipitates are notoriously gelatinous, metastable, and difficult to
settle and filter. This can make the process bottleneck [5]. World Health
Organization (WHO) has set a guideline value of 0.3 mg/L of iron in
drinking water [6]. There are several methods for removal of iron
from drinking water like ion exchange and water softening [7], activated
carbon and other filtration materials [8], supercritical fluid extraction
[9], bioremediation [10] and limestone treatment [11], oxidation by
aeration, chlorination, ozonation followed by filtration [12], by ash
[13], by aerated granular filter [2] and by adsorption [14]. Aeration and
separation is the most common method for removal of iron from
groundwater in public water supply systems, which is however not so
popular at domestic level. The iron content in surface water is very
low due to natural aerial oxidation of iron to its oxides, which subse-
quently separate out. Traditional knowledge or practices sometimes
provide vital clue to solving great problems. Assam is a state in the east-
ern part of India, where the groundwater is highly contaminated with
iron [13,15–17]. The villagers in Assam have been traditionally using
charcoal/ash–sand filtration systems for removal of iron. The charcoal
is sometimes used without ash, often mixed with ash and sometimes
it is mostly ash. The ash–charcoal mixture used is obtained from differ-
ent types of firewood including bamboo. They indiscriminately use any
ash or ash–charcoal mixture. Interestingly, the water, which is obtained
from hand tube-well or ring-well is put in the filter system and collected
through the filter immediately, did not seem to retain iron. The iron free
water was then sometimes subjected to zeolite filter before use. The use
of ash or charcoal is expected to facilitate removal of iron by making the
water alkaline, which subsequently precipitates iron as geothite or
ferrihydrite [17–19]. However, no systematic scientific study on this
traditional practice has been reported, whereas, such a study is also
necessary to ensure safety in using the treated water.
2. Methods of removal of iron
Several methods of iron removal are reported in the literature in
this review article we are trying to summarize all those methods of
iron removal.
2.1. Electro-coagulation (EC) method
Apart from impressive amount of scientific research on the treatment
of iron by different processes, a detail investigation on the economic
analysis of each process is scant. On the other hand, electrocoagulation
(EC) has been found as a promising technique in treating urban waste-
water [20], treatment of restaurant wastewater [21], treatment of
potable water [22], potato chips wastewater [23], arsenic removal [24],
fluorine removal from underground and wastewaters [25], treatment
of poultry slaughterhouse waste water [26], treatment of copper, lead
and cadmium in natural water and simulated waste waters [27], treat-
ment of laundry waste water [28], boron removal [29], olive mill waste
waters [30], alcohol distillery waste water [31]. This is clearly a motivation
for experimental investigation of iron removal from water/wastewater by
EC process. Compared to other processes, EC process bears merits such as
ambient operability, large volume handling ability, non-toxicity because
of non-consumption of chemicals and no eventual secondary pollutants
to discard at acceptable physical and chemical condition. It also requires
comparatively less treatment time and very effective removal efficiency
with simplified operation. In this work, electrocoagulation was tested as
an alternative method for treating the Fe(II) ranging concentration
up to 25 mg/L. Effects of different parameters such as applied current
 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
density, initial concentration of Fe(II) and inter electrode distance over
the extent of Fe(II) removal were studied in detail. Performance of the
EC process and the operating cost for the removal of Fe(II) were calculated
and presented well (Table 1). In the calculation of the operating cost, only
material and energy costs were considered, other cost items such as labor,
maintenance, solid/liquid separation costs were not taken into account.
The simplified cost equation was used to evaluate the operating cost.
This fundamental study will be helpful for further application in designing
an electrocoagulation unit for the treatment of water containing heavy
metal ions beyond their permissible limits [1].
2.2. Mechanism of iron removal
Electrocoagulation or enhanced coagulation accompanied by electro
floatation is an emerging electrochemical water and waste water treat-
ment technology. In electrocoagulation process an applied potential
generates the coagulant species in situ as the sacrificial metal anode
(aluminum or ferric) dissolves, while hydrogen is simultaneously
evolved at the cathode. Coagulant species is believed to be the responsi-
ble in aggregation as well as precipitation of suspended particles and
simultaneously adsorption of dissolved contaminants. Tiny bubbles of
hydrogen and oxygen, which are formed during electrolysis of water,
collide with air bubbles and float the pollutant particles. Choice of elec-
trode material depends on various criteria such as; low cost, low oxida-
tion potential, inertness towards the system under consideration, etc.
Different electrodes have been reported in the literature like carbon
[32], mild steel [33], graphite, titanium [34], iron [35] and aluminum
[36]. But iron and aluminum have been reported to be very effective
and successful in pollutant removal at favorable operating conditions.
The electrode reactions are summarized as follows:
3þ
Anode : Al→Al þ 3e ð1Þ
−
Cathode : 3H2 O þ 3e→ð3=2ÞH2 ↑ þ 3OH ð2Þ
During the final stages, coagulated aggregates interact with bubbles
and float to the surface or settle to the bottom of the EC bath. Flotation is
the dominant pollutant removal path for high operating currents, while
sedimentation is dominant at lower currents. The shift is due to the
bubble number concentration at low currents is insufficient to remove
the aggregated material, allowing sedimentation to dominate [37].
Al(III) and OH− ions generated by electrode reactions (1) and (2)
react to form various monomeric species such as Al (OH)+2, Al(OH)+2,
Al2(OH)24+, Al(OH)4− and polymeric species such as Al6(OH)153+,
Al7(OH)174+, Al8(OH)204+, Al13O4(OH)247+, Al13(OH)345+, which
transform finally into Al (OH)3(S) according to complex precipitation
kinetics
3þ þ
Al þ 3H2 O→AlðOHÞ3 þ 3H ð3Þ
Freshly formed amorphous Al (OH)3 (S) occurs as “sweep flocks”
having large surface areas. These flocks are active in rapid adsorption
of soluble organic compounds and trapping of colloidal particles and
are easily separated from aqueous medium by sedimentation or H2
flotation. These flocks polymerizes as nAl(OH)3 → Aln(OH)3n. Iron
exists in solution in the ferrous state, it can only remain in solution
in the absence of oxygen, and generally when the pH is below 6.5,
ferrous ion is oxidized in air according to the following reaction:
2þ þ 3þ
Fe þ ð1=4ÞO2 þ H ↔Fe þ ð1=2ÞH2 O ð4Þ
Presence of chloride ion may undergo the following reactions Bulk
H2 O→H þ OH
þ −
þ −
NaCl→Na þ Cl
3
2þ −
Fe þ 2Cl →FeCl2
− −
FeCl2 þ 3OH →FeðOHÞ3 ↓ þ 2Cl
þ −
H þ Cl →HCl
−
Anode 2Cl →Cl2 ↑ þ 2e
The state of iron in water depends above all on the pH and the
redox potential. By increasing the pH, dissolved iron, i.e. Fe(II) or
Fe(III) hydrolyzes to form precipitates [38]. The ferrous ion hydro-
lyzes to produce the array of mononuclear species FeOH+ to Fe(OH)4−2
between pH 7 and 14. The ferric ion, Fe (III) hydrolyzes much more read-
ily than the ferrous ion, Fe(II). Baes and Mesmer [39] presented
diagrams, which show that iron at the range of pH 7–8 is a precipitate.
The rates of ferrous ion oxidation by air increase with pH and about
90% conversion may be achieved in a few minutes at a pH of 7 [40–43].
Precipitation depends on the size and shape of the particle which is
formed after coagulation followed by the adsorption on the active sur-
faces of the coagulants formed during the electrocoagulation process.
At the higher pH, removal of iron is achieved mainly by adsorption of
iron hydroxide in the form of brown flocks due to the sufficient availabil-
ity of coagulants in the medium.
2.3. Oxidation/filtration method
The majority of iron treatment systems employ the processes of
oxidation/filtration. The oxidant chemically oxidizes the iron
(forming a particle), and kills iron bacteria and any other disease-
causing bacteria that may be present. The filter then removes the
iron particles.
Oxidation followed by filtration is a relatively simple process. The
source water must be monitored to determine proper oxidant dosage,
and the treated water should be monitored to determine if the oxida-
tion process was successful [44].
2.3.1. Oxidation
Before iron can be filtered, needed to be oxidized to a state in
which it can form insoluble complexes. Oxidation involves the transfer
of electrons from the iron or other chemicals being treated to the oxidiz-
ing agent. Ferrous iron (Fe2+) is oxidized to ferric iron (Fe3+), which
readily forms the insoluble iron hydroxide complex Fe(OH)3 [44].
The most common chemical oxidants in water treatment are chlo-
rine, chlorine dioxide, potassium permanganate, and ozone. Oxidation
using chlorine or potassium permanganate is frequently applied in
small groundwater systems. The dosing is relatively easy, requires simple
equipment, and is fairly inexpensive [44,45].
Chlorination is widely used for oxidation of divalent iron. However,
the formation of trihalomethanes (THMs) in highly colored waters may
be a problem. Chlorine feed rates and contact time requirements can be
determined by simple jar tests.
As an oxidant, potassium permanganate (KMnO4) is normally
more expensive than chlorine and ozone, but for iron and manganese
removal, it has been reported to be as efficient and it requires consid-
erably less equipment and capital investment. The dose of potassium
permanganate, however, must be carefully controlled. Too little
permanganate will not oxidize all the iron and too much will allow
permanganate to enter the distribution system and cause a pink
color. Permanganate can also form precipitates that cause mudball
formations on filters. These are difficult to remove and compromise
filter performance. Ozone may be used for iron oxidation. Ozone
4 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11

Table 1
Summary of all methods.

Method Removal Operating condition Advantage Disadvantage Coast Uses

efficiency
(%)

EC 95–99 Current density 0.01 to EC requires simple equipment and The sacrificial electrodes are Approx. 6.05 US$/m3 adaptable for
0.04 A/m2 is easy to operate with sufficient dissolved into wastewater streams as household
pH should be slightly operational latitude to handle most a result of oxidation, and need to be use
basic approx 7.5 problems encountered on running. regularly replaced.
EC found to be very fast Wastewater treated by EC gives
and effective method for palatable, clear, colorless and odor-
the water containing less water.
iron from low to very EC technique can be conveniently
high concentrations. used in rural areas where electricity
is not available, since a solar paned
attached to the unit may be
sufficient to carry out the process
Oxidation/ 80–90 pH should be in range of The majority of iron treatment The oxidant is difficult to store or Approx. 4.05 US$/m3 In rural areas
filtration 7.5 to 8.5. systems employ the processes of transport safely and system parts can
method Quality of water that oxidation/ filtration. be degraded by corrosion.
used The oxidant chemically oxidizes the The oxidation reaction results in a
iron (forming a particle), and kills solid manganese compound that may
iron bacteria and any other disease- interfere with system operation.
causing bacteria that may be present.
A low-cost method of providing
oxidation is to use the oxygen in air
as the oxidizing agent.
IE ~90 Effective for water Can remove iron that bound with Used only for small quantities of iron $0.05 to $0.20 per barrel Use for
containing less than organics. and manganese because there is a ground and
25 mg/L of dissolved Fe/ risk of rapid clogging surface water
Mn Softener resin can be rejuvenated if any oxidation occurs during the Adoptable
and reused. process, the resulting precipitate can where use of
Water quality such as pH or coat and foul the media. Cleaning water is
alkalinity are not important in the would then be required using acid or minimum
operation of IE sodium bisulfate
Adsorption 84–92 Operated under anoxic Longer filtration runs due to slower Ferrous ion adsorbed at filter media Low cost Useful for
condition suppressing head loss development. which is cleaned by oxygen-rich surface water
the oxidation of ferrous Better filtrate quality. water or by oxidant. like well
iron and iron is removed Shorter ripening time and less
by adsorptive filtration backwash water requirement.
Activated 75–90 Chemical nature of the Its multifunctional nature and the cannot significantly reduce bacterial Low cost Used in
carbon and carbon source, or the fact that it adds nothing contamination municipal
other amount of oxygen and detrimental to treat water. region
filtration hydrogen associated
materials with it.
Chemical composition Some filtration materials not
and concentration of the required any chemicals
contaminant
Subsurface >50 Periodically injection of No costly filter media and Low removal efficiency. Low cost Provide safe
iron removal aerated water is maintenance is needed. drinking
required. The tube well is the 1st preferred water in rural
option for drinking water in rural areas.
areas; and available to a majority of
the rural poor in their household;
Additional hardware beyond the
existing hand pump is affordable
and locally available/repairable.
Aerated 70 pH 7.5–8.0 It is a catalytic reaction rather than Back washing required. Higher than biological Can use at
granular Temperature of water in biological. Filtration rate is fast. Process effective at low temperature. process. laboratory
filter between 15–30 °C scale
UF/MF 80–90 Low pressure or vacuum Can control small pathogenic UF alone, however, is still unable to As advancements are Adaptable for
membrane filtration microorganisms such as viruses. fully eliminate dissolved inorganic made in membrane household
processes No need for chemicals. constituents such as iron and production and module use
Size-exclusion filtration as opposed manganese that can deteriorate the design, capital and
to media depth filtration. quality of water with respect to taste operating costs continue
and color. to decline
Bioremediation 70 Anaerobic condition is Addition of matched microbe strains Heavy metals such as cadmium and Low cost Use for
more suitable to the medium to enhance the lead are not readily absorbed or ground water
resident microbe population's ability captured by microorganisms treatment.
to break down contaminants.
No need of chemicals.
Supercritical ~80 Increased contact Increased contact between the Limited by the complexity of the High cost Remove
fluid between the chelating chelating agent and metal ions process and the cost of ligands metals from
extraction agent and metal ions increases the rate of metal chelate suitable for effective metal extraction sludge to
increased extraction formation and is the principal factor levels
efficiency of Fe in increased extraction efficiency. suitable for
Heavy metal can also be removed. land
application.
 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
may not be effective for oxidation in the presence of humic or fulvic
materials [46].
A low-cost method of providing oxidation is to use the oxygen in
air as the oxidizing agent in a tray aerator. Water is simply passed
down a series of porous trays to provide contact between air and
water. No chemical dosing is required, which allows for unattended
operation. This method is not effective for water in which the iron
is complexed with humic materials or other large organic molecules.
Oxygen is not a strong enough oxidizing agent to break the strong
complexes formed between iron and large organic molecules.
The presence of other oxidizable species in water hinders oxidation
of the desired reduced compounds. Volatile organic chemicals, other
organic compounds, or taste- and odor-causing compounds may result
in an oxidant demand. This additional oxidant demand must be
accounted for when dosing the oxidant. The expense of operation
derives from the chemical use in most cases, and therefore is directly
related to the source water quality [44,47].
2.3.2. Filtration
In general, manganese oxidation is more difficult than iron oxida-
tion because the reaction rate is slower. There are different filtration
media for the removal of iron and manganese, including manganese
greensand, anthra/sand or iron man sand, electromedia, and ceramic.
Manganese greensand is by far the most common medium in use
for removal of iron through pressure filtration. Greensand is a
processed material consisting of nodular grains of the zeolite mineral
glauconite. The material is coated with manganese oxide. The ion
exchange properties of the glauconite facilitate the bonding of the coat-
ing. This treatment gives the media a catalytic effect in the chemical
oxidation–reduction reactions necessary for iron removal. This coating
is maintained through either continuous or intermittent feed of potassi-
um permanganate. In this filtration type, potassium permanganate
(KMnO4), a purple crystal or liquid, is used to precipitate (meaning, to
convert to a solid) Fe/Mn. Chlorine or aeration may also be used. The
KMnO4 can be added either continuously (at a very dilute concentra-
tion) or in a more concentrated form at the time of backwash (batch
mode). In the latter option, the KMnO4 enhances a special oxygen rich
coating on the greensand media that causes precipitation of the
Fe/Mn within the media during normal filter operation [12,46].
For this filtration type, the pH needs to be over 7, at a minimum, and
preferably over 7.5 to assure full precipitation of Fe/Mn. Where manga-
nese concentration is high, a pH greater than 8 is recommended. Where
the pH is low, a chemical feed pump may be needed to raise the pH. A
contact/detention tank is sometimes installed to allow more time for
the oxygen and the Fe/Mn contaminants to produce a sizeable rust
particle.
KMnO4 greensand filtration is effective for very high levels of Fe/Mn.
Where the manganese level is high, feeding a dilute chlorine solution
may improve manganese removal. KMnO4, chlorine or aeration can
also remove hydrogen sulfide odor [46].
Anthra/sand (also iron-man sand) are other types of media available
for removal of iron They consist of select anthracite and sand with a
chemically bonded manganese oxide coating. Unlike manganese green-
sand, these media are conditioned in the filter after media installation.
Electromedia provides a slightly different option from the manga-
nese oxide coated media. This is a proprietary multi-media formulation
which uses a naturally occurring zeolite and does not require potassium
permanganate regeneration.
Finally, macrolite, unlike the other media discussed so far, is not a
naturally occurring material which then undergoes processing for
iron removal purposes. It is a manufactured ceramic material with a
spherical shape and a rough, textured surface. The principal removal
mechanism is physical straining rather than contact oxidation or
adsorption.
Each medium has its advantages and disadvantages. Selection of a
medium and oxidant should be based on pilot testing in which all
5
necessary design criteria can be determined. Pressure filtration
system manufacturers who offer the indicated media also offer fully
automated systems [44].
2.4. Ion exchange (IE)
Ion exchange should be considered only for the removal of small
quantities of iron and manganese because there is a risk of rapid clog-
ging. Ion exchange involves the use of synthetic resins where a
pre-saturant ion on the solid phase (the “adsorbent,” usually sodium)
is exchanged for the unwanted ions in the water [48]. One of the
major difficulties in using this method for controlling iron and man-
ganese is that if any oxidation occurs during the process, the resulting
precipitate can coat and foul the media. Cleaning would then be
required using acid or sodium bisulfate.
Iron that comes in contact with groundwater can react with CO2 to
form ferrous bicarbonate. Ferrous bicarbonate or clear water iron is
soluble in water and is not visible. This type of iron is effectively re-
moved by standard softening resin because it is a positive-charged
ion. The following equation summarizes the reaction that normally
occurs with ion exchange resin (R) [49]:
2RNa þ FeðHCO3 Þ2 þ O2 →R2 Fe þ 2NaHCO3
Two sodium molecules are released from the resin for each molecule
of ferrous iron that is picked up by the resin. A high concentration of salt
(8–26%) will reverse this reaction as seen in the following equation:
R2 Fe þ 2NaCl→2RNa þ FeCl2
Some system modifications should be considered to optimize this
type of water treatment. Frequent regenerations are needed to pre-
vent the iron from precipitating to its insoluble form. The following
chemical reaction occurs when clear water iron precipitates to red
water iron:
4FeðHCO3 Þ2 þ 2H2 O þ O2 →4FeðOHÞ3 þ 8CO2
If dissolved iron oxidizes, fouling can occur on the surface of the
resin as well as within the internal matrix of the bead. This type of
fouling reduces resin capacity and can allow excess iron to bleed
through the system. There are correction factors developed in the
industry to help size softeners for iron removal. A typical correction
factor may state that for each ppm of iron in the water, multiply by
a factor of 5 grains. This correction factor was developed to increase
the frequency of regeneration and decrease the amount of iron fouling
that might otherwise occur. Correction factors should be used as a
general guideline and may have to be increased or decreased in a
given area [44].
Iron fouling effects can also be minimized with the use of chemical
cleaners added into the brine regenerant. Sodium hydrosulfite and
sodium bisulfite are examples of these cleaners. They all chemically
reduce red water iron to clear water iron. A preventative maintenance
procedure utilizing a reducing agent at a pre-determined interval of
time will help keep the resin bed clean. Salt with a commercially
available iron-cleaning chemical can also be very useful when iron
levels are excessive. This will chemically clean the bed during regen-
eration, and it should not have any detrimental effect on the softening
resin.
In situations where iron fouling is heavy, the unit should be treated
manually with a higher concentration of cleaner. Normally, the iron-
cleaning chemicals added by the salt manufacturers are fairly low in
concentration. Other treatments include use of sequestering agents
like polyphosphates, chelating agents like EDTA, or an acid strip using
hydrochloric acid, phosphoric acid or citric acid.
Resin with a smaller particle size “fine mesh resin” appears to
have greater ability to pick up and release clear water iron. The theory
6 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
behind this material has to do with its greater surface area. There
seems to be an enhanced absorption and desorption of iron from
this type of resin because the exchange occurs to a greater degree at
the surface of the material. Any fouling that might occur can more
easily be removed since it occurs on the outer layer of the resin.
Cleaning agents are also more effective on surface iron fouling [50].
2.5. Lime softening
A water softener removes Fe/Mn which is in the dissolved “clear-
water” form. Softening also removes calcium (Ca) and magnesium
(Mg) ions which are the primary minerals responsible for “hard”
water. The treatment process consists of passing the water through
an ion exchange resin media bed. The Fe/Mn ions and also calcium
and magnesium ions in the water are “exchanged” for sodium
(Na +) ions which have been temporarily stored in the resin material.
As the hardness and Fe are removed from the water, sodium is added
proportionally. For every 10 mg/L of hardness and Fe removed,
approximately 5 mg/L of sodium will be added to the treated water.
For those concerned with elevated sodium levels in their drinking
water, potassium chloride (KCl) can be used in place of sodium chloride
(NaCl). The cost of KCl is higher than sodium chloride. Potassium, one of
the three principal elements in fertilizer, is a valuable soil nutrient [44].
Eventually the removal capacity of the ion exchange resin material
will become exhausted and the media will need to be regenerated.
The regeneration process begins with a physical backwash of the
media to remove fine particles. The resin is then immersed in a strong
salt brine solution. The sodium (or potassium) from the salt enters
the resin and displaces the previously removed Fe and hardness.
After a period of time (approximately 20 minutes), the remaining
brine along with the displaced “loosened” Fe and hardness are
flushed out of the device and disposed of into a dry well, septic
tank, or sewer. Studies by the Water Quality Association (a trade
organization of the home water conditioning industry) indicate that
waste brine does not injure leach fields or septic tanks. Additional
studies are now underway [47].
Ion exchange (IE) softening is described as effective for water
containing less than 25 mg/L of dissolved Fe/Mn. IE will not work at
all where the Fe/Mn have turned to a rusty color. Other aspects of
water quality such as pH or alkalinity are not important in the operation
of IE [50].
2.6. Adsorption
Anaerobic groundwater may contain ferrous iron at concentrations
of up to several milligrams per liter without discoloration or turbidity
in the water when directly pumped from a well. On exposure to the
atmosphere, however, the ferrous iron oxidises to ferric iron, giving an
objectionable reddish-brown color; iron promotes the growth of “iron
bacteria,” depositing a slimy coating on the piping; and at levels above
0.3 mg/L, iron stains laundry and plumbing fixtures [51].
The most common method of iron removal from groundwater is
oxidation-floc formation and involves three basic processes, e.g. oxida-
tion of ferrous iron by aeration, settling of the ferric hydroxide floc, and
floc filtration by rapid sand filtration. In adsorption-oxidation (adsorp-
tive filtration) iron removal, the system is operated under anoxic condi-
tion suppressing the oxidation of ferrous iron and iron is removed by
adsorptive filtration. On exhaustion of the ferrous iron adsorption
capacity of the filter media, the anoxic filter bed is regenerated by
backwashing the filter bed with oxygen-rich water or with a chemical
oxidant. A pilot study has demonstrated that adsorptive filtration has
several potential advantages over floc filtration, viz. longer filtration
runs due to slower head loss development, better filtrate quality,
shorter ripening time and less backwash water requirement [52].
Sharma [52] observed that ferrous iron adsorption capacity of filter
media varied widely. Basalt showed the highest ferrous iron adsorption
capacity followed by anthracite, olivine, magnetite, sand, pumice, and
limestone. George and Chaudhuri [53] observed that bituminous coal
was more effective than sand in adsorptive filtration iron removal
from groundwater.
Chaudhari et al. [54] studied the effectiveness of coal and carbona-
ceous shale as filter media in adsorptive filtration iron removal from
groundwater by direct filtration. In whole process water used in the
batch adsorption was a groundwater pumped out under anoxic con-
dition. The coal used was bituminous coal and the carbonaceous
shale was collected from a natural deposit in Batu Gajah, Perak. Coal
and carbonaceous shale were crushed and sieved to a geometric
mean size of 0.5 mm. Their result shows that coal or carbonaceous
shale removed (adsorbed) 83.8% or 91.7% of ferrous iron from the
groundwater (total iron 2.66 mg/L; ferrous iron 2.35 mg/L). Carbona-
ceous shale exhibited higher ferrous iron adsorption capacity than
that of coal. Apparently, carbonaceous shale would be a more effective
filter media in adsorptive filtration iron removal from groundwater.
Direct filtration through carbonaceous shale is a potentially useful
method for adsorptive filtration iron removal from groundwater.
Long-duration in situ direct filtration test should be conducted, includ-
ing regeneration of the filter media by backwashing with oxygen-rich
water or with a chemical oxidant, to make available more performance
data i.e. ripening time, length of filter run, backwash water requirement
and longevity of filter media.
2.7. Activated carbon and other filtration materials
The micro-contaminants present in water cannot be sufficiently
removed by the use traditional methods of water purification. Hence,
one of the most effective processes for removal of these contaminants
seems to be the use of activated carbons [55–57].
2.7.1. Granular activated carbon
Granular activated carbon has been used for the removal of organic
constituents, residual disinfectants and Fe/Mn in water. This not only
improves taste and minimizes health hazardous; it protects other
water treatment units such as reserve osmosis membranes and ion ex-
change resins form possible damage due to oxidation or organic fouling.
Activated carbon is favored water treatment technique because of its
multifunctional nature and the fact that it adds nothing detrimental to
treat water. Most activated carbon made from raw materials such as
nutshell, wood, coal and petroleum [58].
Granular activated carbon is a particularly good adsorbent medium
due to its high surface area to volume ratio. One gram of a typical com-
mercial activated carbon will have a surface area equivalent to 1000 m 2.
This high surface area permits the accumulation of a large number of
contaminant molecules. The specific capacity of a granular activated
carbon to adsorb organic compounds is related to molecular surface
attraction, the total surface area available per unit weight of carbon,
and the concentration of contaminants in the wastewater stream.
2.7.2. Activated carbon (AC) filtration process
AC works by attracting and holding certain chemicals as water
passes through it. AC is a highly porous material; therefore, it has an
extremely high surface area for contaminant adsorption. The equivalent
surface area of 1 pound of AC ranges from 60 to 150 acres [59–61].
AC is made of tiny clusters of carbon atoms stacked upon one
another. The carbon source is a variety of materials, such as peanut
shells or coal. The raw carbon source is slowly heated in the absence
of air to produce a high carbon material. The carbon is activated by
passing oxidizing gases through the material at extremely high tem-
peratures. The activation process produces the pores that result in
such high adsorptive properties.
The adsorption process depends on the following factors: 1) physical
properties of the AC, such as pore size distribution and surface area;
2) the chemical nature of the carbon source, or the amount of oxygen
 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
and hydrogen associated with it; 3) chemical composition and concen-
tration of the contaminant; 4) the temperature and pH of the water; and
5) the flow rate or time exposure of water to AC.
Forces of physical attraction or adsorption of contaminants to the
pore walls are the most important AC filtration process. The amount
and distribution of pores play key roles in determining how well
contaminants are filtered. The best filtration occurs when pores are
barely large enough to admit the contaminant molecule. Because con-
taminants come in all different sizes, they are attracted differently
depending on pore size of the filter. In general AC filters are most
effective in removing contaminants that have relatively large mole-
cules. Type of raw carbon material and its method of activation will
affect types of contaminants that are adsorbed. This is largely due to
the influence that raw material and activation have on pore size and
distribution.
Processes other than physical attraction also affect AC filtration.
The filter surface may actually interact chemically with organic mole-
cules. Also electrical forces between the AC surface and some contam-
inants may result in adsorption or ion exchange. Adsorption, then, is
also affected by the chemical nature of the adsorbing surface. The
chemical properties of the adsorbing surface are determined to a
large extent by the activation process. AC materials formed from
different activation processes will have chemical properties that make
them more or less attractive to various contaminants. For example
chloroform is adsorbed best by AC that has the least amount of oxygen
associated with the pore surfaces [59–61].
Large organic molecules are most effectively adsorbed by AC. A
general rule of thumb is that similar materials tend to associate. Or-
ganic molecules and activated carbon are similar materials; therefore
there is a stronger tendency for most organic chemicals to associate
with the activated carbon in the filter rather than staying dissolved
in a dissimilar material like water. Generally, the least soluble organic
molecules are most strongly adsorbed. Often the smaller organic mol-
ecules are held the tightest, because they fit into the smaller pores.
Concentration of organic contaminants can affect the adsorption
process. A given AC filter may be more effective than another type
of AC filter at low contaminant concentrations, but may be less effec-
tive than the other filter at high concentrations. This type of behavior
has been observed with chloroform removal.
2.7.3. BIRM media
BIRM is a black granular filter material used for removal of iron and/
or manganese from water in pressure or gravity systems. It contains an
active insoluble catalyst to precipitate iron and/or manganese. Because
the presence of iron is most common, iron removal is the usual applica-
tion for BIRM. Under suitable conditions, the iron and dissolved oxygen
in water react on contact with the BIRM filter bed and, as a result, the
iron is precipitated in the form of hydroxide. This is a flocculent material
which is filtered out in the bed of BIRM. Periodic backwashing flushes
out the accumulated iron and the BIRM is again ready to perform its
function. BIRM is not consumed in the iron removal operation. For
BIRM to effectively remove iron, the pH of the raw water must be greater
than 6.8. If both Iron and Manganese are present, the pH should be
between 7.5 and 8.5. For Manganese removal the pH should be between
8.0 and 9.0 for best results [62].
Few advantages of use of BIRM are as: no chemicals to purchase
for maintenance; iron removal efficiency is extremely high; negligible
labor cost. Only periodic backwashing required; durable material
with a long life; wide temperature range application [63].
2.7.4. Anthracite
Crushed Anthracite makes an excellent medium density filtration
media. Because of its angular shape, some of the sediment penetrates
deeper into the bed. When compared to equivalent filter sands, this
means longer filter runs and less head loss. Backwash rates are also
reduced. Because of its unique density, Anthracite can be used in
7
multi-media filters. At 23 kg/ft3 it will hydraulically classify and remain
above heavier media such as Filter Sand or Manganese Greensand,
providing a prefiltration layer [63]. Anthracite Filter Media has many
advantages:
• High carbon content — top quality anthracite.
• Low specific gravity — reduces backwash rates and energy consump-
tion.
• Close attention to gradation, hardness and purity assures consistent
and reliable performance.
• Unique density allows Anthracite to be combined with other filtra-
tion media in multi-media filters.
• Higher service flows and longer filter runs than equivalent sand filters.
• Cost effective — The low bulk density provides more filtration product
per unit cost.
2.7.5. Greensand
Manganese Greensand is formulated from a glauconitic greensand
which is capable of reducing iron, manganese and hydrogen sulfide
from water through oxidation and filtration. Soluble iron and manga-
nese are oxidized and precipitated by contact with higher oxides of
manganese on the greensand granules. The hydrogen sulfide is
reduced by oxidation to an insoluble sulfur precipitate. Precipitates
are then filtered and removed by backwashing. When the oxidizing
capacity power of the Manganese Greensand bed is exhausted, the
bed has to be regenerated with a weak potassium permanganate
(KMnO4) solution thus restoring the oxidizing capacity of the bed. 1 ½
to 2 ounces of potassium permanganate, in solution, per cubic foot of
Manganese Greensand is considered sufficient for normal regeneration.
It is required to vigorously backwash and regenerates the bed when it is
placed in service and before its oxidation capacity is totally exhausted.
Operating the bed after oxidation capacity is exhausted will reduce its
service life and may cause stain [12,46].
2.7.6. Pebbles and sand
Filter Sand and Gravel are naturally occurring, river washed, glacial
deposit products. Their excellent chemical properties — high in silica
content and low in soluble calcium, magnesium and iron compounds —
meet industrial standard specifications. Precision sizing and uniform
grading to close limits meet the rigid specifications of professional engi-
neers throughout the world. These products have been specified and
used nationally and internationally because of their high quality, desir-
able chemical properties, color, and wide range of precision sizing. Filter
Sand is graded specifically for water filtration plants. It can be used in
municipal, industrial or residential applications for sediment filtration
[62,63].
Uncrushed Gravel has a highly spherical shape that promotes good
flow and even distribution in support beds. Gravel is low in soluble
impurities and it will maintain the quality of the treated water, especially
in softeners. Three inch layers are recommended in graded support beds
[63].
2.8. By Subsurface iron removal
Subsurface iron and removal have the potential to be a cost-
effective technology to provide safe drinking water in rural
decentralized applications, using existing shallow tube wells. Subsur-
face or in-situ iron removal has been used in central Europe for many
decades [64–70].
Halem et al. [71] studied the removal of subsurface iron form shal-
low tube well drinking water supply in rural Bangladesh. The principle
of subsurface iron removal is that aerated water is periodically injected
into an anoxic aquifer through a tube well partially displacing the
iron-containing groundwater. The injected water oxidizes adsorbed
ferrous iron on the soil grains, resulting in a surface area of ferric iron
hydroxides for adsorption of soluble ferrous iron and oxyanions [72].
8 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
When the flow is reversed, soluble ferrous iron in the abstracted
groundwater is adsorbed onto the ferric iron coated soil grains and
water with reduced iron concentrations is abstracted. Injection is
started again once elevated iron levels arrive at the well.
By injecting oxygen-rich water into an anoxic aquifer, both
homogenous and heterogeneous oxidation of ferrous iron will occur
in the aquifer. Homogeneous oxidation of ferrous iron takes place in
solution, and predominantly occurs at the interface of injected water
and original, anoxic groundwater. Based on the large surface area of
iron hydroxides on the soil grains in the subsurface, it is thought that
the heterogeneous reaction of ferrous iron oxidation on the surface of
ferric iron hydroxides is dominant during subsurface iron removal. In
literature, the system's efficacy is explained by adsorptive catalytic
oxidation [67,68], where adsorbed ferrous iron is oxidized to form
new adsorption sites. On its way into the aquifer, the injected water
oxidizes adsorbed ferrous iron and thus “regenerates” the subsurface
for adsorption during abstraction:
III II III III  nology only for desalination, membrane processes are increasingly
Fe OFe OHðsÞ þ 0 : 25O2 þ 0 : 5H2 O→Fe OFe OHðsÞ þ OH
Due to the rapid consumption of oxygen during injection of aerated
water, the oxygen front will lag behind the injected water front. When
heterogeneous ferrous iron oxidation is complete, the iron hydroxide
surface is available for adsorption of ferrous iron and oxyanions, during
groundwater abstraction:
III II III II þ (coagulants, flocculates, disinfectants, pH adjustment); size-exclusion
Fe OHðsÞ þ Fe þ H2 O↔Fe OFe OHðsÞ þ 2H
Once the iron oxyhydroxide surface is exhausted, no more iron (II)
will be adsorbed and iron breakthrough will be observed in the pro-
duced water [73]. Hence, during abstraction the iron front is retarded
and more iron-free water can be produced than was injected. Every
period of injection-abstraction is referred to as a cycle.
2.9. Aerated granular filter
In general, iron exists in soluble from as ferrous iron and is
converted to insoluble ferric iron before removal is achieved. There
are several methods for removal of iron used in water purification
processes.
Laboratory scale experiments concerning iron removal from artifi-
cial raw water by artificial filter [74] using anthracite as filter media
were conducted. The major findings were that iron oxidation and
removal by an aerated filter is mainly a catalytic chemical reaction
rather than a biological reaction. Further, iron removal does not per-
form effectively without aeration. Iron removal was very effective
when the pH was weakly acidity. Iron oxide attached to the surface
of the media is identified as ferrihydrite [75–77] which catalyzes the
oxidation of iron. Iron oxidation and removal by an aerated filter is
primarily a chemical catalytic reaction rather than a biological
reaction [2].
2.10. By ultrafiltration/microfiltration membrane process
Ultrafiltration (UF) technologies recently have become more
popular in drinking water treatment, since they can control small
pathogenic microorganisms such as viruses very effectively. The use
of UF membranes and their hybrid processes is thus considered as
an attractive option in solving the issues related to viruses and proto-
zoan oocysts as well as disinfection/disinfection by-products [78–82].
UF alone, however, is still unable to fully eliminate dissolved inorganic
constituents such as iron and manganese that can deteriorate the qual-
ity of water with respect to taste and color.
Ultrafiltration (UF) is a variety of membrane filtration in which hy-
drostatic pressure forces a liquid against a semi permeable membrane.
Suspended solids and solutes of high molecular weight are retained,
while water and low molecular weight solutes pass through the
membrane. This separation process is used in industry and research
for purifying and concentrating macromolecular (103–106 Da) solu-
tions, especially protein solutions. Ultrafiltration is not fundamentally
different from reverse osmosis, microfiltration or nanofiltration, except
in terms of the size of the molecules it retains [83].
Microfiltration (MF) and Ultrafiltration (UF) are low pressure or
vacuum membrane filtration processes that are used for pathogen
and suspended solids removal. MF/UF membrane processes have
gained wide acceptance in the drinking water industry because of
their ability to produce a high-quality and consistent product water.
More recently MF/UF membrane filtration has gained acceptance as
a pretreatment for nanofiltration (NF) and reverse osmosis (RO) for
surface water and seawater applications [84].
A membrane or, more properly, a semipermeable membrane, is a
thin layer of material capable of separating substances when a driving
force is applied across the membrane. Once considered a viable tech-
ð5Þ
employed for removal of bacteria and other microorganisms, particulate
material, and natural organic material, Fe/Mn which can impart color,
tastes, and odors to the water and react with disinfectants to form disin-
fection byproducts (DBP). As advancements are made in membrane
production and module design, capital and operating costs continue to
decline.
This technique has few advantages like, no need for chemicals
ð6Þ
filtration as opposed to media depth filtration; good and constant quality
of the treated water in terms of particle and microbial removal; process
and plant compactness; and simple automation.
Ultrafiltration (UF) is used to remove essentially all colloidal parti-
cles (0.01 to 1.0 microns) from water and some of the largest dissolved
contaminants. The pore size in a UF membrane is mainly responsible for
determining the type and size of contaminants removed. In general,
membrane pores range in size from 0.005 to 0.1 micron. UF membrane
manufacturers classify each UF product as having a specific molecular
weight cutoff (MWC), which is a rough measurement of the size of con-
taminants removed by a given UF membrane. A 100,000 MWC UF mem-
brane means that when water containing a given standard compound
with a molecular weight of around 100,000 daltons is fed to the UF
unit, nearly all of the compound will not pass through the membrane
[83].
UF membrane assisted oxidation process for removal of iron from
ground/ surface water makes it safe for drinking purposes. It is sim-
ple, cost effective, adaptable at both domestic as well we community
level and is capable of removing high levels of iron. Several research
works on this are reported in the literature [12,83–85].
Choo et al. [83] investigate the removal of various levels of iron
and manganese along with chlorine dosages from lake water using
different UF systems in conjunction with an in-line pre-chlorination
step. In particular membrane fouling, caused by oxidized iron and
manganese particles, was assessed in depth with visualization of the
membrane surfaces. For feed water containing 1.0 mg/L of Fe and/or
0.5 mg/L of Mn, substantial iron removal was achieved even without
the addition of chlorine due to the oxidation of ferrous iron to ferric
by dissolved oxygen and the consequent formation of less soluble
iron hydroxide particles. Only negligible amounts of manganese re-
moval occurred in the absence of chlorine, but with a dose of chlorine
the manganese removal efficiency increased markedly and reached a
level of more than 80% (corresponding to less than 0.1 mg/L Mn) at a
chlorine dosage of 3 mg/L as Cl2.With a higher dosage of chlorine
(e.g., 5 mg/L Cl2), there was no significant increase in the removal
of metal ions but more serious membrane fouling occurred. Also,
oxidized manganese claimed a greater responsibility for membrane
fouling during UF with chlorination. This phenomenon was in close
association with the kinetics of manganese oxidation and its oxidized
 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
particles' deposition inside the pores during backwashing, rather than
its accumulation on top of the membrane skin layer. Turbidity and
natural organic matter (NOM) removal levels of efficiency were
enhanced with the addition of chlorine in the presence of iron and
manganese because the metal oxides, created by chlorination, could
serve as adsorbents.
Eills et al. [12] investigated removal of iron and manganese from
groundwater by a process which combines oxidation and MF, espe-
cially when the concentrations of these metals are high and variable.
For both natural and artificial groundwaters, ferrous ion oxidation
with oxygen results in the formation of particles ranging in size from
1.5 to 50 p.m. These oxide particles were filtered continuously at the
laboratory scale on a MF polymeric membrane with an absolute
porosity of 0.2 lam. The MF permeate analysis do not reveal any signif-
icant presence of metal, indicating that the particles are very efficiently
filtered even at relatively high concentrations of iron (10 mg/L). The
permeation flux decline is strongly affected by trans-membrane pres-
sure. A significant permeation flux decline occurs at higher operating
pressures whereas a constant permeation flux of 0.5 m/h is obtained
at lower pressures, i.e., below 10 kPa. Under low pressures MF perme-
ation flux is comparable to slow sand filtration rate at a similar pressure
difference but with a much thinner filtering medium. The effect of tan-
gential flow and iron concentration is much weaker than the pressure
effect within the experimental limits of the present study. Behaviors
of the artificial and natural ground waters are always very similar, indi-
cating that artificial waters can be used to conduct more basic studies.
Korchef [85] studied the kinetics of the oxidation and precipitation
of iron in presence of sulphate and ethylenediamine tetraacetic acid
(EDTA) ions during ultrafiltration process. The presence of these
ions delayed significantly the kinetics of oxidation–precipitation by
the formation of iron–sulphate or more stable iron–EDTA complexes.
This increased the solubility of iron during ultrafiltration process. The
ultrafiltration permitted to separate the iron colloids but not the iron
complexes with sizes lower than the diameter of the membrane
pores. The ultrafiltration of solutions containing iron requires a regular
and efficient cleaning process to avoid the membrane plugging.
2.11. Bioremediation
Bioremediation is the use of microorganism metabolism to
remove pollutants. Technologies can be generally classified as in situ
or ex situ. In situ bioremediation involves treating the contaminated
material at the site, while ex situ involves the removal of the contami-
nated material to be treated elsewhere.
Some examples of bioremediation technologies are phyto-
remediation, bioventing, bioleaching, landfarming, bioreactor,
composting, bioaugmentation, rhizofiltration, and biostimulation.
Bioremediation can occur on its own (natural attenuation or intrin-
sic bioremediation) or can be spurred on via the addition of fertilizers to
increase the bioavailability within the medium (biostimulation). Recent
advancements have also proven successful via the addition of matched
microbe strains to the medium to enhance the resident microbe
population's ability to break down contaminants. Microorganisms
used to perform the function of bioremediation are known as
bioremediators [86].
Not all contaminants, however, are easily treated by bioremediation
using microorganisms. For example, heavy metals such as cadmium and
lead are not readily absorbed or captured by microorganisms. The as-
similation of metals such as mercury into the food chain may worsen
matters. Phytoremediation is useful in these circumstances because
natural plants or transgenic plants are able to bioaccumulate these
toxins in their above-ground parts, which are then harvested for remov-
al [87]. The heavy metals in the harvested biomass may be further con-
centrated by incineration or even recycled for industrial use.
The elimination of a wide range of pollutants and wastes from the
environment requires increasing our understanding of the relative
9
importance of different pathways and regulatory networks to carbon
flux in particular environments and for particular compounds, and
they will certainly accelerate the development of bioremediation
technologies and biotransformation processes [88,89].
The biological treatment of groundwaters is used primarily to
remove electron donors from water sources, providing (biologically)
stable drinking water, which preclude bacterial re-growth during
subsequent water distribution. The dissolved metal cations of ferrous
iron and manganese belong also to the electron donors, which are
common contaminants found in most (anaerobic) ground waters.
The removal of iron and manganese is usually accomplished by the
application of chemical oxidation and filtration. However, biological
oxidation has recently gained increased importance and application
due to the existence of certain advantages, over the conventional
physicochemical treatment. The oxidation of iron and manganese is
accelerated by the presence of certain indigenous bacteria, the
so-called iron and manganese oxidizing bacteria [86].
Zouboulis and. Katsoyiannis [86] studied the bioremediation of
arsenic-contaminated groundwaters. According their treatment
method which was evaluated for long-term operation (10 months)
found that during the whole period of operation, the removal of triva-
lent arsenic was efficient and that the residual arsenic concentration
was below the MCL of 10 Ag/l. The method offers several advantages
towards the application of conventional oxidation (physico-chemical)
treatment. The use of chemical reagents for the oxidation of As(III) to
As(V) can be avoided, which renders the methods more economical
and safer for the environment. It can also provide the simultaneous
removal of major groundwater contaminants, such as iron and arsenic;
whereas when manganese would be also present, it can be core moved
after the completion of biological oxidation of iron, applying a secondary
filtration stage.
2.12. Supercritical fluid extraction
Several research works are reported in literature for metal extraction
using supercritical fluid carbon dioxide and summarized the various
combinations of chelating agents, metal ions, extraction conditions
and matrices used in supercritical fluid extraction (SFE) studies
[90,91]. β-Diketone ligands are commonly used as chelating agents for
SFE due to the ease of complex formation for nearly all metals and the
high solubility of metal β-diketonate complexes in supercritical fluid
CO2 [92–94]. The SFE of a metal ion (Mn+) from an aqueous solution
with a β-diketone chelating agent (HL) and CO2 requires satisfaction
of the following equilibrium conditions:
HLðCO2 Þ↔HLðaqÞ ð7Þ
K2 þ −
HLðaqÞ ↔ H ðaqÞ þ L ðaqÞ ð8Þ
− nþ β
nL ðaqÞ þ M ðaqÞ ↔ MðLÞnðaqÞ ð9Þ
MðLÞnðaqÞ↔MðLÞnðCO2 Þ ð10Þ
Fluorinated β-diketone ligands have been advocated for SFE due to
their favorable pKa in acidic CO2–water environments [95] and the
high CO2 solubility of their metal complexes [90,93]. Non-fluorinated
β-diketonate chelating agents have advantages as well. They are sub-
stantially less expensive than their fluorinated analogues, providing a
practical option for analytical and industrial scale SFE. Moreover,
non-fluorinated β-diketonates form stronger complexes (β) with
metal ions and are less likely to decompose in aqueous SFE environ-
ments than some of the fluorinated chelates [96,97].
Andersen and Bruno used a new magnetically coupled mixing
device [98–100], for entrain supercritical fluid CO2 into the aqueous
phase to increase contact between the hydrophobic chelating agent
10 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
and the aqueous metal ions. While most commercial magnetic stir
bars are designed to prevent gas–liquid entrainment [100], the
entraining rotor used i to maximize contact between gaseous and
liquid phases. Due to this iron (III) was extracted from water with
supercritical fluid CO2 and the chelating agent 2,2,7-trimethyl-
3,5-octanedione (H(tod)). Since H(tod) has low water solubility,
metal chelate formation is limited to the interface between CO2 and
water. Once formed, however, Fe(tod)3 is one of the most CO2-soluble
non-fluorinated β-diketonates reported [94]. Aqueous iron (III) solu-
tions were extracted with and without the entraining rotor.
A gas–liquid entraining rotor was used to achieve an extraction
efficiency of 79% for iron (III) removal from water using supercritical
fluid CO2 and H (tod). The extraction efficiency of the unmixed system
was only 26%. The rotor improves mass transport between the H (tod)
in the CO2 phase and the metal ions in the aqueous phase. This
increased contact between the chelating agent and metal ions increases
the rate of metal chelate formation and is the principal factor in
increased extraction efficiency. Moreover, entrainment mixing also
increases the rate of extraction by increasing the mass transport of
metal chelate into the supercritical fluid CO2 phase. Our results illustrate
that physical entrainment is critical in the optimization of SFE
procedures.
3. Conclusion
Iron is one of the most abundant elements of the earth's crust.
Groundwater easily gets contaminated with iron usually in its (+ II)
valence state. Although iron is an essential mineral for human, its
presence in groundwater above a certain level make the water
unusable mainly for aesthetic considerations such as discoloration,
metallic taste, odor, turbidity, staining of laundry. Providing people
with safe drinking water is a human need of universal relevance.
Therefore, efficient but affordable technologies are needed as the
communities in need (small municipalities and villages) are charac-
terized by their low-income. On the basis of literature search and
several experimental results we can conclude that oxidation/filtration
method is most suitable for rural areas. Various technologies for safe
drinking water provision are available but they are either cost intensive
or not applicable without electricity. Accordingly, suitable technology
should use low cost materials which are readily available and match
or exceed the capability of conventional water treatment technologies.
References
[1] D. Ghosh, H. Solanki, M.K. Purkait, Removal of Fe(II) from tap water by
electrocoagulation technique, J. Hazard. Mater. 155 (2008) 135–143.
[2] Bong-Yeon Cho, Iron removal using an aerated granular filter, Process Biochem.
40 (2005) 3314–3320.
[3] L. Stegpniak, U. Kegpa, E. Stan´czyk-Mazanek, The research on the possibility of
ultrasound field application in iron removal of water, Desalination 223 (2008)
180–186.
[4] Patrick Colvin, Valeriya Filipova, Alma Masic, Iron removal.VVAN01
Decentralized water and wastewater treatment, www.chemeng.lth.se/vvan01/
Arkiv/ExerciseB_Ironremoval.pdf2011.
[5] M. Loan, O.M.G. Newman, R.M.G. Cooper, J.B. Farrow, G.M. Parkinson, Defining the
Paragoethite process for iron removal in zinc hydrometallurgy, Hydrometallurgy
81 (2006) 104–129.
[6] World Health Organization, Guidelines for Drinking Water Quality, In: Recom-
mendations, 1, WHO, Geneva, Switzerland, 1984, p. 79.
[7] K. Vaaramaa, J. Lehto, Removal of metals and anions from drinking water by ion
exchange, Desalination 155 (2003) 157–170.
[8] R. Munter, H. Ojaste, J. Sutt, Complexed iron removal from ground water,
J. Environ. Eng. 131 (2005) 1014–1020.
[9] W.C. Andersen, T.J. Bruno, Application of gas–liquid entraining rotor to super-
critical fluid extraction: removal of iron(III) from water, Anal. Chim. Acta 485
(2003) 1–8.
[10] P. Berbenni, A. Pollice, R. Canziani, L. Stabile, F. Nobili, Removal of iron and man-
ganese from hydrocarbon-contaminated groundwaters, Bioresour. Technol. 74
(2000) 109–114.
[11] H.A. Aziz, M.S. Yusoff, M.N. Adlan, N.H. Adnan, S. Alias, Physicochemical removal
of iron from semiaerobic landfill leachate by limestone filter, Water Manage. 24
(2004) 353–358.
[12] D. Ellis, C. Bouchard, G. Lantagne, Removal of iron and manganese from ground-
water by oxidation and microfiltration, Desalination 130 (2000) 255–264.
[13] B. Das, P. Hazarika, G. Saikia, H. Kalita, D.C. Goswami, H.B. Das, S.N. Dube, R.K.
Dutta, Removal of iron by groundwater by ash: a systematic study of a traditional
method, J. Hazard. Mater. 141 (2007) 834–841.
[14] S.S. Tahir, N. Rauf, Removal of Fe2+ from the waste water of a galvanized pipe
manufacturing industry by adsorption onto bentonite clay, J. Environ. Manage.
73 (2004) 285–292.
[15] D.B. Mahanta, N.N. Das, R.K. Dutta, A chemical and bacteriological study of
drinking water in tea gardens of central Assam, Indian J. Environ. Prot. 24
(2004) 654–660.
[16] R. Sharma, S. Shah, C. Mahanta, Hydrogeochemical study of groundwater fluoride
contamination: a case study from Guwahati city, India, Asian J. Water Environ.
Pollut. 2 (2005) 47–54.
[17] G.J. Houben, Iron oxides in wells. Part 1. Genesis, mineralogy and geochemistry,
Appl. Geochem. 18 (2003) 927–939.
[18] G.J. Houben, Iron oxide incrustation in wells. Part 2. Chemical dissolution and
modelling, Appl. Geochem. 18 (2003) 941–954.
[19] K. Komnitsas, G. Bartzas, I. Paspaliaris, Efficiency of limestone and red mud bar-
riers: laboratory column studies, Miner. Eng. 17 (2004) 183–194.
[20] M.F. Pouet, A. Grasmick, Urban wastewater treatment by electrocoagulation and
flotation, Water Sci. Technol. 31 (3–4) (1995) 275–283.
[21] X. Chen, G. Chen, P.L. Yue, Separation of pollutants from restaurant wastewater
by electrocoagulation, Sep. Purif. Technol. 19 (2000) 65–76.
[22] E.A. Vik, D.A. Carlson, A.S. Eikum, T. Gjessing, Electrocoagulation of potable
water, Water Res. 18 (1984) 1355–1360.
[23] M. Kobyaa, H. Hiz, E. Senturka, C. Aydiner, E. Demirbas, Treatment of potato
chips waste water by electrocoagulation, Desalination 190 (2006) 201–211.
[24] P.R. Kumar, S. Chaudhari, K.C. Khilar, S.P. Mahajan, Removal of arsenic from
water by electrocoagulation, Chemosphere 55 (2004) 1245–1252.
[25] K.V. Drondina, I.V. Drake, Electrochemical technology for fluorine removal from
underground and waste waters, J. Hazard. Mater. 37 (1994) 91–100.
[26] M. Bayramoglu, M. Kobya, M. Eyvaz, E. Senturk, Technical and economic analysis
of electrocoagulation for the treatment of poultry slaughterhouse wastewater,
Sep. Purif. Technol. 51 (2006) 404–408.
[27] C. Escobar, C. Soto-Salazar, M. Ines Toral, Optimization of the electrocoagulation
process for the removal of copper, lead and cadmium in natural water and
simulated waste waters, J. Environ. Manage. 81 (2006) 381–391.
[28] J. Ge, J. Qu, P. Lei, H. Liu, Newbipolar electrocoagulation–electrofloatation
process for laundry waste water, Sep. Purif. Technol. 36 (2004) 33–39.
[29] A. Erdem, Y. Recep, B.M.M. Kocakerim, An empirical model for parameters
affecting energy consumption in boron removal from boron-containing waste
waters by electrocoagulation, J. Hazard. Mater. 144 (1–2) (2007) 101–107.
[30] U.T. Un, S. Ugar, A.S. Koparal, U.B. Ogutveren, Electrocoagulation of olive mill
waste waters, Sep. Purif. Technol. 52 (2006) 136–141.
[31] Y. Yavruz, EC and EF processes for the treatment of alcohol distillery waste
water, Sep. Purif. Technol. 53 (2006) 135–140.
[32] A.A. Gallegos, D. Pletcher, The removal of low level organics via hydrogen peroxide
formed in a reticulated vitreous carbon cathode cell, Part 2: the removal of phenols
and related compounds from aqueous effluents, Electrochim. Acta 44 (1999)
2483–2492.
[33] A.K. Golder, N. Hridaya, A.N. Samanta, S. Ray, Electrocoagulation of methylene
blue and eosin yellowish using mild steel electrodes, J. Hazard. Mater. 127
(1–3) (2005) 134–140.
[34] M. Murugananthan, G.B. Raju, S. Prabhakar, Separation of pollutants from
tannery effluents by electrofloatation, Sep. Purif. Technol. 40 (2004) 69–75.
[35] Y.S. Yildiz, A.S. Koparal, S. Irdemdez, B. Keskinler, Electrocoagulation of synthet-
ically prepared waters containing high concentration of NOM using iron cast
electrodes, J. Hazard. Mater. B139 (2007) 373–380.
[36] I.L. Hernandez, C.B. Diaz, G.R. Movales, B. Bilyeu, U. Nunez, A combined
electrocoagulation–sorption process applied to mixed industrial wastewater,
J. Hazard. Mater. 144 (2007) 240–248.
[37] N. Maximova, O. Dahl, Environmental implications of aggregation phenomena:
current understanding, Curr. Opin. Colloid Interface Sci. 11 (2006) 246–266.
[38] J.D. Hem, Stability field diagrams as aids in iron chemistry studies, J. Am. Water
Works Assoc. 53 (1961) 211.
[39] C.F. Baes, R.E. Mesmer, The Hydrolysis of Cations, Krieger Publishing Company,
Malabar, Florida, 1976.
[40] W. Stumm, G.F. Lee, Oxygenation of ferrous iron, Ind. Eng. Chem. Res. 53 (1961)
143–146.
[41] D.W. Sundstrom, H.E. Klei, Wastewater Treatment, Prentice-Hall Inc., Englewood
Cliffs, NJ, 1979.
[42] H. Tamura, K. Goto, M. Nagayama, The effect of ferric hydroxide on the oxygen-
ation of ferrous ions in neutral solutions, Corros. Sci. 16 (1976) 197–207.
[43] N. Daneshwar, A. Oladegarazope, N. Djafarzadeh, Decolorization of basic dye
solutions by electrocoagulation: an investigation of the effect of operational
parameters, J. Hazard. Mater. B129 (2006) 116–122.
[44] S. Vigneswaran, C. Visvanathan, Water Treatment Processes: Simple Options,
CRC Press, New York, NY, 1995.
[45] R.B. Robinson, State-of the-Art: Iron and Manganese Control, In: Proceedings of the
New England Water Works Association Conference and Exhibition. Marlborough,
MA, 1998.
[46] C. Lessard, D. Ellis, J. Serodes, C. Bouchard, Oxydation du fer et du manganese
dans le traitement des eaux souterraines, Vecteur Environ. 32 (3) (1999) 30–37.
[47] National Research Council, Safe Water from Every Tap: Improving Water Service
to Small Communities, National Academy Press, Washington DC, 1997.
 S. Chaturvedi, P.N. Dave / Desalination 303 (2012) 1–11
[48] Ion Exchange and Demineralization, Env. Tech Brief #DWBLPE56, 1997.
[49] Mike Keller, Iron removal by ion exchange: standing on solid ground, Water
Cond. Purif. (June 2004) 20–23.
[50] Removal of Iron and Manganese from Drinking Water Technical Version, Env
Tech Brief # WD-DWGB-3-7, 2010.
[51] World Health Organization, Guidelines for drinking-water quality incorporating
first addendum, Vol. 1, Recommendations, 3rd ed., 2006. (Geneva, Switzerland).
[52] S.K. Sharma, Adsorptive iron removal from groundwater, IHE Delft/Wegeningen
University, The Netherlands, 2001.
[53] A.D. George, M. Chaudhuri, Removal of iron from groundwater by filtration
through coal, J. Am. Water Works Assoc. 69 (1977) 385–389.
[54] Malay Chaudhuri, Nasiman Bin Sapari, Siti Farhana Bint Mohak, Removal of Iron
from Groundwater by Direct Filtration through Coal and Carbonaceous Shale, In:
Int. Conf. Cons. Build. Tech, 2008.
[55] E. Okoniewska, Z. Debowski, Efektywnosc usuwania manganu z wody w zaleznosci
od warunków impregnacji wegli aktywnych, In: Konferencja Naukowo-
Techniczna, Mikrozanieczyszczenia w srodowisku czlowieka. Czestochowa, 2003,
pp. 172–177, (in Polish).
[56] D. Savova, N. Petrow, M.F. Yardim, The influence of the texture and surface prop-
erties of carbon adsorbents obtained from biomass products on the adsorption
of manganese ions from aqueous solution, Carbon 41 (2003) 1897–1903.
[57] Ewa Okoniewska, Joanna Lach, Malgorzata Kacprzak, Ewa Neczaj, The removal
of manganese, iron and ammonium nitrogen on impregnated activated carbon,
Desalination 206 (2007) 251–258.
[58] Frank DeSilva, Activated carbon filtration, Water quality product Magzi, Jan
2000.
[59] David O. Cooney, Adsorption Design for Wastewater Treatment, Lewis Publisher,
Boca, Raton FL, 1999.
[60] Wes Mac Gowan, Residential Water Processing, Water Quality Association, Lisle,
IL, 1997.
[61] H. Theodore Meltzer, High Purity Water Preparation, Tall Oaks Publishing, Littleton
Co, 1999.
[62] http://www.purewaterproducts.com/articles/birm.
[63] http://clear-ion.tradeindia.com/Exporters_Suppliers/Exporter2483.31736/Sand-
Activated-carbon-Iron-Removal-Filter.html.
[64] R.O. Hallberg, R. Martinell, Vyredox e in situ purification of groundwater,
Ground Water 14 (2) (1976) 88–93.
[65] P.W. Boochs, G. Barovic, Numerical-model describing groundwater treatment by
recharge of oxygenated water, Water Resour. Res. 17 (1) (1981) 49–56.
[66] G. Jechlinger, W. Kasper, F. Scholler, F. Seidelberger, The removal of iron and
manganese in ground waters through aeration underground, Water Supply 3
(1) (1985) 19–25.
[67] R. Rott, M. Friedle, Physical, chemical and biological aspects of the removal of
iron and manganese underground, Water Supply 3 (2) (1985) 143–150.
[68] C.G.E.M. van Beek, Experiences with underground water treatment in the
Netherlands, Water Supply 3 (2) (1985) 1–11.
[69] C.A.J. Appelo, B. Drijver, R. Hekkenberg, M. de Jonge, Modeling in situ iron
removal from ground water, Ground Water 37 (6) (1999) 811–817.
[70] S. Mettler, In-situ removal of iron from groundwater: Fe (II) oxygenation, and
precipitation products in a calcareous aquifer. Ph.D. dissertation, Swiss Federal
Institute of Technology, Zurich, 2002.
[71] D. van Halem, S. Olivero, W.W.J.M. de Vet, J.Q.J.C. Verberk, G.L. Amy, J.C. van Dijk,
Subsurface iron and arsenic removal for shallow tube well drinking water
supply in rural Bangladesh, Water Res. 44 (2010) 5761–5769.
[72] C.A.J. Appelo, W.W.J.M. de Vet, Modeling in situ iron removal from groundwater
with trace elements such as As, In: in: A.H. Welch, K.G. Stollenwerk (Eds.), Arsenic
in Groundwater, Kluwer Academic, Boston, 2003.
[73] D.A. Dzombak, F.M.M. Morel, Surface Complexation Modeling: Hydrous Ferric
Oxide, Wiley0-471-63731-9, 1990.
[74] Hujita Kenchi, B.R. Kansakal, A study on the nitrification by aeration filter, Jpn.
Water Works Assoc. 56 (8) (1987) 2–15.
[75] E. Murad, U. Schwertmann, The Mossbauer spectrum of ferrihydrite and its
relations to those of other iron oxides, Am. Mineral. 65 (1980) 1044–1049.
[76] F.V. Chukhrov, B.B. Zvyagin, A.I. Gorshkov, L.P. Yermilova, V.V. Balashova,
Ferrihydrite, Int. Geol. Rev. 16 (10) (1974) 1131–1143.
11
[77] J.H. Johnston, D.G. Lewis, A detailed study of the transformation of ferrihydrite to
hematite in an aqueous medium at 92°C, Geochim. Cosmochim. Acta 47 (1983)
823–1831.
[78] S.S. Madaeni, A.G. Fane, G.S. Grohmann, Virus removal from water and wastewater
using membranes, J. Membr. Sci. 102 (1995) 65–75.
[79] G.K. Pearce, M. Heijnen, J. Reckhouse, Using ultrafiltration membrane technology to
meet UK Cryptosporidium regulations, Membr. Technol. 1 (2002) 6–9.
[80] Y.J. Chang, K.H. Choo, M.M. Benjamin, S. Reiber, Combined adsorption/UF
process increases TOC removal, J. Am. Water Works Assoc. 90 (5) (1998) 57–71.
[81] S.J. Lee, K.H. Choo, C.H. Lee, Conjunctive use of ultrafiltration with powdered
activated carbon adsorption for removal of synthetic and natural organic matter,
J. Ind. Eng. Chem. 6 (2000) 357–361.
[82] K.W. Lee, K.H. Choo, S.J. Choi, K. Yamamoto, Development of an integrated iron
oxide adsorption/membrane separation system for water treatment, Water
Sci. Technol. Water Supply 2 (2002) 293–300.
[83] Kwang-Ho Choo, Haebum Lee, Sang-June Choi, Iron and manganese removal and
membrane fouling during UF in conjunction with prechlorination for drinking
water treatment, J. Membr. Sci. 267 (2005) 18–26.
[84] Michael Pilutti, Julia E. Nemeth, Technical and Cost Review of Commercially
Available mf/uf Membrane Products, International Desalination Association,
2003. (BAH03-029).
[85] A. Korchef, I. Kerkeni, M.B. Amor, S. Galland, F. Persin, Iron removal from
aqueous solution by oxidation, precipitation and ultrafiltration, Desalin. Water
Treat. 9 (2009) 1–8.
[86] Anastasios I. Zouboulis, Ioannis A. Katsoyiannis, Recent advances in the biore-
mediation of arsenic-contaminated groundwaters, Environ. Int. 31 (2005)
213–219.
[87] R.B. Meagher, Phytoremediation of toxic elemental and organic pollutants, Curr.
Opin. Plant Biol. 3 (2) (2000) 153–162.
[88] In: E. Diaz (Ed.), Microbial Biodegradation: Genomics and Molecular Biology, 1st
ed., Caister Academic Press, ISBN: 1904455174, 2008.
[89] D.R. Lovley, Cleaning up with genomics: applying molecular biology to bioreme-
diation, Nat. Rev. Microbiol. 1 (1) (2003) 35–44.
[90] C.M. Wai, S. Wang, Supercritical fluid extraction: metals as complexes,
J. Chromatogr. A 785 (1997) 369–383.
[91] M. Ashraf-Khorassani, M.T. Combs, L.T. Taylor, Supercritical fluid extraction of
metal ions and metal chelates from different environments, J. Chromatogr. A
774 (1–2) (1997) 37–49.
[92] A.F. Lagalante, B.N. Hansen, T.J. Bruno, R.E. Sievers, Solubilities of copper (II)
β-diketonates in supercritical carbon dioxide, Inorg. Chem. 34 (1995)
5781–5785.
[93] N.G. Smart, T. Carleson, T. Kast, A.A. Clifford, M.D. Burford, C.M. Wai, Solubility of
chelating agents and metal-containing compounds in supercritical fluid carbon
dioxide, Talanta 44 (1997) 137–150.
[94] W.C. Andersen, R.E. Sievers, A.F. Lagalante, T.J. Bruno, Solubilities of Cerium(IV),
Terbium(III), and Iron(III) ß-Diketonates in supercritical carbon dioxide,
J. Chem. Eng. Data 46 (2001) 1045–1049.
[95] K.L. Toews, R.M. Shroll, C.M. Wai, N.G. Smart, pH defining equilibrium between
water and supercritical carbon dioxide. Influence of SFE of organics and metal
chelates, Anal. Chem. 67 (1995) 4040–4043.
[96] M.Z. Ozel, M.D. Burford, A.A. Clifford, K.D. Bartle, A. Shadrin, N.G. Smart, N.D. Tinker,
Supercritical fluid extraction of cobalt with fluorinated and non-fluorinated
β-diketones, Anal. Chim. Acta 346 (1) (1997) 73–80.
[97] M. Ashraf-Khorassani, M.T. Combs, L.T. Taylor, Solubility of metal chelates and
their extraction from an aqueous environment via supercritical CO2, Talanta
44 (5) (1997) 755–763.
[98] T.J. Bruno, M.C. Rybowiak, Vapor entraining magnetic mixer for reaction and
equilibrium applications, Fluid Phase Equilib. 178 (2001) 271–276.
[99] T.J. Bruno, M.C. Rybowiak, Mixing liquids and entrainment mixing of vapor into
liquids, US Patent (TBA), 2002.
[100] Wendy C. Andersen, Thomas J. Bruno, Application of a gas–liquid entraining
rotor to supercritical fluid extraction removal of iron (III) from water, Anal.
Chim. Acta 485 (2003) 1–8.