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Arsenic Removal PDF
Arsenic Removal PDF
Richard Johnston
Consultant to UNICEF and WHO
and
Han Heijnen
WHO Environmental Health Advisor, Bangladesh
Abstract
Arsenic contamination of drinking water has been reported from many parts of
world. In some arsenic affected areas, substitution of drinking water source by a
safe and easily available one may not be possible during part or all of the year,
or may be very expensive. Arsenic removal may be a more appropriate water
supply option in these situations. This paper describes some safe water
technologies for arsenic removal.
Coagulation is the most common arsenic removal technology. As many
Bangladesh waters contain arsenite, oxidation with chlorine or permanganate is
required first. Coagulation with ferric chloride works best at pH below 8. Alum
has a narrower effective range, from pH 6-8. Ion exchange resins are
commercially produced synthetic materials that can remove some compounds
from water. These resins only remove arsenate. Activated alumina, like ion
exchange resins, is commercially available in coarse grains. Activated alumina
beds usually have much longer run times than ion exchange resins, typically
several tens of thousands of beds can be treated before arsenic breakthrough.
Activated alumina works best in slightly acidic waters (pH 5.5 to 6). Membrane
methods for arsenic removal include reverse osmosis and nanofiltration.
Currently available membranes are more expensive than other arsenic removal
options, and are more appropriate in municipal settings, where very low arsenic
levels are required. Other techniques exist for arsenic removal, but are less well
documented. When arsenic-rich water also contains high levels of dissolved iron,
iron removal will also remove much of the arsenic. Introduction of zero-valent
iron filings in three-pitcher filters to treat water in the home is showing great
2 Technologies for Arsenic Removal from Drinking Water
promise. Many new materials are being tested for arsenic removal, from low-
tech iron-coated sand and greensand to specially engineered synthetic resins.
In all cases, technologies should meet several basic technical criteria. The
biggest challenges ahead lie however in applying the technologies described in
poor, rural settings, and in enabling those communities to choose safe sources of
water for drinking and cooking.
INTRODUCTION
In areas where the drinking water supply contains unsafe levels of arsenic, the
immediate concern is finding a safe source of drinking water. There are two main
options: finding a new safe source, and removing arsenic from the contaminated
source. In either case, the drinking water supplied must be free from harmful
levels of arsenic, but also from bacteriological contamination, and other chemical
contaminants. This paper reviews available technologies for arsenic removal.
When arsenic contamination is identified, the immediate priority must be to
find a safe alternate source of drinking and cooking water for affected
communities. Alternate sources must be not only arsenic-free, but also
microbiologically safe it would be a serious mistake to revert back to unsafe
use of surface water sources. In some cases, there may be no one technology that
can provide communities with a sustainable, continuous, affordable, safe water
supply. If a year-round safe water source is not currently available, it may be
necessary as a short-term solution to use one source during wet seasons (e.g.
groundwater, rainwater) and another during dry seasons (e.g. removing arsenic
from contaminated water). If a completely satisfactory, arsenic-free water source
cannot be established, the short-term goal should be to reduce arsenic levels in
drinking water as much as possible, as quickly as possible, even if regulatory
standards cannot be immediately met. It should be recalled that health effects of
arsenic are dose-dependent, and a partial solution is better than no solution. The
implementation of a temporary solution should not be used as a reason to delay
design and implementation of a long-term plan.
In all cases, technologies should meet several basic technical criteria. Water
supply options must first of all be able to produce water of the required quality,
both chemical and bacteriological. Systems should also be able to supply water in
adequate quantity, throughout different seasons. Technologies should be robust.
It is important that operational safety be ensured. Finally, technologies should not
have an undue adverse effect on the environment.
Technologies meeting these technical criteria can be evaluated under several
socioeconomic criteria. First, the systems must be economically feasible.
Introduction of new technologies requires institutional capacity including
production and delivery of materials, training, and quality control monitoring.
New options must be convenient, or people will not use them. Gender impacts
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 3
should be considered, so that the workload of women and girls is not unduly
increased. New technologies require behavioral change on the part of the user,
thus communication interventions should be considered. Finally, technologies
must be socially acceptable to community members in order to be successful as a
long-term safe water supply option.
separated from the water. Gravity settling (also called sedimentation) can
accomplish some of this, but filtration is more effective. Most
commonly, sand filters are used for this purpose.
Physical exclusion: some synthetic membranes are permeable to certain
dissolved compounds but exclude others. These membranes can act as a
molecular filter to remove dissolved arsenic, along with many other
dissolved and particulate compounds.
Biological removal processes: bacteria can play an important role in
catalyzing many of the above processes. Relatively little is known about
the potential for biological removal of arsenic from water.
Boiling does not remove arsenic from water.
Most of the established technologies for arsenic removal make use of several
of these processes, either at the same time or in sequence. All of the removal
technologies have the added benefit of removing other undesirable compounds
along with arsenic depending on the technology, bacteria, turbidity, color, odor,
hardness, phosphate, fluoride, nitrate, iron, manganese, and other metals can be
removed.
Historically, the most common technologies for arsenic removal have been
coagulation with metal salts, lime softening, and iron/manganese removal. Since
the WHO Guideline Value for arsenic in drinking water was lowered from 50 to
10 g/L in 1993, several countries have lowered their drinking water standards,
in some cases to 10 g/L. In January 2001, the USEPA lowered the U.S. drinking
water standard from 50 to 10 g/L(only to postpone/reconsider this decision a
few months later).
Coagulation processes are sometimes unable to efficiently remove arsenic to
these low levels. As a result, various alternate technologies have been developed
or adapted that are capable of removing arsenic to trace levels. These advanced
treatment options include ion exchange, activated alumina, and membrane
methods such as reverse osmosis and nanofiltration. While these technologies
have all been shown to be effective in lab or pilot studies, there is still relatively
little experience with full-scale treatment. In addition, a number of novel removal
technologies are under development, some of which show great promise.
The main arsenic removal technologies are presented below, along with a
brief description of how removal efficiency is affected by arsenic concentration
and speciation, pH, and the presence of other dissolved constituents.
Oxidation
The most heavily documented treatment methods for arsenic removal involve
coagulation and filtration, either using metal salts or lime softening. This
treatment can effectively remove many suspended and dissolved constituents
from water besides arsenic, notably turbidity, iron, manganese, phosphate and
fluoride. Significant reductions are also possible in odor, color, and potential for
trihalomethane formation. Thus coagulation and filtration to remove arsenic will
improve other water quality parameters, resulting in ancillary health and esthetic
benefits. However, the optimal conditions vary for removal of different
constituents, and coagulation to remove arsenic may not be optimal for removal
of other compounds, notably phosphate and fluoride.
Arsenic removal with metal salts has been shown since at least 1934
6 Technologies for Arsenic Removal from Drinking Water
(Buswell, 1943). The most commonly used metal salts are aluminum salts such
as alum, and ferric salts such as ferric chloride or ferric sulfate. Ferrous sulfate
has also been used, but is less effective (Jekel, 1994; Hering et al., 1996; Hering
et al., 1997). Excellent arsenic removal is possible with either ferric or aluminum
salts, with laboratories reporting over 99% removal under optimal conditions,
and residual arsenic concentrations of less than 1 g/L (Cheng et al., 1994). Full-
scale plants typically report a somewhat lower efficiency, from 50% to over 90%
removal.
During coagulation and filtration, arsenic is removed through three main
mechanisms (Edwards, 1994):
precipitation: the formation of the insoluble compounds Al(AsO4) or
Fe(AsO4)
coprecipitation: the incorporation of soluble arsenic species into a
growing metal hydroxide phase
adsorption: the electrostatic binding of soluble arsenic to the external
surfaces of the insoluble metal hydroxide.
All three of these mechanisms can independently contribute towards
contaminant removal. In the case of arsenic removal, direct precipitation has not
been shown to play an important role. However, coprecipitation and adsorption
are both active arsenic removal mechanisms.
Numerous studies have shown that filtration is an important step to ensure
efficient arsenic removal. After coagulation and simple sedimentation, HAO and
HFO along with their sorbed arsenic load can remain suspended in colloidal
form. Hering and others showed that coagulation and sedimentation without
filtration achieved arsenate removal efficiencies of 30%; after filtration through a
1.0 micron filter, efficiency was improved to over 96%. Only marginal
improvements were made by reducing the filter size to 0.1 micron (Hering et al.,
1996). In field applications, some plants improve arsenic removal with two-stage
filtration (Sancha, 1999b).
Ion-Exchange Resins
Synthetic ion exchange resins are widely used in water treatment to remove many
undesirable dissolved solids, most commonly hardness, from water. These resins
are based on a cross-linked polymer skeleton, called the matrix. Most
commonly, this matrix is composed of polystyrene cross-linked with
divinylbenzene. Charged functional groups are attached to the matrix through
covalent bonding, and fall into four groups (Clifford, 1999):
Strongly acidic (e.g. sulfonate, SO3-)
Weakly acidic (e.g. carboxylate, COO-)
Strongly basic [e.g. quaternary amine, N+(CH3)3]
Weakly basic [e.g. tertiary amine, N(CH3)2]
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 7
The acidic resins are negatively charged, and can be loaded with cations (e.g.
Na+), which are easily displaced by other cations during water treatment. This
type of cation exchange is most commonly applied to soften hard waters.
Conversely, strongly basic resins can be pretreated with anions, such as Cl-, and
used to remove a wide range of negatively charged species. Clifford gives the
following relative affinities of some common anions for a type 1 strong-base
anion resins (Clifford, 1999):
CrO42- >> SeO42- >> SO42- >> HSO4- > NO3- > Br- > HAsO42- >
SeO32- >HSO33- >NO2- > Cl-
Different resins will have differing selectivity sequences, and resins have
been developed specifically to optimize removal of sulfate, nitrate, and organic
matter. Various strong-base anion exchange resins are commercially available
which can effectively remove arsenate from solution, producing effluent with
less than 1 g/L arsenic. Arsenite, being uncharged, is not removed. Analysts
have taken advantage of this specificity to develop procedures for analytical
differentiation of arsenite and arsenate (e.g. Ficklin, 1983; Edwards et al., 1998).
Therefore, unless arsenic is present exclusively as arsenate, an oxidation step will
be a necessary precursor to arsenic removal.
Conventional sulfate-selective resins are particularly suited for arsenate
removal. Nitrate-selective resins also remove arsenic, but arsenic breakthrough
occurs earlier. Most commonly, resins are pretreated with hydrochloric acid, to
establish chloride ions at the surface, which are easily displaced by arsenic
(Ghurye et al., 1999), though the resin can be primed with other anions such as
bromide or acetate (Edwards et al., 1998). Packed beds are commonly designed
to have an Empty Bed Contact Time (EBCT) of 1.5 to 3 minutes.
Arsenate removal is relatively independent of pH and influent concentration.
On the other hand, competing anions, especially sulfate, have a strong effect. The
number of bed volumes that can be treated before arsenic breakthrough (defined
as 10% of the influent concentration) can be roughly estimated with two simple
formulas: (Clifford and Majano, 1993; cited in Chen et al., 1999).
For [SO4 2-] < 120 mg/L: Bed Volumes = -606 * ln[SO4 2-] + 3,150
For [SO4 2-] > 120 mg/L: Bed Volumes = -200 * ln[SO4 2-] + 1,250
where [SO4 2-] is the initial sulfate concentration in mg/L. In low-sulfate waters,
ion exchange resin can easily remove over 95% of arsenate, and treat from
several hundreds to over a thousand bed volumes before arsenic breakthrough
occurs. Accordingly, the USEPA recommends that ion exchange resins not be
used in waters with >120 mg/L sulfate or >500 mg/L TDS, and will be most
effective in waters with even lower sulfate levels (<25 mg/L) (USEPA, 2000).
8 Technologies for Arsenic Removal from Drinking Water
2000
Bed Volumes before breakthrough
1500
1000
500
0
0 100 200 300
Sulfate concentration (mg/L)
Activated Alumina
Activated alumina is a granulated form of aluminum oxide (Al2O3) with very
high internal surface area, in the range of 200-300 m2/g. This high surface area
gives the material a very large number of sites where sorption can occur, and
activated alumina has been widely used for removal of fluoride. In the early
1970s Bellack accidentally discovered that activated alumina could remove
arsenic from water (Bellack, 1971; Sorg and Logsdon, 1978).
The mechanisms of arsenic removal are similar to those of a weak base ion
exchange resin, and are often collectively referred to as adsorption, though
ligand exchange and chemisorption are technically more appropriate terms
(Clifford, 1999). The kinetics of arsenic removal onto the alumina surface are
slower than those of ion exchange resins, and some arsenic leakage is often noted
in activated alumina systems.
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 9
Arsenic removal efficiency is excellent (typically > 95%), for both arsenate
and arsenate, but arsenic capacity varies significantly, and is controlled primarily
by pH and influent arsenic concentration and speciation. Arsenate removal
capacity is best in the narrow range from pH 5.5 to 6.0, where the alumina
surfaces are protonated, but acid anions are not yet concentrated enough to
compete with arsenic for sorption sites (Trussell et al., 1980; Rosenblum and
Clifford, 1984; Clifford, 1999). Typically, activated alumina has a point of zero
charge (PZC), below which the surface is positively charged, and above which
the surface bears a negative charge, at pH 8.2. Arsenic removal capacity drops
sharply as the PZC is approached, and above pH 8.5, is reduced to only 2-5% of
capacity at optimal pH (Clifford, 1999). For neutral and basic waters, therefore,
pH adjustment may be necessary for effective arsenic removal.
Fine (28-48 mesh) particles of activated alumina are typically used for
arsenic removal, with an Empty Bed Contact Time of five to eight minutes
(Rubel and Woosely, 1979). When operated in the optimal pH range, activated
alumina beds have much longer run times than ion exchange resins. The number
of bed volumes that can be treated at optimal pH before arsenate breaks through
is mainly controlled by the influent arsenic concentration
Frank and Clifford reported an arsenate capacity (at pH 6) of about 1.6 g/L of
activated alumina, consistent with an earlier reported capacity of 4 mg/g,
assuming a bulk density of 0.5 kg/L (Gupta and Chen, 1978). Fox reported a
somewhat lower capacity of 1 mg/g, but this is likely due to the elevated pH (7.4-
8.0) of the influent water (Fox, 1989).
The sorption sites on the activated alumina surface are also attractive to a
number of anions other than arsenate: Clifford reports the selectivity sequence of
activated alumina in the pH range of 5.5 to 8.5 as (Clifford, 1999):
OH- > H2AsO4- > Si(OH)3O- > HSeO3- > F- > SO42- > CrO42- >> HCO3- >
Cl- > NO3- > Br- > I-
Regeneration is more difficult, and less complete (generally 50-80%) than with
ion exchange resins (Clifford, 1986).
The advantages of activated alumina are that simple removal systems can be
developed at community or household levels that require no chemical addition.
Since activated alumina can treat thousands of bed volumes before breakthrough,
filters could be operated for months before the media need to be changed or
regenerated. Activated alumina will also remove selenite, fluoride, sulfate, and
chromate. Disadvantages include the possibility that the media will be fouled or
clogged by precipitated iron, the relatively narrow pH range for optimal
operation, and the relative difficulty of regeneration. Also, compared with ion
exchange resins, a significantly longer Empty Bed Contact Time is required.
Membrane Methods
Synthetic membranes are available which are selectively permeable: the structure
of the membrane is such that some molecules can pass through, while others are
excluded, or rejected. Membrane filtration has the advantage of removing many
contaminants from water, including bacteria, salts, and various heavy metals.
Two classes of membrane filtration can be considered: low-pressure
membranes, such as microfiltration and ultrafiltration; and high-pressure
membranes such as nanofiltration and reverse osmosis. Low-pressure membranes
have larger nominal pore sizes, and are operated at pressures of 10-30 psi. The
tighter high-pressure membranes are typically operated at pressures from 75 to
250 psi, or even higher (Letterman, 1999).
From Figure 2, it is clear that reverse osmosis (RO) and nanofiltration (NF)
membranes have pore sizes appropriate for removal of dissolved arsenic, which
is in the metal ion size range. Both RO and NF membranes are most often
operated in lateral configurations, in which only a small amount of the raw water
(10-15%) passes through the membrane as permeate. In household systems,
where only a small amount of treated water is required for cooking and drinking,
this low recovery rate may be acceptable. Municipal systems achieve higher
recovery rates (80 to over 90%) by using multiple membrane units in series.
In recent years, a new generation of RO and NF membranes have been
developed that are less expensive and operate at lower pressures, yet allow
improved flux and are capable of efficient rejection of both arsenate and arsenite.
Waypa and others have showed that some of the new membranes, operated at
pressures ranging from 40-400 psi, were able to reject from 96-99% of both
arsenate and arsenite in spiked natural waters. The authors attribute this rejection
of arsenite to the relatively large molecular weight of both arsenate and arsenic,
rather than charge repulsion. At these high arsenic rejection rates, membrane
filtration can result in extremely low arsenic levels in treated water.
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 11
Size,
Microns 0.001 0.01 0.1 1.0 10 100 1000
Viruses Bacteria
Relative
size Aqueous salts
Algae
of
various Humic acids
Cysts
materials
in Metal ions Clays Silt Sand
water
Asbestos fibers
Reverse Osmosis
Microfiltration
Separation
Nanofiltration
processes
Conventional filtration processes
Ultrafiltration
relatively high capital and operating costs, and the risk of membrane fouling.
Also, particularly with RO, the treated water has very low levels of dissolved
solids, and can be very corrosive, and deficient in minerals which can be
important micronutrients for humans.
Emerging Technologies
Fe-Mn Oxidation
Conventional iron and manganese removal can result in significant arsenic
removal, through coprecipitation and sorption onto ferric or manganic
hydroxides. The mechanisms involved are the same as in coagulation and
filtration. Most low-cost technologies for arsenic and manganese removal rely on
aeration and filtration through porous media such as sand and gravel. Any
technology that effectively removes iron and manganese could be evaluated to
see if arsenic is also removed effectively. In this respect arsenic removal is more
convenient than that of fluoride, which does not undergo oxidation, and is not
removed by coprecipitation with iron.
In Bangladesh and West Bengal, elevated arsenic concentrations are often
associated with high iron and manganese levels. One survey in Bangladesh found
that over 80% of arsenic-affected tubewells (>50 g/L) also contained iron
levels of 2 mg/L or more. However, iron alone is not a good indicator of arsenic:
30% of the wells with safe levels of arsenic also had 2 mg/L iron or more
(DPHE/BGS/MML, 1999). Because of the link between arsenic and iron levels,
and the affinity of arsenic for iron hydroxides, there have been calls for a simple
solution to arsenic contamination: simple storage of pumped water to allow iron
to settle out, scavenging arsenic in the process. While this is an appealing idea,
successful application of this type of passive Fe-Mn oxidation is not simple, for
several reasons:
iron removal is not always easily accomplished. Some waters contain
iron in a form that is slow to oxidize, or may be complexed with organic
material that impedes oxidation and filtration. Precipitation may not
occur if alkalinity is low;
without a filtration step, much of the iron can remain suspended as
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 13
Although removal rates are not very high, in all cases it is effective enough to
bring waters into compliance with the Bangladesh drinking water standard of 50
g/L. Plant managers experimented with addition of coagulants (4 mg/L FeCl3)
and oxidants (0.9 mg/L bleaching powder), but found that arsenic removal
efficiency was not significantly improved.
14 Technologies for Arsenic Removal from Drinking Water
Ion exchange resins developed for removal of anions such as sulfate and nitrate
have proven to be reasonably effective at removing arsenic, as discussed above.
As materials engineering becomes more advanced, researchers are increasingly
able to design novel ion-exchange materials with surficial properties that are
particularly specific to arsenate. In particular, several researchers have found that
copper-doped materials have a strong, specific affinity for arsenate (e.g.
Rajakovic and Mitrovicm, 1992; Ramana and Sengupta, 1992; Lorenzen et al.,
1995). Fryxell and others have developed a novel mesoporous silica sorbent
which makes use of Cu(II)-based functional groups. This material has a higher
ion exchange capacity (75 mg As/g) than conventional resins, and shows a
stronger affinity for arsenate and chromate than for sulfate or nitrate. Therefore,
unlike the conventional resins, these materials will not release chromatographic
peaks of arsenic when exposed to high levels of sulfate (Fryxell et al., 1999).
While conventional synthetic ion exchange resins are the most commonly
used media in ion exchange, costs are relatively high ($USD 2-5 per liter of wet
resin). A variety of naturally occurring materials also have high ion exchange
capacities, sometimes after chemical pretreatment. Many of these materials are
not pure ion exchangers: some arsenic removal is through less reversible
chemisorption. Especially in developing countries, researchers have been
evaluating the potential of these materials for use as low-cost arsenic removal
systems.
Zeolites are naturally occurring minerals with a crystalline structure
characterized by large internal pore spaces. Accordingly, they have very large
surface areas, and ion exchange capacities: zeolites were used extensively for
water softening, before the development of synthetic resins with faster exchange
rates, higher capacity, and longer life. A few arsenic removal studies have been
conducted with zeolites.
Natural zeolite minerals such as clinoptilolite and chabazite have a strong
affinity for both arsenite and arsenate. A chabazite filter was able to remove 1000
g/L arsenate from over 235 bed volumes before arsenic was detected in the
effluent (Bonnin, 1997). Adsorption of arsenate onto natural zeolites can be
improved by organically modifying the zeolite structure (Misaelides et al., 1998).
Chitosan and chitin are natural polyaminosaccharides occurring in crustacean
shells, that have good ion exchange properties. Shellfish wastes containing
chitosan have been used to remove arsenic from water contaminated by mining
wastes (Luong and Brown, 1984). Elson and others investigated a mixture of
chitosan and chitin, and found a relatively low arsenic removal capacity of about
0.01 mg As/g (Elson et al., 1980).
Johnston and Heijnen : Safe Water Technology for Arsenic Removal 17
SUMMARY
The Table 2 summarizes some of the key technologies for arsenic removal, with
special reference to experiences gained from field level application. Research
needs are also identified. Arsenic removal efficiency will vary according to many
site-specific chemical, geographic, and economic conditions, so actual
applications may vary from the generalizations listed below. Because of the
many factors that can affect arsenic removal efficiency (including arsenic
concentration, speciation, pH and co-occurring solutes), any technology should
be tested using the actual water to be treated, before implementation of arsenic
removal systems at the field scale.
18 Technologies for Arsenic Removal from Drinking Water
REFERENCES