SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA

Preprint 12-004
METHODS FOR REMOVING ARSENIC FROM AQUEOUS SYSTEMS
L. R. Moore, Kemira Oil and Mining, Atlanta, GA
A. Mahmoudkhani, Kemira Oil and Mining, Atlanta, GA
L. Sanders, Kemira Oil and Mining, Atlanta, GA
J. R. Durand, Kemira Oil and Mining, Atlanta, GA
6

arsenic containing minerals. It is clear that arsenic contamination is a

global issue that calls for immediate action.

ABSTRACT
Arsenic is among the list of major contaminants in mining
aqueous waste streams. Though the elemental form is toxic, the
aqueous oxyanions are more so. The most common forms of arsenic
released during mining processes are arsenate and arsenite. The
common treatment technologies to date can be summed up in these
major categories: oxidation, coagulation, absorption, and media
filtration.
These methods can often involve many expensive
processing steps that may also be limited by variables, such as total
dissolved solids, other cations and anions, and the oxidation state of
the arsenic. An innovative technology, falling in the absorption
category, was developed that can successfully reduce such aqueous
forms to a level below the EPA recommendations.
This new
technology offers a unique and viable solution which is transparent to
the above mentioned limitations.

INTRODUCTION
Arsenic is a naturally occurring metalloid that belongs to the
pnictogen group and in such is chemically similar to phosphorus and
antimony. Arsenic is available in commercial quantities from minerals
containing iron, nickel or cobalt, such as arsenopyrite, realgar,
1
nickeline, oregonite, and others. It is also a contaminant in other sulfur
and metal containing ores. Arsenic has many industrial applications,
such as adding strength to metal alloys of copper and lead (batteries),
a dopant in semiconductor electronic devices (doped silicon), and in
pesticides.

Figure I. Example of a mine site and possible routes for contamination.

The above mentioned activities have led to incidents of arsenic
7
poisoning around the world. (Figure II) Natural groundwater
contamination represents a large portion of this poisoning and has
been observed in Taiwan, Chile, Mexico, Argentina, India, USA, New
Zealand, Poland, Spain, China, Srilanka, Canada, Hungary, Japan,
Vietnam, and Bangladesh. Another major contributor to groundwater
contamination is through industrial processes, such as coal burning
(Mexico and the former Czechoslovakia) and metal processing (Japan,
Australia, India, Canada, Greece, Ghana, USA, Rhodesia, Sweden,
Bulgaria, and others). Though there is little in the way of preventative
measures that can be done from natural contamination, prevention of
industrial contamination is of large interest.

Arsenic is universally known as being highly toxic and is so at the

cellular level by its interaction with the thiol containing proteins.
Exposure to arsenic can lead to peripheral neuropathy, gastrointestinal
symptoms, diabetes, cardiovascular disease, cancer, skin lesions, and
2
The major pathway for human exposure is through the
more.
consumption of water or food that contains elevated levels of arsenic.
Organic forms of contamination are commonly ingested through
seafood, but are significantly less toxic and should be eliminated from
the body with minimal damage. The World Health Organization (WHO)
recommendation for arsenic concentrations in the freshwater supply is
to not exceed 10 ppb. The EPA adopted the same standard, of which
3
systems must maintain below 10 ppb by January 23, 2006. The EPA
listed arsenic in at least 1,149 of the 1,684 sites listed on the National
4
Priorities List. The National Priorities List is a list of sites containing
hazardous waste in the USA that are to the level that make them
5
financially eligible for the Federal Superfund program.
Though arsenic is a widely distributed element in the Earths crust
the most common methods for contamination of the water or
environment are through natural activities, human activities, or
remobilization. Natural activities can refer to dissolution of arsenic
containing minerals, volcanic activity, and others. Human activities are
mainly summed up in mining processes, usage of fossil fuels, or a
more deliberate activity of applying arsenic in the form of pesticides or
timber treatment/preservation. Remobilization occurs through leaching
from tailings or mine drainage water. (Figure I) Arsenic is naturally
present at elevated levels in Argentina, Chile, China, India, Mexico,
Bangladesh, and the USA; which could be due to the dissolution of

Figure II. Global arsenic poisoning.

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Feb. 19 - 22, 2012, Seattle, WA
hazardous waste. The iron coagulants are typically more effective at
removing arsenic than the aluminum, but both may require a
preoxidation step prior to treatment when arsenic (III) is the oxidation
state being treated. (Figure V) This difficulty in treatment is due to the
very stable, water-soluble, arsenite trimer; which is not easily broken
with standard coagulants. An oxidizing agent will disrupt this stable
structure forming a species that is significantly easier to treat,
arsenate.

Arsenic exists in 4 major oxidation states with arsenide (As III)

typically being associated with metals and sulphides in ores
encountered during mining processes. (Figure III) Elemental arsenic is
relatively insoluble in aqueous systems, but there are 2 oxidation
states that are commonly released into the aqueous systems from the
above mentioned processes, arsenite and arsenate. Arsenite and
arsenate are water-soluble oxyanions as such they are the more toxic
8
and problematic for treatment of mine process waters. (Figure IV)
Arsenite is 60 times more toxic than arsenate.

Figure V. Ferric treatment of arsenic contaminated water.

Media Filtration
Media filtration is a physical treatment method that can be as
simple as filtering through sand, clay, alumina, and others; or can be
as exotic as filtering through ion exchange resins or a membrane
(reverse osmosis and nanofiltration). Many of these media are
commonly used in the water treatment industry. Common problems
associated with filtration media include an increased amount of waste
and a potential for fouling or scaling of the membrane. Many of these
types of methods also have sensitivities to other ions, such as; nitrates,
sulfates, and chlorides which lead to the inability to remove arsenite
(As III).

Figure III. Most common oxidation states of arsenic.

Figure IV. Order of Toxicity of arsenic species.

Media filtration is a method that typically isnt very effective at
removing arsenite but may be effective at removing arsenate in some
cases. Chemical oxidation as a method of pretreatment may increase
the effectiveness of the arsenite removal. Another major concern when
using media filtration is in the large amount of hazardous sludge
generated that will need further treatment.

EXISTING TREATMENT TECHNOLOGIES

The common technologies for treatment of contaminated aqueous
systems to date can be summed up in these major categories:
9
oxidation, coagulation, and media filtration. The previously mentioned
methods are typically effective at reducing arsenic concentrations from
aqueous systems, but may require multiple treatment steps due to
certain limitations and sensitivities in order to reduce the arsenic
concentration to a level below 10 ppb.

Ion exchange resins work by reversibly exchanging a more

desirable ion with a contaminated one. These can be altered to fit a
specific ion or left broad enough to remove a series of ions. These
resins may also be regenerated, but ends in a large amount of sludge
that will need post treatment as a hazardous material. There is a high
capital cost, as well as, high operation and maintenance costs
associated with ion exchange resins.

Oxidation/Precipitation
The 2 major technologies in the oxidation/precipitation method are
air oxidation and chemical oxidation. Air oxidation is a very simple
process, but has a significantly longer process time and isnt arsenic
specific. It not being arsenic specific may lead to other inorganics or
organics being oxidized, thus leading to modifications of the process
water that may lead to a need for other treatments. Chemical oxidation
is a much faster process, but leads to other chemical impurities. Such
a method is limited to pH control and is not typically a method that is
used alone, but rather as a pretreatment step for another method, such
as coagulation.

Reverse osmosis (RO) is very commonly applied in water

treatment. RO is efficient at removing large molecules and ions from
solutions by applying osmotic pressure to push the solutions through a
membrane. Such systems are able to maintain a continuous operation
and in many cases able to reject undesirable salts. As with many of the
other treatment methods, once the selenium is removed it must be
further treated as it is considered a hazardous waste.

Coagulation
Coagulation/coprecipitation is a very common technique for
treating process waters and is often thought to be the Best
Demonstrated Available Technology (BDAT) for many water
treatments. They most often involve using lime softening, aluminum
coagulation, iron coagulation, or combination of the three. These
coagulants are effective at removing a broad spectrum of
contaminates, but generate a large amount of sludge that will need
further treatment as leaching is expected, thus is considered

In-Situ Solidification Chemisorption Treatment Method

The focus of this work is to introduce an innovative approach
using in-situ solidification chemisorption method for treatment of
contaminated process waters. Such a method involves the
collaboration of the chemical (coagulation/coprecipitation) and physical
(media) treatment methods mentioned above. An insoluble amorphous
sorbent possessing active sites for the chemisorption of oxyanionic
species, such as arsenate, was prepared by the chemical modification
of an inorganic silica based polymeric material (Figure VI).

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SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
EXPERIMENTAL
Materials
Sodium arsenate (Na2AsO4) was purchased from Aldrich and
used as received with no further purification. Lab-made aqueous
solutions containing arsenate were prepared by dissolution of the
above chemicals in city of Atlanta tap water. Sodium arsenate is
extremely toxic and should be handled and disposed according to
regulations for toxic substances.

Figure VI.
Schematic representation of In-Situ solidification
chemisorption method.

Instruments
In this study, a Thermo Scientific ICP-AES system model iCAP
6500 equipped with a charge injection device (CID) detector and a
CETAC ASX-520 autosampler was used for determination of arsenic
species in water samples. Low detection limits (5 ppb for arsenic) were
achieved by pre-concentration of 100 mL aqueous samples.
Quantitative elemental analysis of trace elements was conducted on a
Bruker S4 Explorer wavelength-dispersive X-ray fluorescence
spectrometer. Element distribution of arsenic before and after
treatments was used for qualitative and quantitative analysis of
chemisorption of the contaminant species on inorganic polymeric solid
sorbent.

Cross-linking an inorganic polymer in solution should allow for

maximization of the amount of active sites available, thus increasing
the potential contact and interaction with the arsenate. Encapsulation
of the chemisorbed contaminant is believed to occur due to the
irregular nature of the cross-linking process, thus providing an
immobilized amorphous solid mass. Such solid mass can be removed
from solution with relative ease by gravitational settling, filtration or
other conventional solid removal methods.
Sludge Disposal
Historically, lime precipitation was the common method applied
for removing inorganic contaminants, such as, arsenic. This method
works by generating a relatively insoluble salt, calcium arsenate (ksp =
-19
6.8 X 10 ). (Figure VII) The industry has dominantly transitioned
away from such treatment as evidence suggests that the
environmental conditions, such as exposure to atmospheric carbon
dioxide, will liberate the water soluble forms of arsenic and generate
calcium carbonate. This mobility suggests that calcium treatment may
be a temporary solution to contamination, but certainly not a
permanent one as the sludge would require disposal as a hazardous
waste or the leachate recollected and retreated.

RESULTS AND DISCUSSION

Adsorption is the process where the contaminant is transferred
from the liquid phase (solution) to the solid surface by concentrating on
that surface or interface of the two phases such as liquid-solid
interface. Chemical adsorption or chemisorption takes place as a result
of a chemical bond or coordination being formed between the solute
(dissolved species) and the adsorbent, comparable with those leading
to the formation of chemical compounds. (Figure VIII) There are many
factors affecting adsorption such as nature of the adsorbent, the
adsorbate, the solvent and others. Adsorption processes are capable
of removing contaminants if the adsorbent (solid surface) is selected
carefully and the solution chemistry is controlled.

O
O

As
O
O

Figure VII. Lime treatment of arsenic contaminated water.

The current industrially favored method, the US EPA Best
Demonstrated Available Technology, for treatment and disposal of
arsenic dissolved in aqueous systems is via the formation of relatively
insoluble ferric arsenate crystals, which is allowed to form sediment at
the bottom of a tailings pond. Until recently, these crystals were
thought to be immobilized and contained. Recent studies suggest that
these iron salts may not possess the long term stability that was once
thought to be the case. This stability can be increased by maintaining
an acidic (pH 3-5) and slight oxidizing environment. The stability can
also be increased by altering the conditions at which the iron salt is
formed, for example; by forming an arsenical ferrihydrite. This
10
structure exists as a chemisorbed arsenate ion on ferrihydrite. To
force the formation of this more stable structure, a temperature of less
o
than 100 C and a lower pH are needed. However, if the ratio of Fe
(III) to As(V) is elevated then the less stable ferric-arsenate structure is
what dominantly precipitates. This is a common issue as arsenate
containing waters generally have higher concentrations of sulfates as
well as the contaminant. Under such conditions, the ferric will interact
with the sulfate, thus leading to a higher concentration of ferric being
needed to obtain the desired arsenate removal. These sulfate-ferric
interactions can be reduced by the addition of lime, which would lead
to the precipitation of calcium sulfate, thus allowing for more of the
ferric to interact with the arsenate. A potential problem when applying
lime is that a pH above 3 may lead to the formation of calcium
arsenate, which was discussed previously as not being a stable
complex. Another major issue is the filtration of this more stable
arsenical ferrihydrite sludge as it lacks the defined crystal structure.

Figure VIII: Chemisorption of arsenic species on inorganic polymeric

sorbent
Treatment of Arsenic Containing Water Samples
The new technology for the treatment of contaminated water
involves the chemisorption of inorganic oxyanions onto the sorbent.
The process consists of formation of the sorbent and chemisorption of
the contaminated species on active sites of the sorbent in a single
stage treatment in a continuously stirred (400 500 rpm) mixing tank.
The inorganic polymer (IP-1*) is dosed at 20 1000 ppm to the
contaminated water and allowed to stir for 1-3 hours after which an
aliquot is transferred into a settling tank to allow for the sedimentation
of the arsenic enriched sorbent. Filtration of the supernatant through a
Whatman qualitative filter paper No. 5 (pore size of 2.5 m) gave a
clear, visible solid free water sample for ICP. The rate of filtration may
be increased by the assistance of an organic flocculant such as anionic
polyacrylamides.
Evaluating the IP-1* sorbent technology and comparing towards
the standard ferrous, ferric and aluminate coagulants it was learned
that all of the treatments have the ability to reduce the arsenate levels
in aqueous systems to a level below the EPA recommended discharge
limit of 10 ppb. (Figure IX) The ferric, ferrous, and IP-1* treatments
provided decontaminated water below the ICP instrument detection
limit, < 5ppb.

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Feb. 19 - 22, 2012, Seattle, WA
complexes generated during the usage of the best demonstrated
12-15
Ferric arsenate complexes are observed in
available technology.
the environment as a mineral such as scorodite, which is considered
moderately insoluble under standard environmental conditions. The
literature suggests this is due to the high crystalline nature of this
complex, which occurs under certain geological conditions. Of course,
these environmental conditions can be altered through various
chemical and biological processes.
When an amorphous scorodite like material is prepared, as in
the case of treatment of arsenic contaminated water with ferric
coagulants, this crystalline structure is generally not obtained, thus
leading to a less stable structure. This stability can be increased by
increasing the ferric/arsenate ratio (Fe/As), but will end in a
significantly higher chemical cost and sludge generation. Work by
Krause suggests that an Fe/As ratio of 1.41 would yield an arsenic
solubility of 110 ppm, while increasing the Fe/As ratio to 15.9 would
yield an arsenic solubility of < 0.05 ppm in the filtrate assays
13
evaluated. Furthermore, at an Fe/As ratio of 2, 0.18 ppm arsenic is
leached into water at a pH of 5 after immediately evaluating the filtrate
assay. After 3 years, this concentration was reported as 0.73 ppm.
The amorphous scorodite is believed to have decomposed to
goethite (FeO(OH)), thus releasing the coordination with arsenate.

Figure IX. Dosage demand comparison of various technologies

towards arsenic removal.
As mining applications may vary by a wide range of pH, the
sensitivity of the treatment to the pH of the process water is a very
important variable that must be understood. (Figure X) When ferrous
coagulants or the IP-1* sorbent is applied the pH sensitivity towards
the removal of arsenic requires that the water entering the treatment
facility, containing this water chemistry, possess a pH greater than 6.
This efficiency can further be increased by increasing the pH. While
the ferric coagulant requires a much tighter pH, it is efficient at
reducing the arsenic concentrations below the EPA recommended limit
under the lab process water conditions at a pH range of 4-5. Water
that approaches the treatment facility with a pH less than 4 has little to
no reduction of the arsenate concentrations when applying the
standard coagulants; however, 98% reduction is observed with the
new IP-1* technology at a pH range of 2-3 for the water entering the
treatment system.

The sludge generated from the successful treatment of lab

generated water containing 25,500 ppb arsenate with IP-1* was
submitted to an external lab for TCLP analysis. Applying the above
mentioned EPA method 1311 it was reported that no detectable
amount of arsenic was leached under either pH experiments.

CONCLUSIONS
A new chemisorption technology was developed that incorporates
both physical and chemical treatment methods. This technology was
developed and evaluated for removing arsenic from aqueous systems.
The arsenate is chemically adsorbed onto the active sites within the
cavities of the sorbent material, thus removing arsenate from water
containing ppm concentrations of the contaminant. Inorganic polymers
based on silicates provide an economical and versatile solution for
treatment of contaminated mining process waters within an operational
and environmental friendly process. The sensitivities that are
commonly associated with the existing treatment technologies, such as
2+
2+
elevated concentrations of common cations and anions (e.g. Ca , Fe ,
2Cl and SO4 ) were not observed in the initial screening of the IP-1*
treatment. Solids formed during the treatment process can be easily
removed by gravity settling or common filtration methods. Another
major benefit of the IP-1* treatment system is in disposal of the solid
waste generated from treatment of arsenate containing water. TCLP
evaluation revealed no detectable amount of arsenic was leached out
under either pH experiments conducted following the EPA method.

REFERENCES

Figure X. Comparison of treatment technologies as a function pH.

Leaching Analysis and Waste Disposal
The industrially accepted method for measuring the strength of
these treatments towards maintaining the immobility of the
contaminants or the ability to resist leaching is referred to as Toxic
Characteristic Leaching Procedure (TCLP). Though this is not a
comprehensive measurement of hazardous waste, it can be applied as
a screening tool of such wastes being contained in an EPA
recommended sanitary landfill.
The EPA preferred method of
measuring the TCLP is known as method 1311, which evaluates the
leach ability of contaminants at a pH of 4.93 and at a pH of 2.88; of
11
which both are adjusted with acetic acid. This method evaluates the
sensitivity of acidic pH on the leaching, but doesnt take into account
other environmental redox (chemically or microbial) conditions or
leaching over an extended amount of time.
Discussions throughout industry, as well as, literature have
expressed concerns directed at the stability of the ferric arsenate

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SME Annual Meeting

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