Arsenic Removal Using Amended Silicates

By Josh C. Gesick, Craig S. Turchi, and John L. Lovell, ADA Technologies, Inc.

Abstract
Arsenic contamination in groundwater is a severe health risk to populations throughout the world. In the United
States, the problem is most pronounced in the West, and in parts of the Midwest and the Northeast. In response,
the EPA announced a tougher drinking water standard for arsenic, lowering the standard from 50 micrograms
per liter (parts-per-billion, or ppb) to 10 ppb. This change is expected to impact 10 percent of the nations
community drinking water systems. While several technologies are readily amenable to be incorporated into
large water treatment processes, practical options are not readily available for small water supply systems,
particularly those serving fewer than 500 users.
ADA Technologies, through funding from the National Institute of Environment Health Science (NIEHS), EPA,
Edwards Air Force Base, and the State of Colorado, is developing approaches to remove arsenic from drinking
water. ADAs Amended Silicate arsenic sorbents have demonstrated to be an effective, low cost arsenic
adsorbent material tested in field applications relevant to water systems impacted by the new arsenic limit of 10
ppb.
The Amended Silicate sorbents promise high arsenic adsorption capacities at relatively low costs. These
Amended Silicate sorbents are based on a process wherein active adsorption sites are distributed onto an
inert, inexpensive silicate substrate. This amendment process can be tailored for the contaminant(s) of interest;
thus, a variety of sorbents are possible. To date, ADA has developed and tested Amended Silicate materials
designed for mercury capture from combustion gases and arsenic capture from drinking water. The arsenic
variant utilizes a ferric hydroxide amendment and has properties similar to other iron-based materials. However,
use of the inexpensive silicate substrate allows for efficient distribution of the iron sorption sites at a low cost.
ADA has developed multiple variations of the arsenic Amended Silicates sorbent. The sorbents can be
classified in two categories and can be produced in a range of particle sizes, depending on the particle size of
the starting substrate material. The first category of sorbent is for use in a fluidized sorbent approach and the
second is a beaded material for use in packed bed systems. The sorbents can be granular or powdered materials,
in general, the fluidized sorbent particle has a low bulk density compared to the beaded material and other ironbased sorbents. Isotherm testing indicates that the Amended Silicates sorbents have rapid arsenic adsorption
kinetics and excellent capacity. In addition Amended Silicates react with the arsenic to produce a leachresistant waste sorbent and possess the ability to capture other water contaminants, such as selenium, copper,
lead, and uranium. Mssbauer analysis indicates the iron form is a nano-scale akaganeite. The formation of
high-surface area, nano-scale akaganeite is believed to be responsible for the capacity of the Amended
Silicate.

Amended Silicates Arsenic Adsorbents

The fluidized sorbent approach is a hybrid system incorporating elements of coagulation/filtration and packed
bed adsorbent technology and makes use of the unique low density (Table 1) and rapid kinetics of the Amended
Silicate (Figure 3). In this approach, the sorbent is injected into the water stream as a concentrated slurry of
small particles, allowed to mix with the water for a specified contact time, and then sieved, filtered, or settled
from the water. A recycle loop would allow reinjection of the Amended Silicate for more efficient utilization.
The Amended Silicate used in such a process would be a much smaller particle size (~100 mesh) than is used
for the packed bed configuration. A moving bed design also allows for easy makeup and blowdown of sorbent
in an automated process, without the need for backwashing of vessel beds or outages to replace spent beds.
Lastly, the recycled sorbent can be regenerated outside of the treatment loop, allowing for continuous renewal
of the sorbent without affecting the treatment process.
Table 1. Physical properties of ADAs fluidized Amended SilicateTM formulation versus
two commercially available iron-based arsenic sorbents as measured by ADA and others
[US EPA, 2004].
Property

Fluidized Amended
Silicate

GFH

AdEdge AD33

Surface Area

380 m2/g (MGME method)

250 m2/g

180 m2/g

Bulk Density

~0.3 kg/L

1.25 kg/L

0.45 kg/L

Particle size (used

by ADA)

-10/+45 mesh

-8/+65 mesh

-10/+35 mesh

Iron Content

~25%

36%

57%

Water Content

~10%

43-48%

<15%

Iron Phase

nano-scale Akaganeite

Akaganeite & ferrihydrite

Goethite

Perhaps the most significant advantage of a fluidized sorbent design lies in the contact time between sorbent
particles and potential fouling species, such as silica. Over time, a sorbent particle within a packed bed will
see a significantly higher amount of silica versus an entrained sorbent particle. Hence, packed beds can be
plugged quickly by silica and require frequent backwashing, or even removal of part of the bed to maintain
sufficient flow. Previous research has shown that a high concentration of silica can reduce the arsenic-binding
capacity of iron-based sorbents [Davis 2000]. In contrast, the entrained particle contacts less silica and even if
the silica adsorbs, there is no effect of system flow rates or pressure drop. This effect explains why
coagulation/filtration processes have been recommended for arsenic capture where high silica concentrations
exist [Brandhuber, 2004].
The advantages of the entrained sorbent approach versus a conventional ferric chloride coagulation process is
that a nontoxic Amended Silicate slurry is used instead of corrosive ferric chloride solution and the sorbent
can be easily removed from the water. The entrained sorbent particles, though smaller than packed bed media,
would be much larger and easier to separate than floc from a ferric chloride coagulation process. The entrained
sorbent design does not require oxidant addition.
Isotherm testing of fluidized material was carried out in multiple water compositions listed in Table 2. All
isotherm tests followed a standard protocol consisting of adding 100 ml of arsenic-spiked water mixtures to 1
gram of sorbent in 250-ml vessels. The vessels were gently mixed for 24 to 72 hours on an orbital shaker at
room temperature. At the appropriate time, the sample liquid is filtered at 0.45 micron and analyzed for total
arsenic via a gaseous hydride atomic absorption method [Clesceri et al., 1998]. Subsequent data have suggested
that 24 hours may not be sufficient time to achieve true equilibrium. This behavior is consistent with data
where packed beds have exceeded the capacity reported in isotherm test.

Table 2. Surrogate groundwater recipes used for testing.

Constituent

Alamosa
Surrogate

Edwards AFB
surrogate

130 ppm

Arsenic Challenge
Water (Clifford & Wu,
2001)
252 ppm

NaHCO3
CaCl22H2O

25 ppm as CaCl2

111 ppm as CaCl2

98 ppm

Na2SO4

13 ppm

--

74 ppm

Mg2SO47H2O
K2SO4

--

62.6 ppm as Mg2SO4

34 ppm

--

--

12 ppm

Na2SiO39H2O
NaF

140 ppm as SiO2

20 ppm as SiO2

34 ppm as SiO2

--

1 ppm as fluoride

--

NaNO3

--

2 ppm as nitrite

0.5 ppm

Na3PO4

--

0.04 ppm as phosphate

0.1 ppm

pH

8.0

8.5

8.0

165 ppm

Concerns regarding the arsenic contamination in Colorados San Luis Valley prompted ADA to generate a
water matrix designed to simulate the groundwater in Alamosa, Colorado. The Alamosa surrogate was most
distinguished by the high concentration of silicate in the water (normally referred to as silica, as its
concentration is determined as SiO2). Discussions with Dr. Gary Amy at CU Boulder indicated that the silica
levels in Alamosa may be some of the highest in the nation. Subsequent testing with the Alamosa surrogate
without silica, demonstrated the performance of various fluidized Amended Silicate formulations. The UV480/20/2 formulations have higher arsenic capacities versus the earlier UC-CC-X001 and two commercial
products tested for comparison. The water used in the isotherms shown in Figure 1 was made following the
Alamosa surrogate shown in Table 2, but without the added silicate.

Capacity [mg As/g sorbent]

1.000
GFH (USFilter)
Ad33L (AdEdge)
UV4-80/20/24
UV4-80/20/2
UC-CC-X001
0.100

0.010

0.001
0.01

0.10

1.00

10.00

100.00

1000.00

Equilibrium Conc. As [ppb]

Figure 1. Isotherms for three fluidized Amended Silicate formulations and two
commercial products in a standard groundwater solution.

ADA also performed isotherm tests using samples of water shipped from southern California (Edwards Air
Force Base), surrogate water made to simulate the Edwards AFB source, and the Arsenic Challenge water (see
Table 2). The challenge water composition was based on the mean values for common water constituents found
in regions having arsenic concentrations above the Maximum Contaminate Level (MCL) of 0.010 mg/L. The
challenge water is in ANSI/NSF Standard 53 for adsorption-based water treatment devices. As such, it is the
established benchmark by which arsenic removal technologies are tested. Figure 2 shows the pseudo
equilibrium capacities (48 hour test for Edwards AFB water and 72 hours for the arsenic challenge water) of the
fluidized Amended Silicate formulation compared to GFH. Fitting the data below 1000 ppb with a
Freundlich isotherm model (represented by the straight lines on Figure 2) shows that the Amended Silicate
sorbent had a higher arsenic capacity versus GFH in both water compositions. Using the Freundlich isotherm
model Figure 2 indicates that the Amended Silicate sorbent has approximately 3.7 times the capacity of the
GFH on a mass basis in the Edwards AFB surrogate water.
The commonly used Freundlich equation, q = KC1/n, provides a convenient framework for evaluating the
sorbents performance in isotherm tests. In the equation, q is sorbent capacity (mg As per g sorbent), C is
equilibrium concentration (g/L) and K and n are sorbent-dependent parameters. Linearizing the equation to
log(q) = log(K) + 1/n*log(C) makes it easy to determine values for the parameters K and 1/n. This exercise
makes it convenient to plot the data on a log-log scale as sorbent capacity versus equilibrium concentration of
contaminant in the liquid phase. High values for K indicate greater sorbent capacity for arsenate. The slope of
the isotherm is indicated by the value 1/n, with 1/n < 1 considered favorable adsorption. (The term 1/n is
traditionally used for the exponent.)

AS EAFB Actual Water

10

AS Surrogate Water

Sorbent Capacity (mg/g)

Sorbent Capacity (mg/g)

10.0

GFH Surrogater Water

1.0

GFH EAFB Actual Water

0.1

0.0
0

10

As(V) in solution (ug/L)

100

1000

Fluidized AS
Formulation
Fluidized AS
Formulation

GFH
0.1

0.01
1

10

100

As(V) in solution (ug/L)

1000

Figure 2. Isotherm results using actual Edwards AFB water and a surrogate water (left)
and Arsenic Challenge water (right). See Table 2 for water matrices. ADAs fluidized
Amended Silicate sorbent (AS) and GFH were used for both tests.
In addition to overall capacity, the rate and strength of adsorption are fundamental characteristics of the sorbent
media that govern much of the adsorbents performance. ADA examined adsorption kinetics in a rapid mixing
test performed with a series of well-stirred flasks. In the test, sorbent is added to flasks containing a specified
arsenic-laden water. Each flask is drained at a specific interval through a coarse filter paper to remove the
sorbent and stop the adsorption process. The results, depicted in Figure 3, show that the Amended Silicate has
rapid adsorption kinetics as well as good overall capacity. The ability of the Amended Silicate to rapid bind
arsenic is a key attribute for its use as a fluidized sorbent material.

As conc. (ppb)

200

GFH
Amended silicate +35 mesh

160

Amended silicate +60 mesh

120
80
40
0
0

10

20

30
Time (min)

40

50

60

Figure 3. Adsorption kinetics for the fluidized Amended Silicate arsenic sorbent and
GFH.
ADAs arsenic Amended Silicate sorbents have also shown the ability to remove other metals, and tests were
run to quantify this ability for some common water contaminants. A standard isotherm protocol similar to that
described above was followed for each metal listed in Table 3. Isotherm liquid was filtered at 0.45 micron and
shipped to ACME Analytical Labs (Vancouver, BC) for metal analysis via ICP/MS. The water matrix used for
all metals, except lead, followed NSF-ANSI 53 standard water for metals. Tests were performed using both the
high pH matrix (pH = 8.5) and low pH matrix (pH = 6.5). The lead water recipe was based on NSF-ANSI 53
standard water for lead. The majority of the metals tested had a percent removal above 90% and final
concentrations well below the desired MCL.
Table 3. Metals tested for removal by Amended Silicate sorbent.
Metal
Ba
Cd
Cr(III)
Cr(VI)
Cu
Hg
Pb
Se
Tl
U
Zn

Initial conc. in test

water (mg/L)
10
0.03
0.3
0.3
3.0
0.006
0.15
0.1
0.02
0.3
10

EPA Max. Contaminate

Level (mg/L)
2.0
0.005
0.1
0.1
1.3
0.002
0.015
0.05
0.002
0.03
5

Removal pH
6.5
99%
91%
58%
94%
98%
97%
81%
98%
99%
97%
99%

Removal
pH 8.5
55%
94%
69%
93%
98%
89%
85%
98%
99%
95%
98%

Leaching Tests
Disposal of spent sorbents and the ultimate fate of contaminants are key concerns when evaluating the life cycle
costs of treatment technologies. For adsorbent media the hazard level is determined by standardized leaching
tests. The two relevant protocols for the arsenic sorbents are the EPA Toxicity Characteristic Leaching Protocol
(TCLP) and the similar California Waste Extraction Test (WET). Both methods consist of tumbling the test
material in a specified chemical solution for a fixed time period and then analyzing the filtrate solution for the
contaminants of concern. The more aggressive WET procedure differs from the TCLP primarily in the leaching
solution (citrate buffer vs. acetate buffer), leaching time of 48 hours compared to 18 hours, and a liquid to solid
ratio of 10:1 vs. 20:1.

ADAs fluidized Amended Silicate sorbent and GFH were saturated with arsenic overnight in a process
similar to the isotherm tests previously discussed (five grams of sorbent in 500 ml of arsenic-spiked surrogate
water). The initial arsenic concentration of the surrogate water was 4,900 g/L and the final equilibrium
concentration was 390 g/L. The final concentration of 390 g/L was 19 times higher than arsenic
concentration typically found in groundwater; thus the leaching test as performed was a more rigorous
challenge to the sorbent than would be expected in actual use. Leaching tests were also performed on
UltrAsorb-F supplied by Kinetico Incorporated (Newbury, OH) saturated with arsenic during standardized
testing of a pilot Point-of-Use system at ADAs laboratory.
Two five-gram samples of the arsenic-laden sorbents were subjected to the TCLP procedure and one ten-gram
sample was used for the WET protocol. The actual amount of sorbent used for the leaching tests varied from the
standard procedure; however the solid to liquid ratio was maintained. This was necessary due to limited amount
of Amended Silicate sorbent produced during small-scale preparation. As seen in Table 4, the leachates from
the WET and TCLP tests were well below the allowable soluble threshold limit of 5,000 g/L. WET test results
are generally higher than TCLP because the WET test digestion is more aggressive and is agitated for a longer
period of time.
Table 4. Amended Silicate leaching test results.
Sorbent / Waste Characterization
test
Amended Silicate / TCLP

Actual Leachate Arsenic

Concentration, g/L
2

Soluble Threshold Limit

Concentration, g/L
5,000

Amended Silicate / WET

154

5,000

GFH / TCLP

38

5,000

GFH / WET

No data

5,000

UltrAsorb-F/ TCLP

5,000

UltrAsorb-F/ WET

270

5,000

The sorption properties of the fluidized Amended Silicate sorbent include: (1) a high arsenic-removal rate, (2)
high arsenic capacity, (3) excellent performance in the presence of common anions and cations, (4) the ability to
chemically bind arsenic: the sorbent reacts with the arsenic to produce a leach-resistant waste material, and (5)
the ability to capture other water contaminants, such as selenium, copper, lead and uranium. However, most
sorbent systems are deployed as granular packed beds and the sorbents unique physical and hydraulic
properties, in particular its relatively low bulk density, are not ideal for use in packed bed systems.
For packed bed applications, ADA strengthened the sorbent particles by mixing a binder with the silicate
substrate to produce a hard porous granular bead or extrudate, which was then subjected to the standard
chemical amendment process. This modified Amended Silicate arsenic sorbent was categorized as a beaded
Amended Silicate sorbent. The main goal with the beaded material was to produce a sorbent with similar
sorption characteristics as the fluidized sorbent but physical and hydraulic properties suitable for packed bed
systems. In addition, the beaded materials rigid structure eliminates many problems associated with handling
of the media that is common of iron-based sorbents (e.g., column loading and removal). It is hypothesized that
the beaded materials spherical particle integrity will be maintained throughout the medias lifetime in a packed
bed system.
Figure 4 shows that the beaded formulation has an arsenic capacity similar to the fluidized formulation when
tested in Edwards AFB surrogate water. Again the capacities of the Amended Silicate sorbents were
significantly higher than that of the commercially available GFH. The beaded material also had a similar
arsenic sorption rate compared to GFH (Figure 5); however, both would be slower than the fluidized material
(Figure 3).

10
Fluidized Formulation

Sorbent Capacity (mg/g)

Beaded Formulation
GFH
1

0.1

0.01
1

10

100

1000

As(V) in solution (ug/L)

Figure 4. Isotherm test of the fluidized and beaded Amended Silicate formulations
compared to GFH. Edward AFB surrogate water was used for the test (Table 2).

1200
GFH

As(V) concentration (ug/L)

1000

Beaded Formulation

800

600

400

200

0
0

10

20

30

40

50

60

70

Time (minutes)

Figure 5. Adsorption kinetic test of the beaded Amended Silicate material compared
to GFH. Edward AFB surrogate water was used for the test (Table 2).
ADA contracted with Dr. Desmond Cook at Old Dominion University (Norfolk, VA) to examine sorbent
samples via Mssbauer spectroscopy. Mssbauer analysis is a powerful technique for identifying the phase of
iron oxide within a sample. It is uniquely suited for iron analysis due to the activity of the 57Fe isotope.
Mssbauer analysis can determine the mineral phase of the iron by revealing the valence state and coordination
and order with the ligand shell of the iron. Additional information includes data on the amount of iron present
and the size of the iron oxide crystallites. In studies of samples prepared by ADA, Dr. Cook identified the iron
form as most probably a nano-scale akaganeite (Figure 6). The formation of high-surface area, nano-scale
akaganeite is believed to be responsible for the capacity of the Amended Silicate formulations.

(a) Un-Modified Silicate: UV4

T = 77 K

(b) Amended Silicates

(i) UV-FC-X002

Intensity

(ii) UV-CC-X003

Figure 6. Mssbauer spectra of four fluidized

samples and the bare substrate (UV4) recorded
at 77K. It was observed that (a) UV4 and (i)
UV-FC-X002 remain non-magnetic at 77K. The
onset of relaxed magnetic field is seen in
samples (ii) UV-CC-X003, and (iii) UV-CCX007. Static Magnetic ordering of Akaganeite
is seen in (iv) V8 (represented of ADAs current
fluidized sorbent).

(iii) UV-CC-X007

(iv) V8

-10-9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9 10

Relative Velocity (mm/s)

Conclusion
ADAs Amended Silicate arsenic adsorbents have demonstrated the ability to adsorb arsenic in a variety of
water compositions containing arsenic above the MCL of 10 g/L. The formation of high-surface area, nanoscale akaganeite is believed to be responsible for the capacity of the Amended Silicate. Two basic forms of
the Amended Silicate have been produced for arsenic control. The first utilizes the sorbents rapid sorption
kinetics and unique physical and hydraulic properties for deployment in a fluidized system. The second
combines the silicate substrate with a binder to produce a ridged spherical particle, ideal for pack bed
applications, while maintaining the excellent sorption capacity of the fluidized sorbent.
Pilot testing of both systems is scheduled to start in the summer of 2005. Field testing with the fluidized and
packed bed systems will determine the viability of both approaches for compliance with the looming 10 g/L
arsenic MCL. Edwards AFB has provided Phase II (SBIR) funding to demonstrate the Amended Silicate
performance in a packed bed pilot system and the fluidized sorbent system will be evaluated through NIEHS
Phase II funding. ADA is also teaming with Old Dominion and Virginia Polytechnic Universities to
characterize and model the behavior of the Amended Silicate sorbent.

References

Brandhuber, Philip, 2004, McGuire Environmental Consultants, personal communication

regarding testing in San Luis Valley.
Clesceri, L.S., A.E. Greenberg, and A.D. Eaton, Eds., 1998, Standard Methods for the
Examination of Water and Wastewater, American Public Health Association, 20th ed.
Clifford, D., and M. Wu, March 27, 2001, Arsenic Treatment Technology Demonstration,
Drinking Water Assistance Program for Small Systems, Montana Water Resources
Center, Bozeman.
Davis, C.C., 2000, Aqueous Silica in the Environment: Effects on Iron Hydroxide Surface
Chemistry and Implications for Natural and Engineered Systems, M.S. Thesis
Virginia Polytechnic Institute and State University, Blacksburg.
US EPA, August 10-11, 2004, Workshop on the Design and Operation of Adsorptive Media
Processes for the Removal of Arsenic from Drinking Water, Cincinnati, OH.

Biographical Sketch
Craig S. Turchi
Sr. Research Engineer
ADA Technologies, Inc.
8100 Shaffer Parkway, #130
Littleton, CO 80127
Phone: 303-792-5615 x285
Fax: 303-792-5633
Email Address: craigt@adatech.com
Dr. Turchi has a BS in Chemical Engineering from Texas A&M and a Ph.D. from NC State
University. Dr. Turchi has been with ADA Technologies for over 7 years, and worked
previously at Zentox Corporation and the National Renewable Energy Laboratory in Golden
Colorado.
John Lovell
Senior Scientist
ADA Technologies, Inc.
8100 Shaffer Parkway, #130
Littleton, CO 80127
Phone: 303-792-5615 x263
Fax: 303-792-5633
Email Address: johnl@adatech.com
Dr. Lovell has a B.Sc. in Chemistry and Geology from Southampton University and a Ph.D.
in Geochemistry from Imperial College, University of London. Dr. Lovell has over thirty
years experience in geochemical research in over thirty different countries, on every
continent. Dr. Lovells understanding of all of the various mechanisms that control the
mobility of metallic anions and cations in the natural environment led to his invention of the
Amended Silicates.
Josh Gesick
Research Engineer
ADA Technologies, Inc.
8100 Shaffer Parkway, #130
Littleton, CO 80127
Phone: 303-792-5615 x240
Fax: 303-792-5633
Email Address: joshg@adatech.com
Mr. Gesick has a BS in Chemical Engineering from Colorado State University. Mr. Gesick
has been with ADA Technologies for over 2 years, and is currently the project manager for
two Small Business Innovative Research Phase II projects involving the removal of arsenic
from drinking water.