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CITATIONS
This document was prepared by
Water Systems Specialist, Inc.
5808 Princeton Ave. N.E
Seatle, WA 98105
Principal Investigators
C. Haussmann, P.E.
T. Wolfe
This document describes research sponsored by EPRI.
The publication is a corporate document that should be cited in the literature in the following
manner:
Arsenic and Selenium Treatment Technology Summary for Power Plant Wastewaters, EPRI,
Palo Alto, CA, 2004.1005365.
iii
ABSTRACT
This report summarizes the most suitable technologies available for the removal of arsenic and
selenium from power plant wastewaters. The information stems from literature searches and
the authors experience in wastewater treatment systems from generally non-power plant
sources since there are limited operating experiences for power plant applications. The report
lists existing and potential technologies that meet the treatment goals of reducing arsenic and
selenium to the levels set for EPA drinking water standards. The most suitable of the standalone technologies for the removal of the targeted pollutants are discussed in detail and
recommended for further evaluation as specifically tailored to power plant wastewaters.
The reader is also encouraged to review EPRI Report TR-107081, Power Plant Wastewater
Treatment Technology Review Report. This 1996 report summarizes information on treatment
process performance, economics, and applications for all key power plant wastewater
applications and target chemicals. Again, it is important on note the limited operating
experiences and the heavy reliance of applications in non-electric utility industries.
EXECUTIVE SUMMARY
Based on the authors years of experience in wastewater treatment system designs for power
plant and other industries and the extensive literature survey conducted, the most viable
technologies for the removal of arsenic and selenium from power plant wastewaters are
presented. The criteria used to identify suitable technologies were that the treatment be
capable of reducing the targeted pollutants to the EPA drinking water standards of 10 ppb for
arsenic and 50 ppb for selenium. Further requirements for the candidates were that their
application be economical, simple and result in a minimum waste residual (hazardous or nonhazardous). The feed water characteristics used as a basis for this evaluation were the ash
pond waters defined in the PISCES Report Metals Removal in Ash Ponds at PISCES Sites #4).
A wide spectrum of standard and new wastewater treatment technologies was reviewed and
evaluated. While many of these methodologies are capable of meeting the established pollutant
reduction criteria, many do so at high capital and operating costs and/or while generating
substantial volumes of process residuals, which must then be disposed of.
Of the technologies evaluated, fixed bed adsorption, especially using granular ferricoxyhydroxide media, appears to be the most promising approach. This simple and economical
process utilizes highly adsorptive, single use media that needs no pretreatment, suffers few
interferences and results in a small spent media residual that is land fillable. Biological
anaerobic treatment is another technology of interest. This technology has been successful in
treating mining operation wastewaters. Other techniques of potential interest are single use
alumina adsorption media and in-situ encapsulation using products that are made from the red
mud residual from aluminum production. Technologies, including coagulation/flocculation,
membrane separation and ion exchange are also viable approaches, but, based on their
economics and/or voluminous process residuals, are only reasonable methodologies if the
arsenic and/or selenium containing waters are co-treated as part of an already existing
treatment system.
Based on the findings of this report, recommendations for follow-on bench scale testing of the
most promising technologies, applied to actual power plant wastewaters, are presented and a
brief description for such screening tests outlined.
GLOSSARY OF TERMS
Term
Description
AA
Activated Alumina
AB
ABMetTM
AMF
BDAT
BSeRTM
TM
BasR
BV
Bed Volumes
ED
Electro-dialysis
EDR
Reverse electro-dialysis
EBCV
FOG
GFH
GFO
IX
Ion Exchange
ICOS
MDL
MF
Micro-filtration
MCL
NF
Nano-filtration
PISCES
PRB
RO
Reverse Osmosis
SMI
TCLP
TDS
UF
Ultra-filtration
CONTENTS
SECTION
1
PAGE
INTRODUCTION ...................................................................................................................1
1.1
GENERAL ......................................................................................................................1
1.2
1.2.1
ARSENIC
2
1.2.2
SELENIUM
2
1.3
OBJECTIVE AND APPROACH ......................................................................................2
1.4
2
WATER CHEMISTRY............................................................................................................4
2.1
ARSENIC........................................................................................................................4
2.2
SELENIUM .....................................................................................................................4
2.3
TECHNOLOGIES ...........................................................................................................7
3.2
REVIEW CRITERIA........................................................................................................7
4.1.1
GENERAL PROCESS DESCRIPTION
9
4.1.2
FERRIC OXIDE / HYDROXIDE MEDIA
10
4.1.2.1
Granular Ferric Hydroxide (GFHTM)................................................................11
4.1.2.2
Granular Ferric Oxide (GFO) .........................................................................12
4.1.2.3
GFHTM and GFO.............................................................................................12
4.1.3
ACTIVATED ALUMINA
14
4.1.3.1
Comparison of AA with Ferric-oxyhydroxide Media .......................................15
4.1.3.2
Activated Alumina TRAMFLOC AAFS50 ....................................................18
4.1.4
BASECONTM AND BAUXSOLTM TECHNOLOGIES
18
4.1.5
IRON OXIDE COATED SAND (ICOS)
20
4.1.6
GREEN SAND
21
4.1.7
SULFUR MODIFIED IRON (SMI)
21
4.1.8
IRON FILINGS
21
4.2
PRECIPITATION CHEMICAL TREATMENT ............................................................22
4.2.1
COAGULATION / FLOCCULATION
22
4.2.2
LIME SOFTENING
23
4.3
ION EXCHANGE ..........................................................................................................23
4.4
MEMBRANE SEPARATION.........................................................................................24
4.5
4.5.1
RO AND NF PROCESS DESCRIPTION
24
4.5.2
RO AND NF TREATMENT RESULTS
25
4.6
ULTRA- AND MICRO-FILTRATION .............................................................................25
4.6.1
UF AND MF PROCESS DESCRIPTION
25
4.6.2
COAGULATION WITH MICRO-FILTERATION
26
4.6.3
ELECTRO-DIALYSIS (AND REVERSE ELECTRO-DIALYSIS)
27
4.7
BIOLOGICAL TREATMENTS ......................................................................................27
4.7.1
BIOFILM REACTORS
27
4.7.1.1
Applied Biosciences .......................................................................................28
4.7.2
CONSTRUCTED WETLANDS
29
4.8
EVAPORATION............................................................................................................29
5
DISCUSSION OF TECHNOLOGIES...................................................................................31
5.1
5.2
5.2.1
5.2.2
31
33
CONCLUSIONS ..................................................................................................................34
RECOMMENDATIONS .......................................................................................................37
7.1
7.2
BIBLIOGRAPHY .........................................................................................................................40
LIST OF TABLES
ITEM
PAGE
TABLE 2-1
TABLE 4-1
16
TABLE 4-2
19
TABLE 5-1
End
TABLE 5-2
End
LIST OF FIGURES
Figure 2-1
Figure 2-2
Figure 2-3:
1 INTRODUCTION
1.1 GENERAL
Power plant wastewaters, including ash pond volumes and ash pond run-off or spillage, can
pose a serious threat to the surroundings by transferring contaminants to the environment.
Among the many pollutants contained in these waters, arsenic and selenium are of special
concern since they are harmful to humans even at very low doses.
Varying levels of both arsenic and selenium, typically in trace amounts, are present in coal and
crude oil. As the fuels are combusted these components are released and partially condense
on fly ash particulates. As the fly ash and other solids are captured and transferred to the ash
holding systems, arsenic and selenium are introduced to the ash ponds in either a solid or a
dissolved form. Other major sources for these pollutants can be from the plant makeup water.
The current USEPA drinking water limits for both arsenic and selenium are 50 ppb. Adopted in
2003 and mandated by January 23, 2006, the USEPA has lowered the arsenic level in drinking
water to 10 ppb.
With the ever-present risk of wastewater spills to the environment (from ash ponds or other
sources), it is imperative for the power industry to have a means of treating stored or discharged
wastewaters for arsenic and selenium. The goal of such a treatment is to reduce the level of
these contaminants to meet existing and future drinking water levels.
The objective of this technology summary report is to identify cost effective treatment processes
that are capable of reducing arsenic to 10 ppb and selenium to 50 ppb. With the capability of
meeting such treatment goals, the power industry could look forward to meeting future NPDES
requirements, which can be anticipated to become more stringent as the new drinking water
rules become effective.
Due to the extensive presence of arsenic in well water world wide and the chemicals
detrimental effect on human health, most of the literature references found in the search for
viable technologies were for the removal of arsenic from drinking waters. With the 50 ppb
arsenic in drinking water allowable in the US until the year 2006, it was further noted that most
small and larger treatment systems for arsenic are located abroad as are the new process
technologies that have recently been developed.
The traditional means of arsenic and selenium removal, used in large scale water treatment
plants, are by co-precipitation methods. This process has the obvious drawback of removing
other, untargeted constituents, thereby resulting in large-volume process residuals. Other
treatment methodologies include membrane separation and ion exchange, which are also nontargeted processes and leave large volumes of undesirable residuals. Recent advances in
sorption media have, however, been successfully applied to remove arsenic without resulting in
large volumes of process by-products. Selenium is also removed by this technology. Since
selenium is not commonly present in drinking water sources, there are little data describing
specific adsorption characteristics for selenium.
1.2.2 SELENIUM
Low levels of selenium are essential in human diet as a necessary nutrient. Higher levels of
dietary selenium may, however, lead to heart problems, irregular breathing and
stomachaches. At even relatively short exposures to levels above the MCL, the EPA has
found selenium to potentially cause hair and fingernail changes or loss, damage to the
peripheral nervous system, flue-like symptoms, fatigue and irritability.
When Marco Polo made his legendary trip to China, his party passed through a region in
which most of his horses became very ill. The hooves of most severely affected horses
literally fell off! This was one of the first recorded instances of a disease now known as
"blind staggers", which is only encountered in areas where the soil is very rich in mineral
selenium.
Long-term selenium exposure to levels above the MCL carries the additional risk of causing
damage to the kidney and liver tissues as well as to the nervous and circulatory systems
and, in severe cases, respiratory failure and death. Selenium has not been found to be a
carcinogen and some studies have suggested that it may even play a cancer preventative
role.
Also sought were technologies for the in-situ treatment for arsenic and selenium in ash pond
waters by either pump-treat-return or by placing a treatment process directly into the pond
system.
2 WATER CHEMISTRY
2.1 ARSENIC
Arsenic can be in an organic or inorganic form with the latter being the most common in power
plant wastewater encounters. Inorganic arsenic occurs in two oxidation states:
Arsenite = As+3 (Reduced)
o Non-ionic at neutral pH (H3AsO4)
o Highly soluble
o More toxic than arsenate (As+5) for many organisms
o More difficult to remove compared to arsenate
o Arsenite consist of mainly H3AsO3 (arsenious acid)
2.2 SELENIUM
Selenium is a metalloid element that is located just below sulfur in the periodic table. It
resembles sulfur and forms many of the same compounds. The solubilities of selenium are
similar to sulfur salts. Also, most selenate salts are more soluble than selenite salts.
Selenium can be in as many as five different oxidation states. Some are anions, some are
neutral and some are cations with the most common forms being:
Selenate
Selenite
Selenium (elemental)
Selenide
Se+6
Se+4
Se0
Se-2
SeO4-2
HSeO3-1
Se
HSe-1
Selenate and selenite are the most common in aqueous solutions. Selenium combines with
oxygen to form several other selenium compounds as well. In oxygenated environments,
selenium is typically present in the selenate form, while selenite should be predominant in
reducing conditions.
TABLE 2-1
ASH POND WATER CHEMISTRY CHARACTERIZATION*)
Influent a (g/L)
Effluent b (g/L)
Median
Range d
Median
Range d
78,000
2,900 to 290,000
580
180 to 1,500
10
3 to 31
Arsenic
340
25 to 1,500
60
6 to 160
Barium
1,200
93 to 7,800
110
70 to 130
15
1 to 49
0.2
0.1 to 0.9
1,200
430 to 5,500
1,100
270 to 7,800
Cadmium
1.5 to 23
0.3
0.1 to 3.6
Chromium
180
2.5
1.0 to 12
Chromium VI
10
1.4
0.05 to 11
Copper
310
4.0
1.1 to 15
Iron
35,000
4,000 to 170,000
180
53 to 480
Lead
120
5 to 250
0.6
0.2 to 2.8
Mercury
0.3
0.05 to 4.0
.002
0.0006 to 0.01
Nickel
110
15 to 350
7.0
3 to 23
Selenium
51
8 to 210
35
5 to 100
Thallium
1.1
0.3 to 9
Vanadium
600
30 to 1,400
59
6 to 100
Zinc
380
7.0
2 to 44
pH
7.3
4.0 to 9.6
7.4
6.0 to 8.9
TDS (mg/l)
270
91 to 860
260
98 to 950
TSS (mg/l)
3,900
41 to 20,000
4 to 17
Aluminum
Antimony
Beryllium
Boron
This data is taken from Table 5-2 of the PISCES Report Metals Removal in Ash Ponds at PISCES Sites#4
Influent samples are 24 hour composite samples taken from water flowing through the ash deltas
Effluent samples were collected outside discharge structures so do not represent permitted outfalls or reflect pH
b
adjustment of some systems.
c
The apparent increase in antimony concentrations from influent to effluent is likely due to the quality of data in the
high-solids influent samples.
d
Range is 5th to 95th percentile
<D.L. = The result was below the method of detection limit (MDL) for conventional method achieved by the
conventional laboratory as defined in 40 CFR 136(22).
*)
a
3.1 TECHNOLOGIES
This technology summary identifies several types of processes as potential treatment
candidates for the removal of arsenic and selenium from power plant wastewaters. They
are as follows:
Sorption / adsorption
Ion exchange
Biological Removal
Evaporation
With the recent concern of arsenic levels in drinking water, most of the literature citations
encountered were focused on the removal of this component. Many of the same processes
are, however, also applicable and effective for the removal of selenium.
One factor that seems to be common to all inorganic arsenic treatment processes is that
As+5 is much more easily and effectively removed compared to As+3. While the more highly
oxidized As+5 is typically the predominant specie, the PISCES report of ash pond waters
indicates up to 5 percent of arsenic in a reduced state.
While the emphasis of this study was to identify proven, ready for use technologies, some
promising treatment processes that are still in the development stage are also cited. Until
such processes are commercially available, however, they cannot be considered real
candidates and are, therefore, not described in detail in this document.
percent, that carries the removed arsenic and/or selenium in a concentrated form, may be
burdensome especially if the liquids and/or solids are of a hazardous nature.
While it is possible to deal with such residual concentrates through evaporation,
crystallization, precipitation or even reverse osmosis, these processes add to the complexity
and cost of the initial treatment. The goal for an optimal treatment technology is, therefore,
that it leaves a minimal residual volume, preferentially in a solid and non-hazardous form
that is suitable for a conventional landfill.
4 TECHNOLOGY CANDIDATES
Of the many different technologies reviewed, only some were deemed to reasonably meet the
selection criteria established for this study. The processes described in this section either meet
or have the potential promise to meet these criteria in power plant applications.
Bulk transport: The adsorbate is transported from the solvent to the boundary layer
surrounding the adsorbent.
External resistance: The adsorbate must overcome this resistance to reach the
adsorbent media.
Internal transport: The adsorbate moves through the pores to the adsorption sites.
Adsorption: The adsorbate is fixed to the adsorbent media surface.
ROSSO, K., RUSTAD, J, Structures and energies of AlOOH and FeOOH polymorphs from plane wave
pseudopotential calculations, American Mineralogist, Volume 86, pages 312317, 2001
largest arsenic treatment plant for drinking water in the U.S., taking 17 ppb arsenic well water to
10 ppb in the effluent.
Compared to other adsorption processes, like activated alumina or green sand filtration, GFHTM
and GFO are effective over a fairly wide pH range with good efficiencies up to a pH of about 8.0
to 8.5. This typically allows the treatment to be performed on the unconditioned influents and
eliminating the need for effluent pH control.
The ferric media removes arsenic, uranium, selenium, antimony, copper and phosphate. Other
components are also affected, but to a lesser degree. If significant levels of arsenite (As+3) are
present then an operation at a pH greater than 7.5 is typically advised to eliminate the need for
arsenite oxidation. Adsorption of selenate is also pH dependent.
Unlike activated alumina, interferences from moderate levels of other components like silica or
sulfates are not a problem. Phosphates will reduce the adsorptive capacity, however.
Suspended solids, including fly ash, precipitated iron and manganese, should be removed prior
to treatment due to the potential of media plugging by trapped solids.
Backwash of the vessels is required on a periodic basis (4-6 weeks of operation for well water)
to prevent compaction of the bed and to remove accumulated particulates. While applications
to ash pond or other stored waters may demand more rigorous backwashing, there should be
the benefit of a stable feed chemistry with little precipitation potential within the treatment
system.
Pal, BN, Granular Ferric Hydroxide for Elimination of Arsenic from Drinking Water, From BUET (BUETUNU, 2001), Technologies for Removal of Arsenic from Drinking Water, p 59-68.
PARAMETER
GFO
1.
Process type
2.
Similar
Similar
3.
4.
5.
Non-hazardous, passes
TCLP tests, i.e. land-fillable
Non-hazardous, passes
TCLP tests, i.e. land-fillable
6.
7.
Technology Status
8.
Technology Source
US Filter / Wastewater
Group, Inc.
9.
Media Name
Media Source
BayoxideE33
Manufactured by Bayer AG
(Germany), sole source via
Severn Trent Services
10.
Chemical name
-ferric hydroxide
Fe(OH)3
-ferric oxyhydroxide
(FeOOH)
11.
Media Cost
$ 3.50 / lb
12.
Grain size
0.3 2.0 mm
0.5 2.0 mm
250-300 m2/g
(75% porosity)
140-180 m2/g
2 % max
n/a
2 % max
1.2 % max
15.
Density
Bulk density
n/a
72 lbs/ft3
16.
2 8 gpm/ft2
2 8 gpm/ft2
13.
14.
PARAMETER
GFO
17.
10-12 gpm/ft2 at 55 F
8 12 gpm/ft2
18.
63
63
19.
7.3 psi
9.0 psi
20.
Typical EBCT
5 minutes
5 minutes
21.
86 F
120 F
22.
12 months
36 months
23.
Wet
Dry
the adsorption rates and bed volume capacities. At more acidic pHs, on the other hand, the
activated alumina begins to dissolve. The optimum AA operating pH range is from 5.5 to 6.5.
Activated alumina is an effective means of removing selenium in its selenite (Se+4) rather than
its selenate (Se+6) form, this especially in the presence of sulfate ions. AA adsorption of
selenate is be significantly higher at low sulfate levels. The adsorption of selenite is pH
dependent, with an approximate three-fold decrease experienced when increasing the pH from
5 to 7.
Media regeneration is normally performed with a 1% to 4% sodium hydroxide solution. This is
followed by a 1% sulfuric acid solution rinse to recondition the alumina. Regeneration is carried
out in an up-flow manner to expand the bed, remove accumulated debris and to minimize
cementing,
During the regeneration procedure not all arsenic is eluted. Pilot tests, described in the
literature, indicate that that a 10% to 15% loss in adsorption capacity may be experienced with
each regeneration cycle.
While activated alumina is not widely used for water or wastewater treatment in general, it is a
proven technology that has been used for many years. The technology and equipment are
available from multiple sources.
The drawbacks of this technology include the need for pre-oxidation of As+3, the relatively
narrow pH operating range and the number of interferences from other components.
Furthermore, regeneration results in a waste stream that contains the removed arsenic,
selenium and other pollutants, which must be disposed of.
Media costs are approximately $ 1.00 to $ 1.30 per pound (density is 47 lbs/ft3). Spent media
can typically be disposed off as a non-hazardous material.
AA
GFO **)
1.
Process type
2.
Cheaper than AA
3.
4.
> 100,000 BV
No quantitative data for
selenium adsoprtion
available.
5.
6.
Media Regeneration
7.
8.
Single-use media
No regeneration.
Spent media is the only
process residual.
9.
Technology Status
10.
Technology Source
Tampa, Florida
11.
Media Name
Media Source
BayoxideE33
Manufactured by Bayer AG
(Germany), sole source via
Severn Trent Services
12.
Chemical name
Aluminum Oxide/Hydroxide
-ferric oxyhydroxide
(FeOOH)
13.
Media Cost
$ 1.00 to 1.30 / lb
14.
Bulk density
47 lbs/ft3
29 lbs/ft3
**)
For simplicity AA is compared to only GFO. For AA comparison to GFH, consult GFO vs. GFH comparisons
shown in Table 4.1
Again, As+5 is much more easily removed than As+3. Although As+3 can be directly reduced
using the BaseconTM reagent ViroMine, it is most effectively removed by pre-oxidation with
subsequent treatment using BauxsolTM.
Most of the BaseconTM product development has been carried out in Australia. As this continent
is selenium deficient, not much work has been done on its removal. Based on possible need in
the U.S. and Europe, there is presently an R&D project underway to determine the materials
effectiveness for selenium. Some earlier work on wastewaters indicated that selenium removal
of 60% is possible. Based on a more recent study, however, better adsorption rates can be
anticipated, especially in relation to a sulfide supplemented technology.
To date most applications of Virotec's reagents have been in the form of an in-situ treatment for
pond waters. Using the usual spray equipment and setup, the material is sprayed over the pond
surface. As the reagents settle through the water, they adsorb and firmly bind heavy metal
pollutants via a number of chemical mechanisms. Another characteristic of the reagents is that
they neutralize acidic solutions, typically buffering the water at a pH of approximately 8.5.
The manufacturer suggests spraying sufficient material to form a thin coating of a few
millimeters at the pond bottom. With time, the reagents have shown to stay active and bind
additional pollutants. TCLP tests of the settled material have demonstrated that the adsorbates
are firmly held and little or no leaching from the encapsulating product occurs. Specific pollutant
reduction data can be found in the Virotec Technology literature #31).
Fixed bed media systems have also shown to be effective for acid mine and acid rock drainage
wastes as well as for other industrial wastewater applications. For the pollutant laden mining
wastewaters, about 2 to 4 tons per million liters of reagent is required in these Active Mineral
Filters (AMF). This translates to a bed volume capacity of approximately 500. For relatively low
feed concentrations, as found in ash pond applications, the media capacity is expected to be
significantly higher. The AMFs presently tested by Virotec are of a gravity bed filter type.
Large-scale systems of the BaseconTM- AMF technology are being implemented or considered
for large mining operations Peru, Australia and Korea.
Other BaseconTM reagents are being developed in a pellet form to improve porosity and metals
binding capacity. This configuration has been successfully tested on mine and tannery
wastewaters.
BaseconTM reagents have also been employed in Permeable Reactive Barriers (PRB). PRBs
are constructed using porous pellets, blocks or by mixing the products with sand, soil or crushed
rock. The barriers are designed to provide the needed reaction time in relation to the
anticipated flow or overflow rates. PRBs have several benefits, including the fact that iron and
aluminum, typically present in larger concentrations, are mainly removed by crystal growth
rather than adsorption mechanisms. Crystal formation, including the precipitation of gypsum,
does not adversely affect the system permeability or exhaust adsorptive capacity. The barrier
bed also supports biological growth, which may aid in the remediation process.
As is typical for PRB systems, the bed must be replaced once the adsorbent capacity has been
exhausted. This technology may be of interest in areas where pond overflow issues are of
concern.
This ferric-hydrite adsorption process (addition of a ferric coagulant) has been identified by the
EPA as a best available technology for selenium removal in mining wastes. The key points for
this technology for selenium applications are:
The optimal removal pH for selenium differs from that best suited for arsenic. If both
components are to be treated in a single process step, compromises have to be made that
affect the effluent quality. In order to achieve the lowest levels of both arsenic and selenium, a
two-step process, operating at different pHs, may be required.
While coagulation / flocculation can be an effective process for removing arsenic and selenium,
it has the major drawback of producing a sludge residual that must be dealt with. The dried
sludge may be a hazardous waste, requiring either further treatment or resulting in high disposal
costs. Compared to other processes described in this summary, coagulation/flocculation is a
complicated, operator intensive operation. It also requires the handling of dangerous chemicals.
In a June 2001 EPA comparative study#18) of several different technologies for the removal of
selenium from mining wastes using a ferric chloride reagent (the system included pH control
and sludge dewater), the estimated the treatment costs were $ 13.90 per 1000 gallons. It must
be noted that the selenium levels in this feed water were several thousand ppb, which required
a ferric chloride addition dosage of more than 1,000 ppm (2000:1 Fe/Se). Since the coagulant
was a major portion of the above listed cost, treatment of less concentrated power plant wastes
are anticipated to be less.
able to remove selenate from acidic feed waters. Strong base resins are able to remove all
anions, including selenium.
There are several drawbacks to the use of ion exchange in this application. Since sulfate is a
competing component, IX is typically only useful if employed on waters of low TDS and low
sulfate concentration.
Resin fouling or scaling is an other potential problem. Although the spent regenerant in this
application may be used several times before discharge, it contains the removed pollutants
making it hazardous waste. Unless there is an on-site opportunity to co-treat this waste stream
with other wastewaters, such as in an evaporator or membrane separation system or chemical
precipitation, disposal of the regenerant may be problematic and expensive.
Reverse osmosis and nano-filtration typically have identical equipment and process
arrangements. Both require pre-filtration for solids removal and possibly pH control of the feed.
With nano-filtration removing mainly multi-valent ions, the osmotic and hydraulic pressure
requirements are much lower compared to RO, allowing the NF process to be carried out at
much lower feed pressures.
Reverse osmosis and nano-filtration normally process the feed water in a single pass operation,
purifying 75 to 90% of the water while discharging the remaining flow as a concentrate that
contains the rejected components. Although not commonly used, batch and semi-batch
operation as well as two pass operations are sometimes employed to either further reduce the
concentrate stream volume (reject) or the improved permeate quality. The critical and limiting
parameters in membrane processing are the solubility limits of the dissolved components and
organic fouling. Both can normally be mitigated by use of inhibitors and membrane cleaners.
Unless a convenient means of dealing with a 10% to 25% residual concentrate stream is
available, membrane separation will be difficult to justify for this application as a stand-alone
process. This especially as the reject stream carries the arsenic, selenium and other pollutants
in concentrated form. If co-treatment of the reject with an already existing process is possible,
then the RO or NF approach may be worth considering.
Membrane module configurations are similar to those of RO and NF, with tubular or hollow fiber
modules used for higher solids concentrations. Materials of construction can vary, and include
various polymers, ceramic and metal compositions.
Membranes are available in different porosities that can be selected to meet specific processing
needs. UF pore sizes are rated in molecular cut-off (or Daltons) that can range from a few
1,000 to several 100-thousands. UF pore sizes range from 0.001 to 0.2 microns while MF pore
sizes typically range from 0.1 to 1.0 microns.
Depending on the design, UF or MF systems deal with the rejected solids stream by different
means. Traditionally the rejected materials are flushed form the membrane and carried away in
the concentrate stream, which may be recycled in a batch mode or purged from the system.
Other designs allow the captured solids to build up on the membranes and are then periodically
purged by back-flushing or back pulsing. The latter design is more complex, but results in a
substantially smaller reject stream.
Since UF and MF processes are only capable of suspended solids removal, their use is limited
to the removal of particulate arsenic or selenium. These particulates may stem from source
waters or from chemical changes or may have resulted from prior coagulation or other chemical
treatment processes.
UF and MF systems are typically designed to operate with solids concentrations of 1% or more
in the recirculating concentrate. With only a few ppm generated in the treated feed, the solids
level in the recirculating concentration will remain low. Batch or semi-batch operating modes, or
dead-head filtration with periodic purging, minimize the reject blowdown stream.
The disadvantage of this process is the complexity of dealing with two integrated process
operations, one of which requires the use of dangerous chemicals. Arsenic and selenium can
only be removed to the extent that they are in solid form. This means that if As+3 is present, it
must be oxidized in order to convert it to the more treatable As+5 form. With the exception of
suspended solids carry-over, the shortcomings, previously described for the coagulation
process also apply.
The capital and operating costs for this technology are the sum of the coagulation plus the MF
processes.
selenium, with each train containing two or more vessels. All trains and vessels would be
arranged in series.
Using pollutant targeted and controlled systems, biofilm reactors have been demonstrated to be
effective for removing both arsenic and selenium to below detection limits on a consistent basis.
The reactors are able to remove selenium and arsenic in either of their respective, common
oxidation states.
The EPA identified both of these chemical treatments as best available technologies in mining
applications. (Ferric hydrite precipitation/adsorption i.e. precipitation with ferric chloride or
sulfate, is discussed earlier in this document.)
The EPA sponsored ABMetTM (BSeRTM ) test was conducted for 187 days on feed water that
contained 1,500 to 2,000 ppb selenium and about 70 ppb arsenic. Both selenium and arsenic,
as well as some other heavy metal components were consistently removed to the drinking water
limits, with most effluent samples showing selenium and arsenic below detection limits. The
bioreactor contact times to achieve these results were typically 5.5 hours.
The demonstration program showed that all three technologies tested were able to meet the
selenium reduction goals under their best operating conditions. The ABMetTM (BSeRTM )
process was the only one to meet the reduction goals consistently, however. The cost
comparisons between the three technologies for this application, showed that the capital costs
for the ABMetTM (BSeRTM ) system were less than one tenth the cost of the other two
technologies and that the operating costs, including nutrients, was $ 0.58 per 1,000 gallons.
Capital costs were estimated to be $ 1.32 per 1,000 gallons treated.
In a more recent publication, the manufacturer claims that the operations and maintenance
costs for their systems are about $ 0.20 per 1000 gallons treated, with the majority of this
amount for the nutrient supplement. Both operating and capital costs vary depending on the
application, feed concentrations and reactor sizing.
For the removal of arsenic and selenium, the manufacturer recommends a three stage system,
consisting of one multi-vessel reactor anaerobic train for arsenic and one for selenium, followed
by an aerobic reactor train to remove undesirable process residuals like ammonia or other
pollutants either intrinsic in the feed water or generated in the anaerobic process.
4.8 EVAPORATION
Evaporation would be an effective means of removing arsenic and/or selenium. While many
power plants have vapor compression or other evaporators as part of their wastewater
management, these units are typically specifically sized for a final volume reduction stage prior
to discharge to evaporation ponds or crystallizers.
Since evaporation processes are non-targeted processes and are typically very high in both
capital and operating costs, they do not meet the selection criteria established for this study and
are, therefore, not further discussed.
5 DISCUSSION OF TECHNOLOGIES
4. Membrane Separation
Reverse osmosis and nano-filtration
Flocculation followed by micro-filtration
5. Biological treatment
Anaerobic Biofilm Reactors
The selection of the most suitable and cost effective technology is usually dependent on the
specific application, including wastewater quality (concentration and composition), the
percentage of As+3 vs. As+5 and/or Se+4 vs. Se+6 present, the levels of interfering inorganic and
organic components as well as liquid volumes (pond volumes) or flow rates to be treated. The
presence of existing treatment systems on site, that may allow co-treatment with other
wastewaters, may also be a decisive factor.
In situations where the ash pond or other arsenic and/or selenium containing wastewaters are to
be addressed on a stand-alone basis, the selection of the most suitable technology narrows. If
only arsenic and/or selenium and perhaps some other heavy metals are to be targeted, then a
process that removes large quantities of peripheral components is of less interest, especially if
this results in significant costs for treatment and the disposal of residuals.
Chemical precipitation, ion exchange and reverse osmosis processes fall into the category of
co-removing non-targeted components at the expense of generating large process residuals.
Iron and alumina adsorption, on the other hand, target mainly heavy metals, including arsenic
and selenium. Since the concentrations of heavy metals in power plant wastewaters are usually
relatively low, their co-removal along with arsenic and selenium should be acceptable, as long
as arsenic and selenium are reduced to the desired limits. Anaerobic bioreactors also represent
a focused treatment since specialized bugs are needed to remove specific components.
Although the BauxsolTM technology does adsorb components other than heavy metals,
according to the manufacturer it does so at low media costs. If the technology is used for in-situ
encapsulation of pollutants, then excess process residuals are not an issue.
Both granular ferric-oxyhydroxide (GFO and GFHTM) and activated alumina adsorption are
capable of lowering arsenic and selenium to the target levels. Single-use media of both ferricoxyhydroxide and special formulations of AA offer a simple and cost effective means for
treatment. Since, however, the presence of trivalent arsenic typically requires a pre-oxidation
step, activated alumina treatment represents a more complex process to achieve the same
ends. The standard application of activated alumina with sodium hydroxide regeneration has
the drawback of a relatively low bed volume capacity and the degeneration of active media sites
with each regeneration. Compared to the ferric-oxyhydroxides, activated alumina (including the
single-use version) operate within a lower pH range and are more adversely affected by
interfering components.
In selecting the most suitable technology for arsenic and selenium removal, other factors may
also come into play. Some of adsorptive media described is impacted by the presence of
interfering components, both organic and inorganic. A problem for all media processes is the
presence of organics such as oils (FOG), which blind adsorption sites. Reverse osmosis and
ion exchange are also adversely affected by FOG as it fouls the active process surfaces.
Suspended solids may be problematic for the above technologies, as they can lead to plugging
and fouling, which then requires increased backwashing and cleaning cycles.
Bio-treatments in the form of anaerobic biofilm reactors are also an effective means of
addressing arsenic and/or selenium. This technology, developed mainly for the mining industry,
is capable of consistently and economically removing both arsenic and selenium to the
detection limits (5 ppb) while leaving only a very small process residual. Biofilm reactors, which
are typically designed and optimized for specific applications and pollutants, can treat arsenic
and selenium in either of their common oxidation states. According to literature references, the
technology to date has been applied mainly in large pilot systems. There are, however, two
operational installations of 300 gpm, treating mining wastewaters in Canada. One 150 gpm
arsenic removal plant is presently under constructions for a gold mining operation.
6 CONCLUSIONS
There are several traditional and new technologies available to remove arsenic and selenium
from power plant wastewaters. These treatment processes, which all appear to be capable of
meeting the contaminant reduction goals, established for this evaluation, are listed in the
previous discussion section. Some of these technologies are targeted while others are general
water purification processes. Due to the variation of wastewaters encountered in power plant
operations, the choice of the most suitable treatment option will be a function of the specific
situation encountered.
In general, however, the removal of arsenic and selenium from power plant wastewaters seems
to be most effective and economical using single-use adsorptive media in the form of granular
ferric-oxyhydroxide, single use activated alumina media, BauxsolTM or anaerobic biofilm
reactors. While ion exchange, membrane separation, coagulation/flocculation or chemical
precipitation are also effective, these methodologies should be mainly considered if the arsenic
and/or selenium laden waters can be co-treated with other wastewaters in already existing
systems.
Metal oxide and hydroxide, fixed bed media systems are low in capital, operating and
maintenance costs and are effective for the removal of both arsenic and selenium. Additionally,
they have the advantage of leaving only a solid process residual that can be land filled.
Of the metal adsorption media options, the granular iron based materials appear to have better
process characteristics compared to activated alumina by having affinity for both common
oxidation states of arsenic and having a significantly higher adsorption capacity.
While there are several forms of granular ferric media available, granular ferric-oxyhydroxide,
GFO and GFHTM, seem to have the most extensive operational histories. Since the arsenic
limits in Europe are lower than in the US at this time, all of the large scale operational plants are
presently located there. Smaller scale units for both media types are currently operating in the
U.S. as demonstration plants. One large arsenic treating GFHTM plant has recently become
operational in Phoenix, Arizona.
While capable of operating on more concentrated feed waters, GFO and GFHTM are typically
employed for low pollutant levels of < 1,000 ppb arsenic and < 5,000 ppb selenium, which fall
well within the concentrations encountered in power plant wastewaters. At higher
concentrations, such as found in mining wastewaters, the economics of single use media may
yield their advantage to other technologies.
The BauxsolTM adsorption process, used for in-situ encapsulation and fixation of pollutants in
pond waters, has proven to be effective in mining applications. Use of related materials in
Active Mineral Filtration (gravity filtration) and Permeable Reactive Barriers filtration has also
shown promise. Data from mining wastewater operations, as well as test data from other areas,
have shown the technology in either of the three application methods to be effective for the
removal of arsenic and other metals. As the BauxsolTM processes were developed in Australia,
where selenium is generally not an issue, the majority of the data available is focused on
arsenic. Recent testing with selenium waters indicates, however, that the treatment may be
effective for this chemical as well.
Based on the treatment results from mining operations, anaerobic biofilm reactors, like
ABMetTM, are capable of treating both arsenic and selenium waters effectively and
economically. In most cases the pollutants are removed to below detection limits. While
biological treatment is not common in power plant operations, this relatively compact anaerobic
biomass technology may offer an effective, stand-alone alternative for the removal of arsenic
and selenium.
In summary, based on the information found in the literature, the stand-alone treatment
technologies identified in this report appear to be capable of removing both arsenic and
selenium to the levels of the EPA drinking water standards. While most arsenic references
found were for drinking water, most selenium references were for mining waste applications.
No references for the viable, stand-alone technologies, identified in this report, were found for.
No references for arsenic and selenium removal from power plant wastewaters using the
identified viable, stand-alone technologies were found in the literature search. Since power
plant wastewaters, such as ash pond or cooling tower (concentrated makeup) waters, typically
have unique compositions with respect to arsenic and selenium concentrations, oxidation
states, co-precipitation opportunities, residence times, TDS levels, pH and/or interfering
components, it is not a given that the identified viable, stand-alone technologies will work in
the same fashion as the referenced drinking or mining waters indicate. It would, therefore, be
prudent to review and corroborate the applicability of the most promising technologies in actual
power plant environments.
7 RECOMMENDATIONS
The major expenses of the recommended screening tests would be for travel, man-hours on site
and chemical analyses.
It is envisioned that the test would consists of the following major tasks:
1. Identify hosting sites
2. Obtain specific recommendations from the manufacturer for best treatment
parameters
3. Assemble test apparatus
4. Receive water samples from identified host sites for analysis
5. Conduct tests at selected sites
6. Analyze samples and interpret results
7. Prepare report and presentation to EPRI
The goal of the screening test(s) would be to identify the most suitable technology(ies) for the
applications tested. Care would have to be taken to ensure that the treatment effectiveness be
matched to the application and not to eliminate a technology that may have failed in one
application, but performed well in others.
The results of the screening would be used as a basis for a longer-term pilot demonstration test
of the technology(ies) deemed most suitable and promising.
BIBLIOGRAPHY
1. EPRI Toxics Release Inventory: Chemical Profile Arsenic
2. EPRI Toxics Release Inventory: Chemical Profile Selenium
3. An EPRI Perspective on USEPAs Arsenic MCL for Drinking Water
4. Water Toxics Summary Report: Summary of Research on Metals in Liquid and Solid Streams,
EPRI Document No. 1005409. Final Report January 2003.
5. EPRI Product Brief: PISCES Plant Multimedia Toxics Characterization Data Base
pisces.epri.com/pls/pisces/epri.data_qual
pisces.epri.com/pls/pisces/epri.t_frames
6. Power Plant Wastewater Treatment Technology Review Report, EPRI, TR-107081, November
1996
7.
Technologies and Costs for Removal of Arsenic from Drinking Water; USEPA, Office of Water,
EPA 815-R-00-028, December 2000
8. Technologies and Costs for Removal of Arsenic from Drinking Water; USEPA, Office of Water,
EPA 815-P-01-001, April 1999
9. Arsenic, Part 2 of 2: Removing Arsenic from Drinking Water, The Importance of pH, Background
Contaminants and Oxidation, Dennis Clifford, Ph.D., P.E., WCP Online
10. Regulations on the Disposal of Arsenic Residuals from Drinking Water Treatment Plants,
Science Application International Corporation, EPA/600/R-00/025/May 2000, National Risk
Management Research Laboratory, Office of Research and Development, USEPA, Cincinnati,
Ohio 45268
11. Technologies and Costs of Removal of Arsenic from Drinking Water; EPA 815-R-00-028, Dec
2000; www.epa.gov/safewater
12. An Overview of Arsenic Removal Technologies in Bangladesh and India, M. Feroze Ahmed,
Department of Civil Engineering, Bangladesh University of Engineering and Technology, Dhaka1000, Bangladesh
13. Wastewater Technology Fact Sheet, Chemical Precipitation, EPA-832-F-00-018, September
2000
14. Arizona Arsenic Master Plan: Part 3 - Compliance Options, Final Report, Arizona Department
of Environmental Quality, Water Infrastructure Finance Authority of Arizona, January 2003
15. An Overview of Arsenic Treatment in Drinking Water, Phil Bandhuber, Ph.D., McGuire
Environmental Consultants, Presented at the RMSAWWS 2000 Annual Conference
16. Arsenic in Drinking Water: Treatment Technologies: Removal
www.epa.gov/ogwdw000/ars/treat.html
17. Rapid Small-Scale Column Testing for Arsenic Adsorption Media, Aragon and Bruce
Thompson, University of New Mexico, Albuquerque, NM, Joe Chwirka, CH2M-Hill
36. An Elemental Iron Reactor for Arsenic Removal From Ground Water, Demitrious Vlassopoulos,
et al,
37. Structures and Energies of AlOOH and FeOOH Polymorphs From Plain Waive Pseudopotential
Calculations, Kelvin M. Rosso and James R. Rustad, W.R. Whiley Environmental Molecular
Science Laboratory, Pacific Northwest National Laboratory, Richland, WA
38. Environmental Technology Verification Program, Reverse Osmosis Membrane Filtration used in
Packaged Drinking Water Treatment Systems , Removal of Arsenic in Drinking Water at Park
City, Utah Hydranautics, Oceanside, CA www.membranes.com
39. As Removal Using Ion Exchange With Spent Brine Recycling, Dennis a. Clifford, et al, 95:6
Journal AWWS, June 2003
40. Membrane Systems Design and Fundamentals Philip Brandhuber, Ph.D., McGuire
Environmental Consultants, 2001 Water Quality Technology Conference
41. Selenium Removal: Bioremediation of Selenium in Waters, Applied Biosciences,
www.bioprocess.com
42. Biological Arsenic Removal (BAsRTM) Process, Applied Biosciences, www.bioprocess.com
43. Effective Biological Water Treatment Through Biological Process Control, Brad Wahlquist and
Tom Pickett, Applied Biosciences Corporation
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TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD
ADVANATAGES
DISADVANTAGES
SORPTION PROCESSES
Granular Ferric Hydroxide
(GFH)
Activated Alumina
Tramfloc AAFS50
TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD
ADVANATAGES
DISADVANTAGES
Promising technology.
Iron CoagulationFlocculation
Alum CoagulationFlocculation
Lime Softening
PRECIPITATION
CHEMICAL TREATMENT
ION EXCHANGE
TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD
IX Processes
ADVANATAGES
DISADVANTAGES
High equipment cost.
Sulfate interference major problem.
Regeneration creates liquid or sludge
disposal problem.
Prefiltration to minimize resin fouling.
MEMBRANE SEPARATION
Reverse Osmosis and
Nano-filtration Processes
ED & EDR
TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD
ADVANATAGES
DISADVANTAGES
goals.
BIOLOGICAL TREATMENTS
Biofilm Reactors
Constructed Wetlands
Standard technology.
TABLE 5-2
OTHER POTENTIAL ARSENIC AND SELENIUM REMOVAL TECHNOLOGIES
METHOD
GENERAL DESCRIPTION
DEVELOPMENT/SOURCES
Ferric Oxyhydroxide
FeO(OH) + Settling
UV FeOx
TABLE 5-2
OTHER POTENTIAL ARSENIC AND SELENIUM REMOVAL TECHNOLOGIES
METHOD
GENERAL DESCRIPTION
DEVELOPMENT/SOURCES
Iron filings with high surface sponge iron are slurried with
elemental sulfur. Sulfur and iron work together to remove As as
elemental As, which is filtered out. Technology is being applied
in California locations
US patent 6,093,328
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