United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600/2-80-100
August 1980
Research and Development
vxEPA
Pilot Study of
Fluoride and Arsenic
Removal from
Potable Water
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-80-100
August 1980
PILOT STUDY OF FLUORIDE AND ARSENIC
REMOVAL FROM POTABLE WATER
by
Frederick Rubel, Jr.
Rubel and Hager, Inc.
Tucson, Arizona 85711
Fred S. Williams
Aluminum Company of America
Alcoa Center, Pennsylvania 15069
Contract No. 68-03-1351
Project Officer
Thomas J. Sorg
Drinking Water Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
-------
DISCLAIMER
This report has been reviewed by the Municipal Environ-
mental Research Laboratory, U.S. Environmental Protection Agency,
and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the
U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommen-
dation for use.
Prote«/on Agency
ii
-------
FOREWORD
The Environmental Protection Agency was created because of
increasing public and government concern about the dangers of
pollution to the health and welfare of the American people.
Noxious air, foul water, and spoiled land are tragic testimony
to the deterioration of our natural environment. The complexity
of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem
solution and it involves defining the problem, measuring its
impact, and searching for solutions. The Municipal Environmental
Research Laboratory develops new and improved technology and
systems for the prevention, treatment, and management of waste-
water and solid and hazardous waste pollutant discharges from
municipal and community sources, for the preservation and treat-
ment of public drinking water supplies, and to minimize the
adverse economic, social, health, and aesthetic effects of
pollution. This publication is one of the products of that
research; a most vital communications link between the researcher
and the user community.
Fluoride and arsenic are two contaminants frequently found in
high concentrations in drinking water. Activated alumina treat-
ment will remove both elements from water, but the operating
procedures vary slightly for each contaminant. Occasionally,
the two contaminants are found together in the same water supply
that presents a unique treatment problem. This report describes
the results of two series of pilot plant tests to determine the
optimum system for removing the two contaminants in combination
in a ground water by activated alumina treatment. Construction
and operating costs for small systems are also presented.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
111
-------
ABSTRACT
Pilot plant studies were conducted on the removal of fluo-
oride and arsenic from potable water using activated alumina as
the adsorbent. The tests were run using water from the commu-
nity of Why, Arizona, that contained 3 mg/L fluoride and
0.15 mg/L arsenic.
The experimental data show that activated alumina is an
effective means of treating this water. Major facts shown by
the data are that: (a) arsenic is preferentially adsorbed on
the activated alumina, (b) a stronger sodium hydroxide solution
(4%) is required during regeneration of the activated alumina
for arsenic than is required for fluoride (1%), and (c) the
capacity of the alumina for removing fluoride is decreased by
any arsenic remaining in the alumina. The pilot studies indi-
cate that the preferred method of treating water with these com-
bined contaminants is the use of two activated alumina columns
in series.
A schematic of a full-sized treatment plant is included,
along with engineering estimates of operating and capital equip-
ment costs for small communities. Operating costs are approxi-
mately 5£/kL of treated water. (19C/1000 gal.)
This report was submitted in fulfillment of Contract No.
68-03-1351 by the Aluminum Company of America under the sponsor-
ship of the U.S. Environmental Protection Agency. This report
covers the period 6/78 to 4/79, and work was completed as of
8/79.
IV
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CONTENTS
Foreword iii
Abstract iv
Figures vi
Tables vi
1. Introduction 1
2. Conclusions 3
3. Description of Test Site and Apparatus 5
4. Experimental Results 10
5. Cost Estimates 17
References 20
Appendices
A. Fluoride/arsenic removal project - Phase I .... 21
B. Fluoride/arsenic removal project - Phase II .... 27
C. Water Analyses 36
-------
FIGURES
Number
Page
1 Process Schematic Flow Diagrams - Phase I .... 6
2 Regeneration Process Schematic Flow
Diagrams - Phase I 7
3 Process Schematic Flow Diagrams - Phase II ... 8
4 Plots of Phase II Run 3 Water Concentrations . . 14
5 Treatment Plant Equipment Layout Plan 18
TABLES
Number
1 Phase I Pilot Plant Fluoride and Arsenic
Removal Summary
Page
2 Phase II Pilot Plant Fluoride and Arsenic
Removal Summary ............... 13
3 Data on the Dissolution of Alumina During
Regeneration ................ 15
4 Arsenic Oxidation States ........... 16
5 Preliminary Operating Cost Estimates for
Small Systems ................ 19
6 Preliminary Capital Cost Estimates for
Small Systems ................ 19
VI
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SECTION 1
INTRODUCTION
As of June 24, 1977, communities throughout the United
States are required to comply with the U.S. Environmental Pro-
tection Agency (EPA) National Interim Primary Drinking Water
Regulations, dated December 24, 1975.1 Maximum contaminant
levels in potable water supplies have been established for 10
inorganic chemicals, including fluoride and arsenic. The maxi-
mum contaminant level for fluoride varies from 1.4 to 2.4 mg/L,
depending on the annual average of the maximum daily air temper-
atures. The maximum contaminant level for arsenic is 0.05 mg/L.
Techniques for the successful removal of excess fluoride
from potable water sources with activated alumina have been de-
veloped by Rubel and Hager, Inc., Tucson, Arizona, and have been
used in three full-scale operating plants. The first plant, in
Desert Center, California, has been in operation since 1970.
The second plant, at X-9 Ranch near Tucson, Arizona, has been
in operation since 1972; and the third plant, in Gila Bend,
Arizona, has been operating since 1978. These plants have been
removing fluoride at operating costs of 2.5 to 4.0*/kL (10-15C/
1,000 gal) of treated water for fluoride waters containing 4.5
to 7.5 mg/L fluoride. Further details on the operating tech-
niques used in these plants are decribed in a 1978 EPA technical
report2 and in the Journal of the American Water Works Associ-
ation. 3
A number of excellent articles are available that discuss
the stability and solubility of inorganic arsenic in various
water environments.5'6'7 The depth of these articles is an indi-
cation of the complexity of arsenic chemistry. In a natural
water system, however, it is demonstrated that arsenic would
most commonly be found in +5 and +3 oxidation states. A recent
article by Gupta and Chen8 presents the experimental results of
using activated alumina, bauxite, and carbon as sorbents for
arsenic in batch equilibrium tests. One of the base waters used
in this study was fresh water to which was -added concentrations
of As+3 in the form NaAs02 and As+5 in the form Na2HAsOi,. Their
data show that activated alumina has about 20 times greater ca-
pacity for removal of As+5 than for As+3. They conclude that
removal of arsenic from waste waters to meet water quality cri-
teria is technically feasible.
-------
_In 1978, Rubel and Hager and the Aluminum Company of
America conducted a pilot plant experiment on a potable water
test well that contained 2 mg/L arsenic and 1 mg/L fluoride.
Reports on this work have not yet been published, principally
because the oxidation states of the test water were not iden-
tified. The work, however, was significant in that it demon-
strated (1) that the activated alumina had a capacity for arsenic
removal on this water comparable to that experienced with fluo-
ride in fluoride-contaminated water, and (2) that there was a
problem associated with regenerating the activated alumina.
A serious question developed concerning the ability of activated
alumina to remove excessive levels of two contaminants in com-
bination in a single water supply. Specifically, arsenic is not
removed from an activated alumina treatment bed during regener-
ation as easily as fluoride. This has also been reported for
test work by Bellack.1* Our tests indicated that higher sodium
hydroxide concentrations were required to remove arsenic from
activated alumina than the 1% caustic concentration used for
fluoride removal at the full-scale fluoride removal plants. The
pilot work also showed that arsenic retained on the activated
alumina after regeneration interfered with the removal of fluo-
ride during subsequent treatment runs.
To determine the extent of this interference, a pilot plant
study program was established to investigate the performance of
the activated alumina fluoride removal process on a water supply
that contained excessive levels of both fluoride and arsenic.
Through the cooperation of the Arizona Department of Health
Services, a community that met the water criteria was located,
and planning was initiated. The Why Utility Corporation at Why,
Arizona, has a water supply with a history of excessive levels
of high fluoride (2.4 to 3.3 mg/L) and arsenic (0.10 to 0.17
mg/L). Complete water analyses are included in Appendix C. On
April 4, 1978, the Why Utility Corporation granted permission to
perform the desired pilot test program. This report covers
Phases I and II of the test program. Phase I included three
treatment runs and regenerations for a single-stage treatment
system. Phase II included three treatment runs and separate re-
generations of each stage of a two-stage treatment system.
During the course of the pilot test work in this report, the
fluoride level was approximately 3.0 mg/L (maximum allowable is
1.4 mg/L for this climate), and the arsenic level was approxi-
mately 0.15 mg/L.
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SECTION 2
CONCLUSIONS
Phase I of the pilot plant program demonstrated that high
arsenic (0.14 ppm) in combination with high fluoride (3 ppm) in
a single potable water supply degrades the efficiency of the
activated alumina for fluoride removal. The amount of fluoride
being adsorbed by the activated alumina after two regenerations
in the pilot plant was one-half to two-thirds the values that
have been observed in operating fluoride plants and previous
fluoride removal pilot studies. These experiments also demon-
strated that using a 1% sodium hydroxide solution for the
regeneration fluid left approximately 25% of the adsorbed
fluoride and 70% of the adsorbed arsenic on the activated
alumina. A 4% sodium hydroxide solution, however, removed quan-
tities of fluoride and arsenic almost equivalent to that which
had been adsorbed on the previous treatment run.
In Phase II of the pilot study, a two-stage treatment proc-
ess was tested. These experiments demonstrated that for the
particular potable water concentrations being tested, arsenic
continues to be adsorbed on the activated alumina after the
fluoride capacity is reached. Thus arsenic is preferentially
adsorbed on activated alumina. The fluoride removal capacity of
the first column was approximately 4,300 g/m3, or a third higher
than that shown in the Phase I study, because in the Phase II
study, the first column did continue to adsorb flouride after
fluoride breakthrough. The fluoride removal capacity of the
second column was approximately 3,300 g/m3, which was lower than
expected. The use of a 4% sodium hydroxide regeneration solution
in column one and a 1% solution in column two resulted in ac-
ceptable alumina regenerations. A much longer pilot study beyond
the scope of this project would be necessary to optimize proc-
essing variables.
No attempt was made in these studies to purposely alter the
fluoride or arsenic concentrations or oxidation states. There-
fore, no conclusions can be drawn from these data on the capa-
city of activated alumina for arsenic removal or of the effect
that a change in the relative concentrations of the two contam-
inants might have on the activated aluminas useful adsorptive
capacity. However, these pilot studies do demonstrate the
feasibility of removing both arsenic and fluoride from a potable
water system with activated alumina.
-------
Analysis of the 4% sodium hydroxide regeneration solution
indicates that a significantly higher percentage of the acti-
vated alumina is solubilized by this strength caustic. The
authors estimate that an annual 10% replacement of activated
alumina would be necessary in the proposed two-tower system,
compared with 3% replacement experienced in fluoride removal
plants that use 1% caustic regeneration solutions.
Limited analyses of water samples for arsenic oxidation
states show that the test water contained 90% As+5-10% As+3,
and that more than 97% of the As"1"5 and 60% of the As+3 was being
removed by the activated alumina column.
The estimated operating costs of systems treating water
for small towns (1,000 to 10,000 persons) varies from 4£ to
5.5C/kL (15* to 21<=/1,000 gal). These costs are approximately
30% higher than those experienced in plants removing fluoride
only. Estimated capital equipment costs for these same systems
varies from $200,000 to $800,000.
-------
SECTION 3
DESCRIPTION OF TEST SITE AND APPARATUS
Why, Arizona, is a small community located 213 km west of
Tucson, Arizona. The terrain is desert with rugged mountains.
The climate is hot and arid. The community is unincorporated.
Except for copper mining at Ajo, Arizona, 17 km away, there are
no major industries. The population includes approximately
100 permanent residents, which can expand to 1,000 persons during
vacation seasons.
The Why Utility Corporation provides the water supply for
the community. There are 75 meter connections on the system.
One deep well provides the entire water supply. This well is
equipped with a pump that delivers water at the rate of 3.8 L/s
to an interim storage tank at the well site.
A distribution pump delivers water to a pressurization tank
on a hill from which the water is distributed. The annual con-
sumption for the community is 24,000 kL. The average daily con-
sumption is 66 kL; maximum daily consumption is 95 kL.
Raw water used for testing was taken from the interim stor-
age tank. The raw water was metered (flow rate and total flow)
by a calibrated flow totalizer and then run through the treat-
ment system. By means of plastic valves and hoses, the; raw water
was directed either downflow through the system for treatment and
rinse, or upflow through the test column(s) for backwash and
rinse (see Figures 1, 2, and 3). The test columns are 25-cm dia-
meter, schedule 40 PVC by 1.5 m high, supported on a wood frame.
The inside cross sectional area is 0.05 m2. The treatment beds
contained in the test columns were 0.56 m deep or 0.028 m
(1 ft3) in volume of Alcoa F-l grade (0.30 to 0.59 mm or 28 to
48 mesh) activated alumina. The activated alumina weight was
24 kg per bed. An acid feed system (consisting of batch tank,
chemical pumps, chemical tubing and injection check valves) in-
jected dilute sulfuric acid solution into the raw water for pH
adjustment. In Phases I and II, the acid was injected prior to
entry to the treatment column. In Phase II acid was also in-
jected between stages during the post regeneration neutralization
step.
After completion of a treatment run, each treatment bed was
regenerated. The raw water supply was shut off and disconnected
-------
Raw Meter
Water
O
Pump
Dilute
H2 S04
1
Sample
Raw Water
Test Column
Sample
Treated Water
Treated
Water
Treatment & Downflow
Vent
Raw
Meter
Water
Pump
(_ IW t
i r*1-
Te
Test Column
Sample
Dilute
H2 SO 4
Backwash & Upflow Rinse Schematic
Figure 1. Process schematic flow diagrams
To Waste
- Phase I,
-------
Pump
Dilute
Caustic
Vent
T<
Test Column
To Waste
Upflow Regeneration
Pump
Dilute
Caustic
w-H* Vent
Test Column
*H-K!-
Downflow Regeneration
To Waste
Figure 2. Regeneration process schematic
flow diagrams - Phase I,
-------
Met
+ (
* l.No.l
4-
I ^
W W*
ole
fxts
d
Col. No. 2
en i ^
J 1
i
Raw
Water
Sample
( 1
^H&WttfS Qatn^l o
v3CUU£JXe
Automatic Sampler '
^
Note: Treatment schematic for Phase II is as follows:
(1) Downflow rinse schematic same as Phase I (see Figure 1)
(2) Backwash & upflow rinse schematic same as Phase I
(see Figure 1).
(3) Upflow regeneration schematic same as Phase I
(see Figure 2).
(4) Downflow regeneration schematic same as Phase I
(see Figure 2).
Figure 3. Process schematic flow diagrams - Phase II.
-------
and a separate dilute caustic soda feed system was connected to
the treatment column being regenerated. 'This system (similar to
the acid feed system) consisted of a batch tank, chemical pump,
and chemical tubing. Regeneration wastewater was collected in
55-gallon drums in which contaminant levels were measured.
Toxic wastes were transported to a lined waste evaporation pond.
The pilot test equipment was mounted in a mobile trailer
which was set at the well site. This trailer also housed a
mobile water testing laboratory which was primarily set up for
analysis of fluoride (SPADNS), arsenic (Silver DDC) and pH.
During the test program duplicate samples were collected and
mailed to both the Alcoa Laboratories in Pittsburgh, Pennsyl-
vania and the EPA Laboratory in Cincinnati, Ohio.
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SECTION 4
EXPERIMENTAL RESULTS
Data for the test program are tabulated in Appendix A for
Phase I and Appendix B for Phase II of this report.
During Phase I the treatment column was used for three ad-
sorption cycles and caustic regenerations. The treatment flow
rate was maintained at approximately 5.7 L/m throughout each
treatment run. Each run was continuous until fluoride break-
through. Fluoride breakthrough was defined as the point where
the fluoride concentration exceeded an individual sample analy-
sis of 2.4 mg/L or the point at which the average concentration
of treated water through the column exceeded 1.1 mg/L fluoride.
A summary of the experimental results is given in Table 1.
From this table it can be seen that in each treatment run there
was a deterioration in the activated alumina's capacity for
fluoride removal. There was no evidence of arsenic saturation
in the treatment bed during any of the runs.
The first treatment run showed an acceptable fluoride capa-
city of over 4,600 g/m3 (2,000 grains/ft3). Arsenic loading on
the bed at that point was 340 g/m3 (149 grains/ft3). The 0.028
m3 of activated alumina treated 64 kL (17,000 gal) of water.
The first regeneration was conducted as if it were a fluoride
removal plant with a 1% caustic solution. Both fluoride and ar-
senic recovery were inadequate in that only 71% of the fluoride
and 41% of the arsenic was removed. During the second treatment
run the new amount of fluoride retained on the activated alumina
bed was approximately 27% lower than in the first run but the
total amount of fluoride retained has approximately the same.
The arsenic concentration on the bed increased to 480 g/m3.
The second regeneration employed 33% more of the 1% NaOH regen-
erative solution than in the first regeneration. Eighty-three
percent of the retained fluoride was removed in this regenera-
tion, but only 32% of the retained arsenic was removed. On the
third treatment run the new fluoride retained was 35% lower than
the first treatment. The arsenic retained had increased to
580 g/m3. The regeneration procedure was modified for the third
regeneration to employ a sodium hydroxide concentration of 4%.
This treatment effected a 92% removal of the total retained
fluoride and 44% removal of the total retained arsenic.
10
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TABLE 1. PHASE I PILOT PLANT FLUORIDE AND ARSENIC REMOVAL SIM/IARY
Mode
Treatment
Run No. 1
Regenera-
tion No. 1
Treatment
Run No. 2
Regenera-
tion No. 2
Treatment
Run No. 3
Regenera-
tion No. 3
Total
Fluoride
added to
treatment
bed*
(g/m3)
4,652
—
3,378
—
3,014
—
-
Fluoride
retrieved
from
treatment
bed
(g/m3)
-
3,300
—
3,938
-
3,506
-
Fluoride
retained
in
treatment Arsenic
bed added
(g/m3) (g/m3)
4,652 340
1,352
4,730 275
792
3,806 247
300
300
Arsenic Arsenic Treated
removed retained water
(g/m3) (g/m3) (kL)
340 64.2
140 200
485 51.9
153 332
579 46.5
256 323
323 162.6
Waste- %
water Waste-
(kL) water
-
1.8 2.8
-
1.4 2.8
-
1.4 3.0
4.6 2.8
*rr/m3
:g/m3 x 0.437 - grains/ft3.
-------
These three sorption and regeneration runs confirmed the
decrease in fluoride capacity and difficulty of removing arsenic
from the activated alumina which had been observed in the earlier
pilot plant runs. In an effort to improve treatment efficiency
and eventual operating cost economics, the decision was made to
extend the test program into a second phase.
In Phase II the test apparatus was modified to provide two
treatment beds in series (Figure 3). Each column was charged
with 0.028 m3 of fresh activated alumina. The data collected in
the unreported pilot plant run on high arsenic water had shown
that arsenic was preferentially adsorbed by the activated alumina
and that the bed would continue to remove arsenic even after it
was saturated with fluoride. Thus in a two-column system, the
first stage is designated as a sacrificial bed which is pro-
vided primarily for the removal of arsenic. The second stage
is employed primarily for the removal of fluoride.
During the course of the Phase II experimental runs,
samples were taken between columns as a means of checking to
make sure that only a negligible amount of arsenic was in the
first column effluent prior to fluoride saturation of the second
stage. The treatment flow rate was maintained between 4.7 and
5.7 L/m throughout each treatment run. Each run was continuous
until second stage fluoride breakthrough dictated completion of
the run.
During the Phase II experiments.l runs, small process up-
sets occurred in treatment runs No. 1 and 2. These upsets are
noted in the tabulated data in Appendix B. While these upsets
may have affected the absolute numbers determined in these two
experimental runs, the authors do not believe that they infringe
in any way on the final report conclusions.
Experimental data for Phase II runs are summarized in
Table 2. A plot of the experimental data from the number three
treatment run is shown in Figure 4. These data confirm that the
first column preferentially adsorbed arsenic with the result
that during the majority of each of the three runs the arsenic
concentration leaving the first column was less than 5 ppb (the
detection limit of our analytical method) and in no case did it
exceed 11 ppb at the end of a run. The run was terminated as in
Phase I study when fluoride concentration in the effluent from
the second column exceeded 1.1 mg/L average concentration for
all treated water or 2.4 mg/L for an individual sample. The
average treated water analyses in these three runs was approxi-
mately 0.7 mg/L.
The scope of work for Phase II of this project included
three treatment regeneration cycles. The data obtained demon-
strate the technical feasibility of the two column system which
12
-------
TABLE 21 PHASE II PILOT PLANT FLUORIDE AMD ARSENIC REMOVAL SUMMARY
Mode
Treat-
ment
No. 1
Regen.
No. 1
Treat-
ment
w No. 2
Regen.
No. 2
Treat-
ment
No. 3
Regen.
No. 3
Total
F F
added removed
to from
Col. Col.
No.l No.l
(g/m3) (g/n3)
6080 -
5576
4357
4298
4333 -
4577
-
F
retained
in
Col.
No.l
(g/m3)
6080
504
4861
563
4896
319
319
As
added
to
Col.
No.l
(gAi3)
593
-
476
-
491
-
-
As
removed
from
Col.
No.l
(g/m3)
346
.
360
.
374
-
As
retained
in
Col.
No.l
(g/m3)
593
249
723
363
854
480
480
F
added
to
Col.
No. 2
(g/m3)
5293
-
3527
-
3379
-
F
removed
from
Col.
No. 2
(g/m3)
3577
.
3108
.
3259
-
F
retained
in
Col.
No. 2
(g/%3)
5293
1716
5243
2135
5514
2255
2255
66°B'
Treated Waste- % H2S04
water water Waste used
(k/L) (k/L) (L)
120.6 - - 6.5
2.0 1.7
100.2 - - 5.0
2.3 2.3
102.5 - - 5.0
2.0 2.0
322.8 * 6.3 2.0 16. Ot
*18 L 50% NaOH @ 20C/L = $3.60
Therefore caustic cost was 1.12C/kL treated water.
t!6 L 660B'H2SOi, @ 6.6C/L = $1.06
Therefore acid cost was 0.33%/kL treated water.
-------
As Concentration mg/L
As Concentration mg/L
H-
00
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PJ P> h->
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9
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P> rt
fd, H-
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I—^ * *
P) Ui
O
b
o
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O
b
o
N)
F Concentration mg/L
o -* ro
T
T
I
Concentration mg/L
-* IO CO
B)
»p»
O
o
O
CO
o
cn
O
CT)
O
I3
= 00
ro
o
o
cn
PH
o>
cn
PH
-------
was the purpose of this phase of the project. Further experi-
mental work to determine the number 'of cycles the first column
can be effective in removing As is desirable; however, the time
and expense would far exceed the limits of this project. The
investigation into the lower than expected F removal capacity of
column two is also desirable, but again beyond the limits of
this project. Cost projections appearing later in this report
are based upon the limited data obtained.
Data on the losses of alumina with each Phase II regen-
eration were measured and are shown in Table 3.
TABLE 3. DATA ON THE DISSOLUTION OF
ALUMINA DURING REGENERATION
Regeneration
Column
Wt % of total bed
in solution
1 1
2
2 1
2
3 1
2
2.9
1.2
1.9
0.5
1.5
0.6
The above data show alarmingly high values of alumina being re-
moved from the activated alumina bed. However, a decreasing
trend is evident with each regeneration. It is known that early
regenerations of fresh activated alumina do remove unusually
high amounts of material because the individual alumina parti-
cles have attached pieces which become displaced by attrition.
Plant experience with regenerations similar to second column
regenerations with 1% caustic has resulted in the need for
approximately 3% bed replacement per year. Based on the facts
in Table 3 and plant experience, it is the authors' estimate
that an overall bed replacement of 10% for the two columns
should be anticipated with the majority of that alumina being
needed in the first column.
During the course of Phase II experiments, a limited num-
ber of samples were sent to the chemistry department at the
University of Arizona for analysis of the arsenic oxidation
stages present in raw water, treated water, and regeneration
solutions. The results are summarized in Table 4 below.
15
-------
TABLE 4. ARSENIC OXIDATION STATES
Sample % Distribution
Raw water
Treated water
Regenerated solution
_ +3
As
10
60
5
As+5
90
40
95
The articles in the literature5'6'7 which discuss the oxi-
dation states of arsenic in water systems conclude that well
water samples would be expected to have the majority of the
arsenic present as As+3. Table 4 indicates that this partic-
ular water is just the opposite with 90% of the arsenic present
as As+5. The authors cannot verify that As"1"5 is or is not the
typical form of arsenic present in Arizona wells contaminated
with arsenic. The article by Gupta and Chen8 indicates that
activated alumina should be much more effective in removal of
As+5 than As+3. The effluent samples listed in Table 4 were
taken near the end of treatment runs when the arsenic level was
around 9 ppb. The data showing 60% As+3 and 40% As+5 do confirm
that As"1"5 form is being removed to a much higher degree than the
As+3 form. If it is assumed that none of the As+3 is oxidized
to As"1"5 in the course of pH adjustment and movement through the
activated alumina bed, at the end of the run when the samples
were taken, at least 60% of the As+3 is being removed by the
activated alumina and 97% of the As+s. The above data would
also say that during the course of a treatment run when the
effluent values from the first column were <^ 5 ppb As that more
than 70% of the As+3 was being removed (assuming that all efflu-
ent As was in the form of As+ ) . The regeneration solution
results are interesting in that the form of arsenic present in
these solutions is greater than 95% +5. Using the raw water
and effluent analyses, the calculated value expected in the
regeneration solution would be a 7% to 93% split between As+3
and As"1"5. One could conclude that this difference between cal-
culated and measured values is (a) not pignificant because of
the accuracy of the analytical techniques, (b) due to a trans-
formation of As+3 to As+ by the combination of treatment and
regeneration procedures, and (c) the caustic regeneration is not
effective in removing As4"3 from the activated alumina. A longer
experimental program with field-mounted analytical capability
would be necessary before there can be confidence in any of the
above conclusions.
16
-------
SECTION 5
COST ESTIMATES
Operating and capital cost estimates are based on Phase II
pilot plant data. Cost estimates have been developed for this
report using the following design criteria:
1) Maximum consumption 1.1 kL (300 gal) per day per person
2) Average consumption 640 L (170 gal) per day per person
3) Average fluoride - raw water - 3.0 mg/L
4) Average fluoride - treated water - 1.0 mg/L
5) Minimum fluoride capacity for activated alumina -
2300 g/m3 (1,000 grains/ft3)
6) Activated alumina replacement rate - 10%/year
7) Wastewater pond evaporation rate - 1.8 m/year
8) 50% NaOH delivered cost - 20C/L
9) 66° B'HaSOi* delivered cost - 6.6C/L
10) Electric utility rate - 5«/kWh
11) Plant operating labor rate - $6/hr
A typical plant layout is illustrated on Figure 5. Pre-
liminary operating and capital costs for small systems are tab-
ulated in Tables 5 and 6. The operating costs of 4.0 to 5.5*/kL
are approximately 30% higher for removal of the combined fluo-
ride and arsenic than for fluoride removal only. The capital
costs are approximately the same. As pointed out in the design
criteria, cost estimates assume that the wastewater from the
media regeneration will be contained in an evaporation pond.
17
-------
o
o
O:
Figure 5. Typical fluoride and arsenic removal plant plan.
18
-------
TABLE 5. PRELIMINARY OPERATING COST ESTIMATES FOR SMALL SYSTEMS*
10
Item
Acid
Caustic soda
Operation labor
Electric utility
.Media replacement
Spare parts & misc.
Total
-------
REFERENCES
1. Environmental Protection agency National Interim Primary
Drinking Water Regulations, dated December 24, 1975.
2. Rubel, F. and Woosley, R. D., Removal of Excess Fluoride
from Drinking Water, Technical Report-EPA 570/9-78-001,
January, 1978.
3. Rubel, F. and Woosley, R. D., The Removal of Excess
Fluoride from Drinking Water by Activated Alumina,
Journal AWWA, Volume 71, No. 1, January, 1979, 45-49.
4. Bellack, Ervin, Arsenic Removal from Potable Water,
Journal AWWA, Volume 63, No. 7, July, 1971, 454-458.
5. Sergeyeva, E. I. and Khadakovskiy, I. L., Physicochemical
Conditions of Formation of Native Arsenic in Hydrothermal
Deposits, Geochemistry International (Geokhimiga 7),
846-859. •
6. Wageman, R., Some Theoretical Aspects of Stability and
Solubility of Inorganic Arsenic in the Freshwater Environ-
ment, Water Research, Volume 12, 139-145.
7. Ferguson, J. F., and Gavis, J., A Review of the Arsenic
Cycle in Natural Waters, Water Research, Volume 6,
1259-1274.
8. Gupta, S. K., and Chen, K. Y., Arsenic Removal by Ad-
sorption, Journal WPCF, March, 1978, 493-506.
20
-------
APPENDIX A. FLUORIDE/ARSENIC REMOVAL PROJECT - PHASE I
TABLE A-l. TREATMENT RUN NO. 1
Date
6/13
6/13
6/14
6/14
6/14
6/15
6/15
6/15
6/16
6/16
6/16
6/16
6/17
6/17
6/17'
6/18
6/18
6/19
6/19
6/20
6/21
6/21
6/22
Time
1530
2000
0400
1100
2000
0600
1100
1700
0200
0900
1600
2100
0700
1245
1915
0300
2100
0700
1300
2000
1000
1830
0800
A
Flow
(kL)
_
1.5
2.8
2.1
3.1
1.8
1.5
2.9
3.0
2.5
2.8
1.8
3.8
2.4
2.6
3.1
2.5
3.7
2.6
3.2
5.2
3.7
5.5
Total
flow
(XL)
_
1.5
4.3
6.4
9.5
11.3
12.8
15.7
18.7
21.3
24.1
25.9
29.7
32.1
34.7
37.8
40.3
44.0
46.6
49.8
55.0
58.7
64.2
Adjusted
raw
water
(pH)
5.6
5.7
5.6
5.6
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
Treated
water
(pH)
7.6
7.3
6.5
5.8
5.6
5.5
5.6
5.6
5.6
5.6
5.5
5.4
5.4
5.5
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
Raw
water
F
(mg/L)
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
Treated
water
F
(mg/L)
0.9
0.3
0.2
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
0.4
0.5
0.7
0.9
1.1
1.3
1.5
1.6
1.9
2.2
2.4
F
removed
in
increment
(g)
3.5
7.5
5.7
8.8
5.0
4.3
8.0
8.5
7.1
7.9
4.8
10.0
6.0
6.0
6.4
4.8
6.3
3.9
4.2
6.0
3.1
3.3
Total
F
removed
(g)
3.5
11.0
16.7
25.5
30.5
34.8
42.8
51.3
58.4
66.3
71.1
81.1
87.1
93.1
99.5
104.3
110.6
114.5
118.7
124.7
127.8
131.1
Raw
water
As
(mg/L)
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
Treated
water
As
(mg/L)
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
As
removed
in
increment
(g)
0.23
0.42
0.32
0.47
0.26
0.23
0.43
0.45
0.38
0.42
0.26
0.58
0.37
0.39
0.46
0.38
0.56
0.40
0.46
0.78
0.55
0.83
Total
As
removed
(g)
-
0.23
0.65
0.97
1.44
1.70
1.93
2.37
2.82
3.20
3.62
3.88
4.46
4.83
5.22
5.68
6.06
6.62
7.02
7.48
8.26
8.81
9.64
-------
M
TABLE A-2. REGENERATION NO. 1:
DOUBLE REGENERATION PROCEDURE EMPLOYING 1% SODIUM HYDROXIDE, JUNE 22, 1978
Step
Backwash
Up flow
regeneration
Upflow rinse
Upflow rinse
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low rinse
Flow
rate
(L/m)
18.9
1.9
5.7
5.7
5.7
5.7
1.9
1.5
Time
(min)
16
36
25
36
36
36
36
98
Flow
(L)
302
68
140
208
208
208
68
140
55-gal
Waste
drum
no.
1
1
2
3
4
5
5
Fluoride
mg/L
N.A.
310
310
80
20
6
25
25
g/drum
N.A.
64.6
64.6
16.8
4.1
1.2
5.2
5.2
Arsenic
mg/L
N.A.
9.2
9.2
4.4
0.4
-
4.7
4.7
g/drum Remarks
N.A. Some
turbidity
1.94
1.94
0.84
0.07
-
0.97
0.97
Downflow
neutralization
Downflow
neutralization
Total
5.7
5.7
36
36
208
208
1,760
5 1.0
2.5 0.5
93.4
0.7
0.13
Rinse water
pH - 2.5
Rinse water
pH - 2.5
3.95
-------
TABLE A-3. TREATMENT RUN NO. 2
Date
6/26
6/26
6/26
6/27
6/27
6/27
6/28
to 6/28
U)
6/28
6/29
6/29
6/29
6/30
6/30
6/30
' 7/1
7/1
7/2
7/2
7/3
Time
1830
2100
2300
0700
1440
2045
0600
1130
2045
0600
1115
2215
0700
1130
2030
0620
1330
0900
2030
0700
A
Flow
(kL)
_
0.9
0.6
2.9
2.2
2.4
3.3
1.8
3.3
3.4
1.5
3.7
2.9
1.5
3.0
3.2
2.3
6.1
3.7
3.3
Total
flow
(kL)
_
0.9
1.5
4.4
6.6
9.0
12.3
14.1
17.4
20.8
22.3
26.0
28.9
30.4
33.4
36.6
38.9
45.0
48.7
52.0
Adjusted
raw
water
(pH)
2.5
2.5
4.0
5.5
5.5
5.5
5.6
5.5
5.6
5.5
5.6
5.5
5.5
5.5
5.6
5.5
5.5
5.5
5.6
5.5
Treated
water
(pH)
10.9
9.9
9.0
6.4
5.9
5.8
5.7
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.6
5.5
Raw
water
F
(mg/L)
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
Treated
water
F
(mg/L)
1.2
0.4
0.3
<0.1
<0 . 1
<0 . 1
<0 . 1
<0 . 1
0.2
0.6
0.7
0.9
1.1
1.3
1.5
1.7
1.9
2.1
2.3
2.4
F
removed
in
increment
(g)
_
1.9
1.5
7.7
6.3
6.8
9.1
5.1
9.1
8.6
3.3
7.7
5.5
2.6
4.5
4.2
2.5
4.9
2.5
1.8
Total
F
removed
(g)
_
1.9
3.4
11.1
17.4
24.2
33.3
38.4
47.5
56.1
59.4
67.1
72.6
75.2
79.7
83.9
86.4
91.3
93.8
95.6
Raw
water
As
(mg/L)
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
As
Treated removed
water in
As increment
(mg/L) (g)
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
-
0.14
0.09
0.42
0.34
0.36
0.49
0.27
0.50
0.52
0.21
0.56
0.44
0.23
0.45
0.48
0.34
0.93"
0.54
0.49
Total
As
removed
(g)
0.14
0.23
0.65
0.99
1.35
1.84
2.11
2.61
3.13
3.34
3.90
4.34
4.57
5.02
5.50
5.84
6.77
7.31
7.80
-------
to
TABLE A-4. REGENERATION NO. 2:
DOUBLE REGENERATION PROCEDURE EMPLOYING 1% SODIUM HYDROXIDE, JULY 4, 1978
Step
Backwash
Up flow
regeneration
Upflow rinse
Upflow rinse
Upflow rinse
Upflow rinse
Flow
rate
(L/m)
22.7
2.8
5.7
5.7
5.7
5.7
Time
(min)
15
32
20
36
36
10
Flow
(L)
341
91
117
208
208
57
55-gal
Waste
drum
no.
1
1
2
3
4
Fluoride
mg/L
N.A.
390
390
75
17
4
g/drum
N.A.
81.3
81.3
15.6
3.6
0.2
Arsenic
mg/L
N.A.
9.7
9.7
4.8
0.7
_
g/drum
N.A.
2.01
2.01
0.97
0.13
_
Remarks
Some
turbidity
Downflow
regeneration 2.8 32 91
Downflow
neutralization 5.7 20 117
Downflow
neutralization 5.7 36 208
40
8.3
5.6 1.17
40 8.3 5.6 1.17 Rinse water
pH - 2.5
12 2.5 0.4 0.06 Rinse water
pH - 2.5
Total
1,438
111.5
4.34
-------
TABLE A-5. TREATMENT RUN NO. 3
Date
7/4
7/4
7/4
7/5
7/5
7/5
8 7/6
7/6
7/6
7/7
7/7
7/7
7/8
7/8
7/9
7/9
7/10
Time
1330
1600
2115
0600
1500
2030
0600
1100
2030
0630
1130
2115
0615
1530
0915
2000
0530
A
Flow
(kL)
_
0.8
1.8
2.9
2.8
1.7
3.2
1.6
3.3
3.6
2.3
2.8
3.3
3.3
6.0
3.1
4.0
Total
flow
(kL)
_
0.8
2.6
5.5
8.3
10.0
13.2
14.8
18.1
21.7
24.0
26.8
30.1
33.4
39.4
42.5
46.5
Adjusted
raw
water
(pH)
2.5
4.0
5.6
5.5
5.6
5.6
5.6
5.6
5.6
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
Treated
water
(pH)
10.2
9.0
7.0
5.8
5.6
5.6
5.6
5.6
5.6
5.6
5.5
5.5
5.5
5.5
5.5
5.5
5.5
Raw
water
F
(mg/L)
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
2.9
Treated
water
F
(mg/L)
1.1
0.7
0.2
<0.1
<0.1
<0.1
<0.1
0.1
0.4
0.7
1.0
1.3
1.6
1.9
2.1
2.2
2.4
F
removed
in
increment
(g)
_
1.6
4.6
7.9
7.9
4.6
9.0
4.7
8.6
8.6
4.1
5.1
4.6
3.9
5.4
2.3
2.4
Total
F
removed
(g)
_
1.6
6.2
14.1
22.0
26.6
35.6
40.3
48.9
57.5
61.6
66.7
71.3
75.2
80.6
82.9
85.3
Raw
water
As
(mg/L)
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
Treated
water
As
(mg/L)
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
As
removed
in
increment
(g)
-
0.12
0.27
0.43
0.42
0.26
0.48
0.36
0.38
0.45
0.33
0.44
0.48
0.51
0.89
0.47
0.60.
Total
As
removed
(g)
-
0.12
0.39 .
0.82
1.24
1.50
1.98
2.34
2.72
3.27
3.60
4.04
4.52
5.03
5.92
6.39
6.99
-------
NJ
TABLE A-6. REGENERATION NO. 3:
DOUBLE REGENERATION PROCEDURE EMPLOYING 4% SODIUM HYDROXIDE, JULY 22, 1978
Step
Backwash
Up flow
regeneration
Upflow rinse
Upflow rinse
Upflow rinse
Flow
rate
(L/m)
26.5
2.8
3.8
3.8
3.8
Time
(min)
15
32
31
55
55
Flow
(L)
397
91
117
208
208
55-gal
Waste
drum
no.
1
1
2
3
Fluoride
mg/L
N.A.
410
410
15
6.9
g/drum
N.A.
85.4
85.4
3.1
1.4
Arsenic
mg/L
N.A.
25.8
25.8
1.1
0.67
g/drum
N.A.
5.38
5.38
0.19
0.13
Remarks
High
turbidity
Downflow
regeneration 2.8 32 91
Downflow
neutralization 5.7 20 117
Downflow
neutralization 5.7 36 208
41
41
8.6
7.2
1.49
8.6 7.2 1.49 Rinse water
pH - 2.0
3.9 0.8
0.34 0.07
Rinse water
pH - 2.0
Total
1,437
99.3
7.26
-------
APPENDIX B. FLUORIDE/ARSENIC REMOVAL PROJECT - PHASE II
TABLE B-l. TREATMENT RON NO. 1 - COLUMN NO. 1
Date
1/22
1/23
1/24
1/25
1/26
1/27
1/28
1/29
1/30
1/31
2/4
2/5
2/6
2/7
2.8
2/9'
2/10
2/11
A
Flow
(kL)
6.8
8.3
8.5
7.7
6.9
6.7
6.3
5.9
7.5
2.8
4.3
7.4
7.4
7.4
7.4
7.5
7.4
4.6
Total
flow
(kL)
6.8
15.1
23.6
31.3
38.2
44.9
51.2
57.1*
64.6
67.4*
71.7
79.1
86.5
93.9
101.3
108.8
116.2
120.6
Adjusted
raw
water
(pH)
5.5
5.4
5.4
5.3
5.5
5.4
5.2
4.8
5.5
3.1
5.3
5.3
5.4
5.2
5.2
5.5
5.5
5.4
Effluent
(pH)
6.0
5.5
5.4
5.3
5.3
5.4
5.4
5.2
5.3
5.0
5.3
5.3
5.4
5.2
5.3
5.4
5.5
5.5
Raw
water
F
(mg/L)
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.1
3.1
3.1
3.1
3.1
3.1
3.1
3.1
Effluent
F
(mg/L)
<0.1
<0.1
0.1
0.4
1.7
1.4
2.1
3.0
1.7
6.9
2.7
1.8
2.7
2.9
2.3
2.4
2.3
3.0
F
removed
in
increment
(g)
21.8
25.1
26.4
22.7
14.8
11.1
9.1
3.8
6.4
(3.1)
1.7
6.3
6.3
2.2
3.7
5.6
5.6
2,1
Total F
removed
(g)
21.8
47.5
73.9
96.6
111.4
122.5
131.6
135.4
141.8
138.7
140.4
146.7
153.0
155.2
158.9
164.5
170.1
172.2
Raw
water
As
(mg/L)
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
.0.140
0.140
Treated
water
As
(mg/L)
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
.005
.006
As
removed
in
increment
(g)
1.0
1.1
1=2
l.l
1.0
0.9
0.9
0.8
1.1
0.4
0.5
1.1
1.0
1.1
1.0
1.0
1.1
0.'5
As
removed
(g)
1.0
2.1
3.3
4.4
5.4
6.3
7.2
8.0
9.1
9.5
10.0
11.1
12.1
13.2
14.2
15.2
16.3
16.8
"Filters plugged, flow rate reduced, process upset.
-------
TABLE B-2. TREATMENT RUN NO. 1 - COLUMN NO. 2
to
00
Date
1/22
1/23
1/24
1/25
1/26
1/27
1/28
1/29
1/30
1/31
2/4
2/5
2/6
2/7
2/8
2/9
2/10
2/11
A
Flow
(L)
6.3
8.3
8.5
7.7
6.9
6.7
6.3
5.9
7.5
2.8
4.3
7.4
7.4
7.4
7.4
7.5
7.4
7.6
Total
flow
(L)
6.8
15.1
23.6
31.3
38.2
44.9
51.2
57.1*
64.6
67.4*
71.7
79.1
86.5
93.9
101.3
108.8
116.2
120.6
Influent
(pH)
6.0
5.5
5.4
5.3
5.3
5.4
5.4
5.2
5.3
5.0
5.3
5.3
5.4
5.2
5.3
5.4
5.5
5.5
Effluent
(pH)
7.6
5.9
5.5
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
5.4
Influent
F
(mg/L)
<0.1
<0.1
0.1
0.4
1.7
1.4
2.1
3.0
1.7
6.9
2.7
1.8
2.7
2.9
2.3
2.4
2.3
3.0
Treated
water
F
(mg/L)
0.3
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
0.6
0.8
1.0
0.9
1.2
1.2
1.6
1.8
2.4
F removed
increment
(g)
_
-
-
1.9
7.2
10.7
11.0
15.0
16.5
10.9
17.6
10.0
9.6
13.0
10.4
7.1
4.8
4.2
Total F
removed
(g)
-
-
1.9
9.1
19.8
30.8
45.8
62.3
73.2
90.8
100.8
110.4
123.4
133.8
140.9
145.7
149.9
*Filters plugged, flow rate reduced, process upset.
-------
TABLE B-3. REGENERATION NO. 1:
DOUBLE REGENERATION PROCEDURE, MARCH 2,
1979
to
VD
Column
No.
1
1
1
1
1
1
Subtotal
2
2
2
2
2
,2
Subtotal
Total
Step
Backwash
Up flow
regeneration
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 1
Backwash
Upflow
regeneration
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 2
NaOH
(%)
N.A.
4
N.A.
N.A.
1
N.A.
-
N.A.
1
N.A.
N.A.
1
N.A.
-
-
FlOW
rate
(L/min)
26.5
2.8
5.7
5.7
2.8
5.7
-
26.5
2.8
5.7
5.7
2.8
5.7
-
-
Time
(min)
15
32
21
37
32
21
-
15
32
21
37
32
21
-
-
Flow
(L)
397
91
117
208
91
117
1,021
397
91-
117
208
91
117
1,021
2,042
55-gal
waste
drum
no.
N.A.
1
1
2
3
3
-
N.A.
1
1
2
3
3
-
-
Fluoride
mg/L
N.A.
727
727
17
14
14
-
N.A.
360
360
100
26
26
-
-
Drum
(g)
N.A.
151.5
151.5
3.5
2.9
2.9
157.9
N.A.
75.0
75.0
20.9
5.4
5.4
101.3
259.2
Arsenic
Drum
mg/L (g)
N.A. N.A.
41.1 8.6
41.1 8.6
2.5 0.5
3.5 0.7
3.5 0.7
9.8
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
-
9.8
-------
TABLE B-4. TREATMENT RUN NO. 2 - COLUMN NO. 1
Date
3/2
3/3
3/4
3/5
3/6
3/7
3/8
3/9
3/10
3/11
3/12
3/13
3/14
3/15
2/16
A
Flow
(kL)
0.5
5.7
7.9
7.8
7.9
6.0
6.8
6.9
7.1
7.6
7.1
7.5
7.3
7.0
7.1
Total
flow
(kL)
0.5
6.2
14.1
21.9
29.8
35.8
42.6
49.5
56.6
64.2
71.3
78.8
86.1
93.1
100.2
Adjusted
raw
water
(pH)
2.5
4.0
5.3
5.3
5.5
5<3
5.3
*7.2
5.3
5.3
5.3
5.3
5.4
5.4
5.4
Effluent
(pH)
10.8
5.6
5.5
5.3
5.5
5.3
5.3
6.5
5.4
5.3
5.3
5.3
5.3
5.3
5.3
Raw
water
F
(mg/L)
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
Effluent
F
(mg/L)
2.5
0.2
0.3
0.1
0.1
0.7
2.2
6.5
2.2
2.0
2.4
2.6
2.4
2.5
3.0
F
removed
in
increment
(g)
_
9.4
21.7
21.8
22.9
15.6
10.5
(3.5)
(0.7)
6.8
5.7
3.8
3.7
3.9
1.8
Total F
removed
(g)
9.4
31.1
52.8
75.8
91.4
101.9
98.4
97.7
104.5
110.2
114.0
117.7
121.6
123.4
Raw
water
As
(mg/L)
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
Treated
water
As
(mg/L)
<.005
<.005
<.005
<.005
<.005
<-005
<.005
<.005
.007
.007
.007
.007
.008
.010
.010
As
removed
in
increment
(g)
0.7
1.1
1.1
1.1
0.8
1.0
0.9
1.0
1.0
1.0
0.9
1.0
1.0
0.9
As
removed
(g)
0.7
1.8
2.9
4.0
4.8
5.8
6.7
7.7
8.7
9.7
10.6
11.6
12.6
13.5
*Acia pump suction tubing loosened, acid feed stopped, process upset.
-------
TABLE B-5. TREATMENT RUN NO. 2 - COLUMN NO. 2
Date
3/2
3/3
3/4
3/5
3/6
3/7
3/8
3/9
3/10
3/11
3/12
3/13
3/14
3/15
3/16
A
Flow
(L)
0.5
5.7
7.9
7.8
7.9
6.0
6.8
6.9
7.1
7.6
7.1
7.5
7.3
7.0
7.1
Total
Flow
(L)
0.5
6.2
14.1
21.9
29.8
35.8
42.6
49.5
56.6
64.2
71.3
78.8
86.1
93.1
100.2
Influent
(pH)
10.8
5.6
5.5
5.3
5.5
5.3
5.3
*6.5
5.4
5.3
5.3
5.3
5.3
5.3
5.3
Effluent
(pH)
—
8.8
5.6
5.4
5.4
5.4
5.3
6.3
5.7
5.4
5.4
5.4
5.3
5.3
5.3
Influent
F
(mg/L)
2.5
0.2
0.3
0.1
0.1
0.7
2.2
6.5
2.2
2.0
2.4
2.6
2.4
2.5
3.0
Treated
water
F
(mg/L)
1.1
0.1
<0.1
<0.1
<0.1
0.1
<0.1
0.1
0.5
1.1
1.3
1.8
2.1
2.1
2.5
F removed
increment
(g)
_
4.3
1.6
1.6
0.8
1.8
9.5
24.5
22.0
9.9
7.1
7.1
4.0
2.5
3.2
Total F
removed
(g)
_
4.3
5.9
7.5
8.3
10.1
19.6
44.1
66.1
76.0
83.1
90.2
94.2
96.7
99.9
*Acid pump suction tubing loosened, acid feed stopped, process upset.
-------
TABLE B-6. REGENERATION NO. 2:
DOUBLE REGENERATION PROCEDURE, MARCH 25, 1979
Column
No.
1
1
1
1
1
1
(jj T
NJ
Subtotal
2
2
2
2
2
2
Subtotal
Total
Step
Backwash
Upflow
regeneration
Upflow rinse
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 1
Backwash
Upflow
regeneration
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 2
NaOH
N.A.
4
N.A.
N.A.
N.A.
1
N.A.
-
N.A.
1
N.A.
N.A.
1
N.A.
-
-
Flow
rate
(L/min)
26.
2.
5.
5.
5.
2.
5.
-
26.
2.
5.
5.
2.
5.
-
-
5
8
7
7
7
8
7
5
8
7
7
8
7
Time Flow
(min) (L)
15
32
21
37
37
32
21
-
15
32
21
37
32
21
-
-
397
91
117
208
208
91
117
1,230
397
91
117
208
91
117
1,021
2,251
55-gal
waste
drum
no.
N.A.
1
1
2
3
4
4
-
N.A.
1
1
2
3
3
-
-
Fluoride
mg/L
N.A.
534
534
20
6
24
24
-
N.A.
314
314
58
50
50
-
-
Arsenic
Drum
(g) mg/L
N.A.
111.
111.
4.
1.
5.
5.
121.
N.A.
65.
65.
12.
10.
10.
88.
209.
N.A.
3 43.7
3 43.7
2 1.6
2 0.5
0 3.3
0 3.3
7
N.A.
5 N.A.
5 N.A.
1 N.A.
4 N.A.
4 N.A.
0
7
Drum
(g)
N.A.
9.2
9.2
0.3
0.1
0.6
0.6
10.2
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
-
10.2
-------
TABLE B-7. TREATMENT RUN NO. 3 - COLUMN NO. 1
Date
3/25
3/26
3/27
3/28
3/29
3/30
3/31
4/1
4/2
4/3
4/4
4/5
4/6
4/7
4/8
A
Flow
(XL)
1.3
6.5
7.3
7.1
7.6
7.6
7.2
7.6
7.2
7.6
7.7
6.9
7.1
7.0
6.8
Total
flow
(kL)
1.3
7.8
15.1
22.2
29.8
37.4
44.6
52.2
59.4
67.0
74.7
81.6
88.7
95.7
102.5
Adjusted
raw
water
(pH)
4.0
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.2
5.4
5.4
5.3
5.3
5.3
5.3
Raw
water
Effluent F
(pH) (mg/L)
8.6
5.4
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.4
5.3
5.3
5.3
5.3
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
Effluent
F
0.2
<0.1
<0. 1
<0.1
0.6
1.5
1.9
2.2
2.3
2.5
2.5
2.6
2.5
2.5
2.5
F
removed
in Total F
increment removed
(g) (g)
3.4
17.6
19.7
19.2
19.0
13.3
7.9
5.7
4.0
3.0
2.3
1.7
1.8
2.1
•2.0
3.4
21.0
40.7
59.9
78.9
92.2
100.1
105.8
109.8
112.8
115. 1
116.8
118.6
120.7
122.7
Raw Treated
water water
As As
(mg/L) (mg/L)
0.140
0.140 ,.
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
0.140
_
<.005
<.005
<.005
<.005
<.005
<.005
<.005
<.005
.007
.009
.010
.008
.009
.011
As
removed
in As
increment removed
(g) (g)
_
1.0
1.0
1.0
1.0
1.1
1.0
. 1.1
1.0
1.0
1.0
0.9
1.0
0.9
0.9
_
1.0
2.0
3.0
4.0
5.1
6.1
7.2
8.2
9.2
10.2
11.1
12.1
13.0
13.9
-------
TABLE B-8. TREATMENT RUN NO, 3 - COLUMN NO. 2
Date
3/25
3/26
3/27
3/28
3/29
3/30
3/31
4/1
4/2
4/3
4/4
4/5
4/6
4/7
4/8
A
Flow
(L)
1.3
6.5
7.3
7.1
7.6
7.6
7.2
7.6
7.2
7.6
7.6
6.9
7.1
7.0
6.8
Total
Flow
(L)
1.3
7.8
15.1
22.2
29.8
37.4
44.6
52.2
59.4
67.0
74.7
81.6
88.7
95.7
102.5
Influent
(pH)
5.5
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.4
5.3
5.3
5.3
5.3
Effluent
(pH)
5.5
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.4
5.4
5.3
5.3
5.3
Influent
F
(mg/L)
0.2
<0 . 1
<0 . 1
<0 . 1
0.6
1.5
1.9
2.2
2.3
2.5
2.5
2.6
2.5
2.5
2.5
Treated
water
F
(mg/L)
0.1
<0 . 1
<0 . 1
<0 . 1
<0 . 1
<0.1
0.5
1.0
1.0
1.8
1.7
1.8
2.3
F removed
increment
(g)
-
-
2.3
8.0
12.2
11.8
15.5
12.5
11.4
7.9
5.7
5.3
3.1
Total F
removed
(g)
-
-
2.3
10.3
22.5
34.3
49.8
62.3
73.7
81.6
87.3
92.6
95.7
-------
TABLE B-9. REGENERATION NO. 3:
DOUBLE REGENERATION PROCEDURE, APRIL 15, 1979
en
Column
No.
1
1
1
1
1
1
Subtotal
2
2
2
2
2
2
Subtotal
Total
Step
Backwash
Upflow
regeneration
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 1
Backwash
Upflow
regeneration
Upflow rinse
Upflow rinse
Downf low
regeneration
Downf low
neutralization
Column 2
NaOH
/ Q, \
\ "O /
N.A.
4
N.A.
N.A.
1
N.A.
-
N.A.
1
N.A.
N.A.
1
-
-
-
Flow
rate
(L/min)
26.5
2.8
5.7
5.7
2.8
5.7
-
26.5
2.8
5.7
5.7
2.8
-
-
-
Time
(min)
15
32
21
37
32
21
-
15
32
21
37
32
21
-
-
Flow
(D
397
91
117
208
91
117
1,021
397
91
117
208
91
117
1,021
2,042
55-gal
waste
drum
no.
N.A.
1
1
2
3
3
-
N.A.
1
1
2
3
3
-
-
Fluoride
mg/L
N.A.
587
587
17
18
18
-
N.A.
248
248
138
57
57
-
-
Drum
(g)
N.A.
122.3
122.3
3.5
3.8
3.8
129.6
N.A.
51.7
51.7
28.8
11.8
11.8
92.3
225.9
Arsenic
Drum
mg/L (g)
N.A. N.A.
44.6 9.3
44.6 9.3
2.5 0.5
3.9 0.8
3.9 0.8
10.6
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
N.A. N.A.
-
10.6
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APPENDIX C. WATER ANALYSES
TABLE C-l. ANALYSES OF WHY, ARIZONA, WELL WATER
Characteristic Amount* Amount**
Total hardness as CaC03, mg/L
Calcium as CaCOs, mg/L
Magnesium as CaCOs, mg/L
Phenolphthalein alkalinity
as CaCOs, mg/L
Methyl orange alkalinity
as CaCOs, mg/L
Sulf ate as SOt» , mg/L
Chloride as Cl, mg/L
Silica as SiOa, mg/L
Arsenic, mg/L
Fluoride, mg/L
Sodium, mg/L
Iron, mg/L
Copper , mg/L
Manganese, mg/L
Zinc, mg/L
Nitrate, mg/L
Silver, mg/L
Chromium , mg/L
Cadmium, mg/L
Lead , mg/L
Selenium, mg/L
Mercury , mg/L
Barium, mg/L
PH
Specific conductance, ymhos
108
76
32
0
106
124
130
45
0.17
2.4
7.81
950
105
29
8
0
106
147
136
0.10
2.7
145
0.1
<0.05
<0.05
0.2
3.8
<0.01
0.01
<0.005
<0.02
<0.005
<0.001
<0.2
7.5
*Tests performed by Ray W. Hawksley Company,
Richmond, California, February 28, 1978
**Tests performed by Arizona Testing Laboratories,
Phoenix, Arizona, December 19, 1977
36
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-80-100
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
PILOT STUDY OF FLUORIDE AND ARSENIC REMOVAL FROM
POTABLE WATER
5. REPORT DATE
August 1980 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Frederick Rubel,
Fred S. Williams
8. PERFORMING ORGANIZATION REPORT NO
Jr.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Aluminum Company of America
Alcoa Center, Pennsylvania 15069
10. PROGRAM ELEMENT NO.
C110 1CC824 Task 02
11. CONTRACT/GRANT NO.
68-03-1351
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory—Gin.,OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Research 6/78 - 4/79
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officer: Thomas J. Sorg
684-7370
16. ABSTRACT ~~~
Pilot plant studies were conducted on the removal of fluoride and arsenic
from potable water using activated alumina as the adsorbent. The tests were run
using water from the community of Why, Arizona, that contained 3 mg/L fluoride
and 0.15 mg/L arsenic.
The experimental data show that activated alumina is an effective means of
treating this water. Major facts shown by the data are that: (a) arsenic is
preferentially adsorbed on the activated alumina, (b) a stronger sodium hydroxide
solution (4%) is required during regeneration of the activated alumina for arsenic
than is required for fluoride (1%), and (c) the capacity of the alumina for removing
fluoride is decreased by any arsenic remaining in the alumina. The pilot studies
indicate that the preferred method of treating water with these combined contaminants
is the use of two activated alumina columns in series.
A schematic of a full-sized treatment plant is included, along with engineering
estimates of operating and capital equipment costs for small communities.
Operating costs are approximately 5£/kL of treated water. (19C/1000 gal.)
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Potable Water
Water Treatment
Adsorption
Fluorides
Arsenic
Pilot Plants
13B
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
43
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
37
ft U.S. GOVERNMENT PRINTING OFFICE: 1980-657-165/0087
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