United States
Environmental Protection
Agency, J
Office of Research and
Development
Washington, DC 20460
EPA/600/R-00/088
October 2000
http://www.epa.gov
Arsenic Removal from
Drinking Water by Ion
Exchange? and Activated
Alumina Plants
As (III)
As(V)
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EPAJ&OOJR-OQJOB8
October 2000
Arsenic Removal from Drinking Water
by Ion Exchange and
Activated Alumina Plants
by
Lili Wang
Abraham Chen
Keith Fields
Battelle
Columbus, OH 43201-2693
Contract No. 68-C7-0008
Work Assignment No. 3-09
for
Work Assignment Manager
Thomas J. Sorg
Water Supply and Water Resources Division
National Risk Management Research Laboratory
Cincinnati, OH 45268
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Printed on Recycled Paper
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Disclaimer
The information in this document has been funded by the United States Environ-
mental Protection Agency (EPA) under Work Assignment (WA) No. 2-09 of Contract
No. 68-C7-0008 to Battelle. It has been subjected to the Agency's peer and admin-
istrative reviews and has been approved for publication as an EPA document. Men-
tion of trade names or commercial products does not constitute an endorsement or
recommendation for use.
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Foreword
The United States Environmental Protection Agency (EPA) is charged by Congress
with protecting the Nation's land, air, and water resources. Under a mandate of
national environmental laws, the Agency strives to formulate and implement action
leading to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research program
is providing data and technical support for solving environmental problems today and
building a science knowledge base necessary to manage our ecological resources
wisely, understand how pollutants affect our health, and prevent or reduce environ-
mental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's
center for investigation of technological and management approaches for reducing
risks from threats to human health and the environment. The focus of the
Laboratory's research program is on methods for prevention and control of pollution
to air, land, water, and subsurface resources: protection of water quality in public
water systems; remediation of contaminated sites and groundwater; and prevention
and control of indoor air. The goal of this research effort is to evaluate the
performance on a full-scale level of five processes, including coagulation/filtration,
lime softening, iron oxidation/filtration, ion exchange, and activated alumina, to
consistently remove arsenic over a sustained period of time (1 year).
This publication has been produced as part of NRMRL's strategic long-term research
plan. It is published and made available by EPA's Office of Research and Develop-
ment to assist the user community and to link researchers with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
in
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Abstract
This report documents treatment plant information as well as results of year-long sam-
pling and analysis at two ion exchange (IX) plants (referred to as Plants A and B) and
two activated alumina (AA) plants (referred to as Plants C and D), with capacities vary-
ing from 800 to 3,000 gallons per day (gpd). The objective of sampling and analysis
was to evaluate the performance of the full-scale water treatment plants to consistently
remove arsenic from source water. Additionally, data were collected to evaluate the
chemical characteristics of residuals produced by these treatment processes.
The study was divided into three phases: source water sampling, preliminary sam-
pling, and long-term evaluation. Source water sampling was conducted to evaluate
source water characteristics at each plant. Preliminary sampling was initiated in
August 1998 and consisted of four sampling events conducted at each facility on
either a weekly or biweekly basis to refine procedures for subsequent events during
the third phase. Long-term evaluation consisted of weekly or biweekly sampling at
each facility from September 1998 to September 1999. Samples from resin regen-
eration were collected at Plant A from March to June 1999. Spent AA samples were
collected at Plants C and D during the-media change-out events in December 1998
and May 1999, respectively.
Results from the long-term evaluation demonstrated that both the IX and AA systems
are capable of achieving arsenic levels of less than 5 ug/L in the treated water, pro-
vided that the IX resin was regenerated or the AA medium was changed out before
arsenic breakthrough occurred. The two IX systems had inlet arsenic concentrations
between 45 and 65 ug/L [primarily As(V)]. When Plant A was operated beyond 3,000
to 3,200 bed volumes (BV) of water, arsenic chromatographic peaking occurred.
Arsenic breakthrough was not observed at Plant B where an average 97% of removal
efficiency was achieved, leaving only 0.8 to 4.5 ug/L arsenic in the finished water.
Both AA systems consisted of two parallel treatment trains with a roughing AA col-
umn followed by a polishing column in each train. The systems operated on a media
throwaway basis. The average arsenic removal efficiencies achieved at Plants C and
D were 87% and 98%, respectively. The raw water at Plant C (34 to 76 ug/L total
arsenic) contained approximately 0.3 to 28.8 ug/L As(lil), which was nearly com-
pletely removed, even though no oxidation treatment was provided. The water at
Plant D contained slightly higher total arsenic concentrations (53.3 to 87 yg/L) but no
As(lll), which was consistently removed to less than 5 ug/L in the finished water. The
AA media in the roughing tanks were exhausted and disposed of about every 1 to
1.5 years after treating approximately 9,600 BV at Plant C and 5,260 BV at Plant D.
The regeneration process at Plant A recovered from 67 to 86% of arsenic from the
spent brine. The spent AA at Plants C and D passed the Toxicity Characteristic
Leaching Procedure (TCLP) test for metals including arsenic, and therefore was
disposed of as nonhazardous waste.
IV
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Contents
Foreword iii
Abstract iv
Appendices vi
Figures viii
Tables ix
Acronyms and Abbreviations xi
1.0 Introduction 1
1.1 Background 1
1.1.1 General Chemistry of Arsenic 1
1.1.2 Determination of Arsenic Species 3
1.1.3 Treatment Technologies for Arsenic Removal 3
1.1.3.1 Ion Exchange 3
1.1.3.2 Activated Alumina 4
1.1.4 Data Gaps 5
1.2 Objectives 5
1.3 Report Organization 6
2.0 Conclusions 7
3.0 Materials and Methods 8
3.1 General Project Approach 8
3.2 Preparation of Sampling Kits and Sample Coolers 9
3.2.1 Preparation of Arsenic Speciation Kits 9
3.2.2 Preparation of Sample Coolers 10
3.3 Sampling Procedures 11
3.3.1 General Approach and Sampling Schedules 11
3.3.2 Arsenic Field Speciation Procedure ..... 11
3.3.3 Backwash, Spent Brine, and Spent AA Sampling Procedure 13
3.3.4 Sampling Procedure for Other Water Quality Parameters 14
3.4 Technical Approaches for Special Studies 14
3.4.1 Short-Term Special Study at Plant A 14
3.4.2 Short-Term Special Study at Plant D 16
3.5 Analytical Procedures 17
4.0 Results and Discussion 19
4.1 Plant Selection 19
4.2 Plant A 19
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4.2.1 Plant A Description 19
4.2.2 Initial Source Water Sampling 21
4.2.3 Preliminary Sampling 21
4.2.4 Long-Term Sampling 25
4.2.4.1 Arsenic 25
4.2.4.2 Other Water Quality Parameters 27
4.2.4.3 Backwash/Regeneration Wastewater 27
4.2.5 Special Study at Plant A 29
4.3 Plant B 31
4.3.1 Plant B Description 31
4.3.2 Initial Source Water Sampling 32
4.3.3 Preliminary Sampling 32
4.3.4 Long-Term Sampling 35
4.3.4.1 Arsenic 36
4.3.4.2 Other Water Quality Parameters 36
4.4 Plant C 39
4.4.1 Plant C Description 39
4.4.2 Initial Source Water Sampling 42
4.4.3 Preliminary Sampling 42
4.4.4 Long-Term Sampling 43
4.4.4.1 Arsenic 43
4.4.4.2 Other Water Quality Parameters 46
4.4.4.3 Spent AA Samples 50
4.5 Plant D 51
4.5.1 Plant D Description 51
4.5.2 Initial Source Water Sampling 53
4.5.3 Preliminary Sampling 53
4.5.4 Long-Term Sampling 55
4.5.4.1 Arsenic 55
4.5.4.2 Other Water Quality Parameters 57
4.5.4.3 Spent AA Samples 57
4.5.5 Special Study at Plant D 61
4.5.5.1 Regeneration of Spent AA Using Caustic Solution 61
4.5.5.2 Adsorption of Arsenic onto AA 61
5.0 Quality Assurance/Quality Control 64
5.1 Quality Assurance Objectives 64
5.2 Overall Assessment of Data Quality 64
5.2.1 Total Arsenic, Aluminum, Iron, and Manganese 64
5.2.2 Water Quality Parameters 65
5.2.3 TCLP Metals i 65
6.0 "References 66
Appendices
APPENDIX A: Plant A Data 69
A.1 Complete Analytical Results from Long-Term Sampling at Plant A 70
A.2 Technical Data on Puroliteฎ A-300 82
A.3 Water Usage Report 87
APPENDIX B: Plant B Data i 89
B.1 Complete Analytical Results from Long-Term Sampling at Plant B 90
VI
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APPENDIX C: Plant C Data 101
C.1 Complete Analytical Results from Long^Term Sampling at Plant C 102
C.2 Technical Data on DD-2 AA 108
C.3 Water Usage Report 116
APPENDIX D: Plant D Data 121
D.1 Complete Analytical Results from Long-Term Sampling at Plant D 122
D.2 System Plumbing Diagram 130
D.3 Water Usage Report 132
VII
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Figures
Figure 1-1. Concentration-pH Diagrams for As(lll) and As(V) 2
Figure 3-1. Example of Sample Bottle Label 11
Figure 3-2. Photographs of a Typical Sample Cooler (with Four Sample
Compartments) and a Color-Coded Instruction Sheet 12
Figure 3-3. Instruction Sheet for Arsenic Field Speciation 15
Figure 4-1. Process Flow Diagram and Sampling Locations at Plant A 20
Figure 4-2. Cross Section of Filox Filter and A300X IX Filter at Plant A 22
Figure 4-3. Total Arsenic Analytical Results during Long-Term Sampling at
Plant A 26
Figure 4-4. Water Treated between Regenerations of the IX System at
Plant A 26
Figure 4-5. Inlet and Outlet Sulfate Concentrations and Percent Removal at
Plant A 28
Figure 4-6. inlet and Outlet pH and Alkalinity Analytical Results at Plant A 28
Figure 4-7. TDS, Total Arsenic, and Sulfate during the IX System
Regeneration at Plant A (June 13, 1999) 30
Figure 4-8. TDS, TSS, pH, and Flowrate during the IX System Regeneration
at Plant A (June 13,1999) 30
Figure 4-9. Process Flow Diagrams and Sampling Locations at Plant B 33
Figure 4-10. Photograph of the IX System at Plant B 34
Figure 4-11. Total Arsenic Analytical Results during Long-Term Sampling at
PlantB 37
Figure 4-12. Inlet and Outlet Sulfate Analytical Results and Percent Removal
at PlantB 38
Figure 4-13. Inlet and Outlet Alkalinity and pH Analytical Results at Plant B 38
Figure 4-14. Process Flow Diagrams and Sampling Locations at Plant C 40
Figure 4-15. Cross Section of AA Tank at Plant C (Source: Aqua Specialties,
1999) 41
Figure 4-16. Arsenic Form and Species Analytical Results during Long-Term
Sampling at Plant C 46
Figure 4-17. Total Arsenic Analytical Results during Long-Term Sampling at
Plant C 47
Figure 4-18. Inlet and Outlet Alkalinity, pH, Fluoride, and Sulfate Analytical
Results at Plant C 49
Figure 4-19. Process Flow Diagrams and Sampling Locations at Plant D 52
Figure 4-20. Total Arsenic Analytical Results during Long-Term Sampling at
Plant D 58
Figure 4-21. Inlet and Outlet Alkalinity, pH, Fluoride, and Sulfate Analytical
Results at Plant D 60
Figure 4-22. Kinetics of Arsenic Adsorption on AA Media 62
Figure 4-23. Arsenic Adsorption Isotherm on AA Media 62
VIII
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Tables
Table 3-1. Sample Containers and Preservation Methods 10
Table 3-2. Summary of Sampling Activities at Plants A, B, C, and D 13
Table 3-3. Summary of Sampling Schedule for Plants A and B 13
Table 3-4. Summary of Sampling Schedule for Plants C and D 14
Table 3-5. Sampling Schedule for the Special Study at Plant A 16
Table 3-6. Summary of Analytical Methods for Arsenic Treatment Study 18
Table 4-1. Initial List of Treatment Facilities Identified for the Study 19
Table 4-2. Typical Chemical and Physical Characteristics of Purolite A-300
Anion Exchange Resin 23
Table 4-3. Regeneration Schedule of the A300X Resin Column at Plant A 23
Table 4-4. Source Water Analytical Results at Plant A (June 9, 1998) 23
Table 4-5. Analytical Results from Preliminary Sampling at Plant A (August
6, 1998 to August 26, 1998) 24
Table 4-6. Summary of Arsenic Analytical Results at Plant A (September 1,
1998 to June 17, 1999) 25
Table 4-7. Summary of Water Quality Parameter Analytical Results at
Plant A (September 1,1998 to June 17, 1999) 27
Table 4-8. Summary of Analytical Results from Backwash/Regeneration
Samples at Plant A (August 6,1998 to June 13, 1999) 29
Table 4-9. Percent Recoveries of Arsenic during the Resin Regeneration at
Plant A 31
Table 4-10. Typical Source Water Quality Data at Plant B (November 12,
1995) 32
Table 4-11. Source Water Analytical Results at Plant B (June 9,1998) 34
Table 4-12. Analytical Results from Preliminary Sampling at Plant B (August 6
through 25, 1998) 35
Table 4-13. Summary of Arsenic Analytical Results at Plant B (September 1,
1998 to May 25, 1999) 36
Table 4-14. Summary of Water Quality Parameter Analytical Results at
Plant B (September 1,1998 to May 25,1999) 37
Table 4-15. Typical Characteristics of DD-2 Activated Alumina 42
Table 4-16. Arsenic Concentrations (ug/L) from Quarterly Water Sampling at
Plant C 42
Table 4-17. Source Water Quality Measurements at Plant C (December 30,
1994) 42
Table 4-18. Source Water Sampling Analytical Results at Plant C (June 10,
1998) 43
Table 4-19. Analytical Results from Preliminary Sampling at Plant C (August 5
through September 16, 1998) 44
Table 4-20. Summary of Arsenic Analytical Results at Plant C (September 30,
1998 to June 9,1999) 45
Table 4-21. Summary of Water Quality Parameter Analytical Results at
Plant C (September 30, 1998 to June 9, 1999) 48
IX
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Table 4-22. Analytical Results of Spent AA Samples at Plant C 50
Table 4-23. Typical Characteristics of CPN Activated Alumina 53
Table 4-24. Arsenic Concentrations (ug/L) from Monthly Water Sampling at
Plant D (March 6, 1992 to December 29, 1999) 54
Table 4-25. Typical Source Water Quality Measurements at Plant D 55
Table 4-26. Source Water Sampling Analytical Results at Plant D (June 10,
1998) 55
Table 4-27. Analytical Results from Preliminary Sampling at Plant D (August 5
through September 16,1998) 56
Table 4-28. Summary of Arsenic Analytical Results at Plant D (September 30,
1998 to September 1, 1999) 57
Table 4-29. Summary of Water Quality Parameter Analytical Results at
Plant D (September 30,1998 to September 1,1999) 59
Table 4-30. Analytical Results of Spent AA Samples at Plant D 61
Table 4-31. Analytical Results of Caustic Wash and Acid Digestion of Spent
AA Samples at Plant D 61
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Acronyms and Abbreviations
AA activated alumina
ADD average daily demand
As arsenic
AWWA American Water Works Association
BV bed volumes
DA disinfectant addition
DI distilled
DL detection limit
EBCT empty bed contact time
EDR electrodialysis reversal
EPA United States Environmental Protection Agency
GAG granular activated carbon
GFAAS graphite-furnace atomic-absorption spectrophotometer
Gl gastrointestinal
gpd gallons per day
gpm gallons per minute
GW groundwater
HCI hydrochloric acid
HOPE high-density polyethylene
hp horsepower
ICP-MS inductively coupled plasma-mass spectrometry
ID identification
IN inlet sampling location
IOCS iron oxide-coated sand
IX ion exchange
MCL maximum contaminant level
MDL method detection limit
MS matrix spike
MSD matrix spike duplicate
MSDS material safety data sheet
NA not available
ND not detected
NOM natural organic matter
NS not sampled
NTU nephelometric turbidity units
XI
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O&M operations and maintenance
OU outlet sampling location
pCi picocuries
POC point of contact
POE point of entry
ppm parts per million
psi pounds per square inch
PVC polyvinyl chloride
QA quality assurance
QAPP quality assurance project plan
QA/QC quality assurance/quality control
RPD relative percent difference
SBA strong-base anion
SDWA Safe Drinking Water Act
TCLP Toxicity Characteristic Leaching Procedure
TDS total dissolved solids
TOC total organic carbon
TSS total suspended solids
WA work assignment
WAM Work Assignment Manager
WBA weak-base anion
XRD x-ray diffraction
ZPC zero point charge
%R percent recovery
XII
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Acknowledgments
We wish to thank Paul Kempt and Jeffrey Folger of the Drinking Water Program,
Department of Human Services, the State of Maine, and Bernie Lucey of the Depart-
ment of Environmental Services, the State of New Hampshire, for their assistance in
system selection and participation in the studies. Sincere appreciation also is extended
to all facility personnel who assisted in collecting samples weekly or biweekly for up
to 12 months. Their work on this project was uncompensated, making their superb
efforts even more remarkable. Personnel from all facilities are thanked for their hard
work and dedication throughout the duration of this project.
XIII
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1.0 Introduction
This project consists, in part, of a field study in which two
water treatment processes were evaluated for their abil-
ity and effectiveness at reducing arsenic (As) levels in
source water. The first part of the study involved collect-
ing water samples from various locations at two ion ex-
change (IX) and two activated alumina (AA) plants. The
second part of the study involved sampling and analysis
of spent brine and spent AA media to determine the
quantities and chemical characteristics of residuals pro-
duced by the IX and AA treatment processes, respec-
tively. This report describes the design and operation of
four treatment plants and presents the analytical results
of the samples collected from the plants during 1 year of
operation.
1.1 Background
The Safe Drinking Water Act (SDWA) of 1974 mandates
that the United States Environmental Protection Agency
(EPA) identify and regulate drinking water contaminants
that may have an adverse human health effect and that
are known or anticipated to occur in public water supply
systems. Arsenic is a naturally occurring contaminant
that has known adverse human health effects. Excessive
amounts of arsenic can cause acute gastrointestinal (Gl)
and cardiac damage. Chronic doses can cause vascular
disorders such as blackfoot disease (Chen et al., 1994a),
and epidemiological studies have linked arsenic to skin
and lung cancer (Tate and Arnold, 1990). In 1975, under
the SDWA, the EPA established a maximum contam-
inant level (MCL) for arsenic at 0.05 mg/L. Since that
time, revision of the MCL has been considered a number
of times, but no change has been made. The SDWA was
amended in 1996 and these amendments require that
the EPA develop an arsenic research strategy and pub-
lish a proposal to revise the arsenic MCL by January
2000.
A draft arsenic research plan was prepared by the EPA
in December 1996 and was finalized in February 1998
based upon a technical review by the EPA's Board of
Scientific Counselors (EPA, 1998). The plan identifies
the research needed by the EPA to support a proposed
revision of the arsenic MCL. The plan also identifies a
number of treatment technologies available for arsenic
removal, and recognizes the need to determine the
capability of these technologies to remove arsenic to a
level significantly lower than the current MCL.
This field study was conducted as part of an EPA Work
Assignment (WA) to evaluate the performance of nine
full-scale water treatment plants to remove arsenic from
drinking water. These nine plants represent five arsenic
removal unit processes: conventional coagulation/filtra-
tion, lime softening, iron/manganese removal, IX, and
AA. Long-term operational data were developed in these
studies to support the ability and effectiveness of these
treatment processes to consistently remove arsenic from
drinking water.
7.1.1 General Chemistry of Arsenic
Arsenic is a common, naturally occurring drinking water
contaminant that originates from arsenic-containing rocks
and soil and is transported to natural waters through
erosion and dissolution. Arsenic occurs in natural waters
in both organic and inorganic forms. However, inorganic
arsenic is predominant in natural waters and is the most
likely form of arsenic to exist at concentrations that cause
regulatory concern (Edwards et al., 1998).
The valence and species of inorganic arsenic are de-
pendent on the oxidation-reduction conditions and the
pH of the water. As a general rule of thumb, the reduced,
trivalent form [As(III)] normally is found in groundwater
(assuming anaerobic conditions) and the oxidized, penta-
valent form [As(V)j is found in surface water (assuming
aerobic conditions); this rule does not always hold true for
groundwater, where both forms have been found together
in the same water source. Arsenate exists in four forms in
aqueous solution, depending on pH: H3AsO4, H2AsO4~
HAsO/", and AsO/". Similarly, arsenite exists in five
forms: H4AsO3+, H3AsO3, H2AsO3- HAsO/-, and AsO/-.
As shown in Figure 1-1, which contains solubility dia-
grams for As(lll) and As(V), ionic forms of arsenate domi-
nate at pH>3, while arsenite is neutral at pH<9 and i<5nic
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.1
.032
I
a .01
.0032
.001
7^"
H3Asฐ3(a)
U-~W24sO3+
\
Conditions
.Ippm
10
12
14
pH
Q,
.0032 -
Figure 1-1. Concentration-pH Diagrams for As(lll) and As(V)
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at pH>9. Ion exchange and AA treatment technologies,
often used by small drinking water systems for arsenic
removal, function by exchanging arsenate with counter
ions of an anionic resin (e.g., Cl~) and by adsorbing arse-
nate onto alumina granules, respectively. Therefore, the
valence and species of soluble arsenic are very impor-
tant in evaluating arsenic removal.
1.1.2 Determination of Arsenic Species
Although total arsenic can be effectively preserved in
field samples, presently no method exists to consistently
preserve inorganic arsenic species in field samples.
Preservation of total arsenic is accomplished by acidify-
ing the sample to pH<2 in the field. However, a high
level of uncertainty over exact levels of As(lll) and As(V)
exists when acids such as nitric acid (HNO3) or hydro-
chloric acid (HCI) are used to preserve inorganic species
of arsenic. Interconversion of As(III) and As(V) in sam-
ples preserved with 0.05 N HCI have been reported to
occur within 1 day (Andreae, 1977). Another laboratory
study conducted by Eaton et al. (1997) examined the
preservation of arsenic using humic acid, ascorbic acid,
and HCI; the study concluded that no effective methods
exist for preserving As(lll) and As(V) in water samples.
Some researchers have frozen samples to preserve the
inorganic species of arsenic. However, freezing is neither
a cost-effective nor a practical method for field sampling.
In response to the lack of techniques available for ade-
quately preserving arsenic species, field speciation pro-
tocols have been developed by Ficklin (1983), Clifford et
al. (1983), and Edwards et al. (1998). In each of these
studies, an anion exchange resin column was used for
field speciation of arsenic. Ficklin (1983) used a strong
anion exchange resin (Dowex 1x8, 100-200 mesh,
acetate form) in a 10 cm x 7 mm glass column to sepa-
rate As(lll) from As(V) in water samples that had been
filtered through a 0.45-um membrane filter and acidified
with 1% HCI. The resin was supplied in chloride form
and was converted to the acetate form. However, in the
protocol by Clifford et al. (1983), a chloride-form strong
'base anion resin (ASB-2, 30-60 mesh) was used to sepa-
rate As(lll) from As(V). In this method, the sample was not
filtered or preserved with acid. Both Ficklin and Clifford
used a graphite-furnace atomic-absorption spectropho-
tometer (GFAAS) to determine the arsenic concentration.
More recently, Edwards et al. (1998) made the following
modifications to Ficklin's method: (1) Substituted 50-100
mesh resin for the 100-200 mesh resin to allow faster
sample flow. (2) Used 12 cm x 15 mm polypropylene col-
umns to improve safety and speed of sample treatment.
(3) Used 0.05% H^SO,, instead of 1% HCI to acidify
samples prior to resin treatment. Edwards et al.'s use of
H2SO4 helped to prevent potential problems associated
with overacidification of the sample, and also helped to
prevent CI" from interfering with the inductively coupled
plasma-mass spectrometry (ICP-MS) analysis. The re-
ported recoveries of As(lll) and As(V) ranged from 80 to
120% by Ficklin (1983), 95 to 117% by Clifford et al.
(1983), and 100 to 105% by Edwards et al. (1998). For
this study, the decision was made to use a field speciation
technique similar to that used by Edwards et al. (1998).
1.1.3 Treatment Technologies for
Arsenic Removal
Several common treatment technologies are used for re-
moval of inorganic contaminants, including arsenic, from
drinking water supplies. Large-scale treatment facilities
often use conventional coagulation with alum or iron salts
followed by filtration to remove arsenic (Chen et al.,
1994b; Hering et al., 1996; Scott et al., 1995; and Sorg,
1993). Lime softening and iron removal also are com-
mon, conventional treatment processes that can poten-
tially remove arsenic from source waters (McNeill and
Edwards, 1997). Small-scale systems and point-of-entry
(POE) systems often use IX and AA adsorption because
of their ease of handling and sludge-free operations. Re-
cently, iron-based adsorption media, such as granular
ferric hydroxide, have been developed and shown high
arsenic removal capacities in laboratory and pilot tests
(Joshi and Chaudhuri, 1996; Driehaus, et al. 1998). Their
full-scale applications, however, are still limited. Other
technologies that also have been used for arsenic re-
moval include manganese greensand, reverse osmosis,
electrodialysis reversal (EDR), nanofiltration, and ad-
sorption on activated carbon.
This report focuses on the IX and AA treatment pro-
cesses used primarily by small drinking water systems.
Two additional reports also have been developed to
cover conventional treatment processes, including coag-
ulation/filtration and lime softening (Battelle, 1999) and
iron removal (Battelle, 2000a).
1.1.3.1 Ion Exchange
Ion exchange is a physical/chemical process in which
ions held electrostatically on the surface of a solid phase
are exchanged for ions of similar charge in a solution (i.e.,
drinking water). The solid is typically a synthetic anion
exchange resin which is used to preferentially remove
particular contaminants of concern. Ion exchange is com-
monly used in drinking water treatment for softening (i.e.,
removal of calcium, magnesium, and other cations in ex-
change of sodium), as well as removing nitrate, arsenate,
chromate, and selenate from municipal water (Clifford,
1999). Due to its higher treatment cost compared to con-
ventional treatment technologies, IX application is limited
primarily to small/medium-scale and POE systems.
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Anion exchange resins come in two classes, strong-base
anion (SBA) and weak-base anion (WBA). The quarter-
nary ammonium functional groups (-R3'NT where FT
represents organic radicals such as CH3) on the SBA
resins are strongly basic and ionized to act as ion
exchangers over the pH range of 0 to 13. The WBA
resins are useful only in the acidic pH region where the
primary, secondary, and tertiary amine functional groups .
are protonated to form positively charged exchange sites
for anions. Both SBA and WBA resins may be present in
the hydroxide or chloride form. Typically, SBA resins are
used for arsenic removal because they tend to be more
effective over a larger pH range than WBA resins.
Ion exchange does not remove As(III) because As(III)
occurs predominantly as an uncharged ion (H3AsO3) in
water with a pH value of less than 9.0 (Ficklin, 1983;
Clifford, 1999). The predominant species of As(V),
HjAsO/" and HAsO/~, are negatively charged, and thus
are removable by IX. If As(lll) is present, it is necessary
to oxidize As(lll) to As(V) before removal by IX (Fox,
1989; Clifford and Lin, 1986).
To remove arsenic from drinking water, water is passed
through one or more IX resin beds. Arsenate ions
(HjAsO,,- and HAsO/~) and several other anions (most
notably sulfate) are preferentially removed according to
the order of preference for exchange. When all available
sites on the resin have been exhausted, the bed is re-
generated with a brine solution (chloride exchange).
The efficiency of the IX process for arsenic removal is
strongly affected by competing ions, such as total dis-
solved solids (TDS) and sulfate (Clifford 1999). Other
factors affecting the use of the IX process include empty
bed contact time (EBCT) and spent regenerant disposal.
Competition from background ions for available IX sites
can greatly affect the efficiency and economics of IX sys-
tems. The level of these background ions often deter-
mines the applicability of the IX process at a particular
site. The following selectivity sequence was established
for SBA resins (Clifford, 1999):
SO/' > NO3- > HASO/- > NO2', OP >
S!(OH)4, H3AS04
Therefore, high sulfate and TDS levels can significantly
reduce arsenic removal efficiency (Clifford and Lin, 1986,
1991). In general, the IX process is not economically
attractive if source water contains high TDS (>500 mg/L)
and sulfate (>150 mg/L) (Clifford, 1999). Also, the pres-
ence of Fe(lll) in feed water can affect arsenic removal
by forming Fe(lll)-arsenic complexes, which cannot be
removed by IX resins (Clifford et al., 1998).
When the sulfate concentration is high, sulfate may dis-
place previously sorbed ions (such as arsenate) from a
resin bed, thereby causing higher arsenic concentrations
in the effluent than in the influent. This phenomenon is
called chromatographic peaking (dumping), and is a po-
tentially risky situation when toxic ions such as arsenic
are involved. To avoid peaking, the resin bed must be
monitored and regenerated well in advance of the onset
of the peaking.
For- chloride-form resins, concentrated NaCI solution com-
monly is used as a regenerant. Arsenic elutes readily
from IX columns mainly because it is subject to selec-
tivity reversal in a high ionic strength (>1 M) solution
(Clifford and Lin, 1995). The regenerated resin then is
ready for another exhaustion cycle.
Clifford et al. (1998) found that dilute regenerants at 0.5-
1.0 M were more efficient than concentrated ones at
2.0-4.0 M for eluting arsenic (in terms of the ratio of re-
generant equivalent to resin equivalent). However, dilute
regenerants could require longer regeneration time and
produce larger volumes of spent regenerant.
1.1.3.2 Activated Alumina
AA adsorption is a physical/chemical process by which
ions in solution (i.e., drinking water) are removed by the
available adsorption sites on an oxide surface. AA is
usually prepared through dehydration of AI(OH)3 at high
temperatures and consists of amorphous and gamma
alumina oxide (Chen and Snoeyink, 1987). AA is used
primarily in packed beds to remove contaminants such
as fluoride, arsenic, selenium, silica, and natural organic
matter (NOM). To remove contaminants, feed water is
passed continuously through one or more AA beds. When
all available adsorption sites are occupied, the AA media
may be regenerated with a strong base, NaOH, or sim-
ply disposed of.
Many studies have shown that AA is an effective treatment
technique for arsenic removal. Factors such as arsenic
oxidation state, pH, competing ions, and EBCT signifi-
cantly affect arsenic removal. Other factors affecting the
use of the AA process include regeneration practice,
spent regenerant disposal, and alumina disposal. The fol-
lowing subsections briefly discuss some of these factors.
Effects of Arsenic Oxidation State. Like all other treat-
ment technologies, the AA process is more effective in
removing As(V) than As(lll). In a study by Frank and
Clifford (1986), an AA column treating water containing
0.1 mg/L As(V) was able to treat about 23,400 BV before
the effluent arsenic levels reached 0.05 mg/L. A similar
column treating water containing 0.1 mg/L As(lll), how-
ever, began to break through after treating only 300 BV
-------
of water. Therefore, preoxidation of As(lll) to As(V) often
is recommended when treating water containing As(lll).
Effect of pH. The AA process is sensitive to pH. Anions
(including arsenic) are best adsorbed below pH 8.2, a
typical zero point charge (ZPC) for AA. Below this pH,
the AA surface has a net positive charge that can be
balanced by adsorbing anions, such as hydroxide, fluo-
ride, and arsenate. Several studies have shown that the
optimum pH for arsenic removal ranges from 5.5 to 6.0
(Singh and Clifford, 1981; Rosenblum and Clifford, 1984).
The arsenic capacity of AA deteriorates as the pH in-
creases from 6.0 to 9.0 (Hathaway and Rubel, 1987).
Column studies conducted by Clifford and Lin (1991)
also showed a similar trend. For a target arsenic effluent
concentration of 0.05 mg/L, a column operating at pH
6.0 was able to treat 8,760 BV of water, but a column
operating at pH 7.3 treated only 1 ,944 BV.
Some small AA systems are operated on a media throw-
away basis without pH adjustments for an optimal run
length. These systems, save costs for pH adjustments
and for operations and maintenance (O&M) related to
media regeneration. Upon breakthrough, however, AA
must be replaced and the spent AA must pass the Tox-
icity Characteristic Leaching Procedure (TCLP) to be
disposed of as a nonhazardous waste.
Effect of Competing Ions. Like IX resins, AA exhibits
preferences for certain ions. The order of preference,
however, can be quite different from those of IX resins.
Activated alumina appears to have a higher preference
for arsenic than for most competing ions in water (includ-
ing sulfate) (Clifford, 1999; Vagliasindi et al., 1996). Fur-
ther, as indicated by the general selectivity sequence
shown below (Clifford, 1999), AA preferentially adsorbs
H2AsO4- over H3AsO3 [As(lll)]:
OH~ > H2AsO4"> Si(OH)3CT
HSeO~ > TOC
SO/-> H3As03
Several studies have examined the effects of some of
these competing ions. Vagliasindi et al. (1996) found that
increasing sulfate from 0 to 100 mg/L had only a small
impact on the sorption of As(V), and the presence of
chloride did not affect As(V) removal at all. The addition
of 4 mg/L dissolved organic matter, however, reduced
As(V) sorption about 50%. Also, the addition of 360 mg/L
of sulfate and almost 1,000 mg/L TDS reduced the
sorption of As(V) by approximately 50%, compared to
sorption from deionized (Dl) water (Clifford and Lin,
1986). Rosenblum and Clifford (1984) also reported that
sulfate and chloride significantly reduced AA's ability to
remove arsenic from water. For water containing approx-
imately 530 mg/L of chloride, the arsenic removal was
16% lower than that for a nonchloride-containing water.
And for water containing 720 mg/L sulfate, the arsenic
removal was 50% lower than that for a nonsulfate-
containing water.
Effect of Empty Bed Contact Time. Simms and Azizian
(1997) conducted AA column tests using 3-, 6-, and 12-
minute EBCTs and found a linear relationship between
EBCT and arsenic adsorption. However, Vagliasindi and
Benjamin (1997) found that arsenic adsorption increased
only slightly with increasing EBCTs.
1.1.4 Data Gaps
The removal of arsenic from drinking water by IX and AA
has been studied extensively at laboratory- and pilot-
scale levels. Although some short-term full-scale evalua-
tions have been performed for both treatment processes,
few data exist on the capability of these processes to
reduce arsenic on a sustained basis. Thus, a need exists
to determine the effectiveness of IX and AA to produce
drinking water containing low levels of arsenic on a long-
term basis and under varying operational and seasonal
conditions.
Another data gap that exists is the production and dis-
posal of spent regenerants and spent media. Due to high
arsenic concentrations in the spent regenerants, direct
discharge to a sanitary sewer may not be always possi-
ble depending on the local regulations. Therefore, the
spent regenerants may need to be treated prior to dis-
posal. Arsenic can be removed from regenerants by
coprecipitation with ferric iron or aluminum salts, and the
arsenic-laden sludge can be subsequently dried and
landfilled if toxicity limits are not exceeded. Brine reuse
has recently been studied to examine its potential in
reducing the brine consumption and the discharge vol-
ume (Clifford et al., 1998). Also, the spent AA media
from throwaway systems may be landfilled as a non-
hazardous waste if they pass the TCLP tests.
Few data currently exist on the amounts and the chem-
ical compositions of residuals generated by the IX and
AA processes and on the methods that are environmen-
tally acceptable for their disposal. Therefore, information
needs to be collected on the chemical characteristics of
the wastes produced by these processes.
1.2 Objectives
The primary objective of this study was to evaluate the
effectiveness of IX and AA systems to consistently
reduce arsenic concentrations in source water to low
levels. This report presents the results of weekly and
biweekly monitoring for approximately 1 year at two IX
plants and two AA plants.
-------
The second objective of this study was to examine resid-
uals produced during IX and AA treatment processes.
Information was collected on the quantities and chemical
characteristics of the wastes produced by these two
treatment processes.
The third objective of this study was to conduct two short-
term special studies to collect more definitive data to help
explain unusual performance conditions or variations ob-
served during long-term sampling at the IX and AA plants.
1.3 Report Organization
presents the conclusions from the study of the two IX
plants and two AA plants. Section 3.0 describes the
materials and methods used to conduct this study.
Section 4.0 discusses the results of the study and Sec-
tion 5.0 provides specific information on quality assur-
ance/quality control (QA/QC) procedures. Section 6.0 is
a list of references cited in the text. Appendices A, B, C,
and D present the complete set of analytical data and
miscellaneous information collected at Plants A, B, C,
and D, respectively, during long-term sampling.
Section 1.0 provides background information for this field
study and project objectives. Section 2.0 of this report
-------
2.0 Conclusions
The EPA currently is in the process of revising the arse-
nic MCL. A proposed arsenic MCL of 0.005 mg/L was
published in the Federal Register on June 22, 2000,
which is significantly lower than the current MCL of
0.05 mg/L. The low arsenic standard will inevitably affect
many water treatment facilities with high arsenic con-
centrations in water supplies. Therefore, there is a need
to evaluate the ability of existing treatment processes to
consistently remove arsenic to low levels. The primary
objectives of this project were to document arsenic re-
moval at two IX plants (Plants A and B) and two AA
plants (Plants C and D), and to assess chemical charac-
teristics of residuals (spent brine and spent AA) at these
treatment plants.
The primary focus of this study was the long-term evalu-
ation of arsenic removal at the IX and AA plants. The
two IX plants demonstrated the ability to consistently
achieve low levels of arsenic in the treated water (i.e.,
<5 ug/L) when the resin was properly regenerated. Dur-
ing the long-term study, Plants A and B achieved an
average of 53% and 97% arsenic removal, respectively.
Initially, Plant A was regenerated once every 3 months;
however, early arsenic breakthrough (50 jxg/L) was de-
tected in the treated water before the scheduled regen-
eration of the system. Also, chromatographic effect was
observed, which likely was caused by sulfate in the
source water, resulting in effluent arsenic concentrations
exceeding the influent levels. After a run length to arse-
nic breakthrough (50 ug/L) of approximately 3,000-3,200
BV was determined, a monthly regeneration schedule
was recommended and implemented at Plant A. As
such, early arsenic breakthrough did not happen again.
During the Plant A study, up to 23.4 ug/L of arsenic was
detected immediately after the regeneration. Further
study revealed that this "leakage" actually was due to an
artifact caused by the arsenic already present in the
2,400-gal storage tank located just upstream from the
sampling point. At Plant B, noticeable arsenic break-
through was not detected throughout the course of the
study because of the frequent column regeneration (i.e.,
once every 6 days). As(III) removal was not observed at
either plant because source water contained primarily
As(V).
The two AA plants evaluated also were capable of
achieving arsenic levels of 5 ug/L or less in the treated
water, provided that the AA was changed out at the
proper time before arsenic breakthrough. Both AA plants
are operated on a media throwaway basis under raw pH
conditions (i.e., pH 8.0 to 8.6). Arsenic removal efficien-
cies achieved at Plants C and D during the long-term
study were 87% and 98%, respectively. The AA medium
in the roughing tanks was exhausted and disposed of
about every 1 to 1.5 years after treating 9,600 BV at
Plant C and 5,260 BV at Plant D. Near complete As(lll)
removal by AA was observed at Plant C, as the source
water contained 0.3 to 28.8 ug/L As(lll), and the finished
water contained less-than-detect levels of As(lll).
The secondary focus of this study was on residual pro-
duction and the chemical characteristics of the residuals.
Data from resin regeneration at Plant A demonstrated that
the regeneration efficiency at Plant A ranged from 67% to
86%, comparable with literature data. None of the spent
AA sampled at Plants C and D qualified as a hazardous
waste based on TCLP testing for metals including arsenic.
Therefore, the spent AA was disposed of as nonhazardous
waste. Using caustic wash, it was possible to recover
approximately 50% of the arsenic from the spent AA at
Plant D. The AA capacity obtained from the column oper-
ation at Plant D (0.25 g/kg) was less than that obtained
from the batch adsorption isotherm (1.09 g/kg).
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3.0 Materials and Methods
This section discusses the materials and methods used
for performing the source water, preliminary, and long-
term sampling and data collection at two IX plants and
two AA plants. Section 3.1 describes the general project
approach. Section 3.2 describes the preparation of arse-
nic speciation kits and sample coolers. Section 3.3 pro-
vides detailed sampling procedures. Section 3.4 discusses
the technical approach for the short-term special studies.
Section 3.5 discusses pertinent analytical procedures.
3.1 General Project Approach
Several consecutive tasks were performed to accomplish
the project objectives described in Section 1.2. These
tasks involved the following activities:
Select treatment plants and conduct an initial site
visit to collect source water samples at each
selected plant
Prepare a preliminary sampling and data collection
plan for each plant
Finalize the sampling and data collection plan after
completion of four weekly (Plants A and B) or
biweekly (Plants C and D) preliminary sampling
events at each plant
Implement the final sampling and data collection
plan with weekly or biweekly sampling events at
each plant for 9 months up to one full year
Select treatment plants with unusual performance
conditions or variations and conduct two short-term
special studies.
For initial plant selection, the EPA Work Assignment
Manager (WAM) initiated contacts with representatives
of the states of Maine and New Hampshire for small-
scale IX and AA systems currently in operation. Two IX
plants (designated as Plants A and B) and three AA
plants (designated as Plants C, D, and E) were selected
for initial site visits and source water sampling. The infor-
mation collected during the site visits, including the con-
centration and speciation of arsenic in each source water,
was tabulated and used as the basis for the final plant
selection.
Following the final plant selection (Plants A, B, C, and D
were selected), a preliminary sampling and data collection
plan was prepared for each plant to document the plant's
operation and performance for arsenic removal and the
critical parameters that would impact the removal. Each
preliminary plan also described the data collection effort to
characterize the residuals produced by the treatment
process. The approved preliminary plans were imple-
mented at Plants A and B during a 4-week trial period,
and Plants C and D during an 8-week trial period. Two
Battelle staff members revisited the plants during the first
week of the trial period to perform sampling, conduct
training of plant support personnel, and establish/coor-
dinate all required logistics (such as receiving/shipping of
sample coolers, chain-of-custody coordination, commun-
ication methods, and emergency/contingency plans). The
remaining three sampling events during the preliminary
sampling were performed by a designated point of con-
tact (POC) or an alternate at each plant. The experience
gained during the trial period was used to finalize the
long-term sampling and data collection plans.
All water and residual samples were collected and ana-
lyzed in accordance with the Category III Quality Assur-
ance Project Plan (QAPP) prepared by Battelle (1998)
for this project. Water samples (source water and treated
water) were collected weekly from Plants A and B. Water
samples were collected biweekly from Plants C and D at
the following four locations: (1) inlet; (2) after the first AA
tank of train 1; (3) after the second AA tank of train 1;
and, (4) after treatment through both trains. During the
preliminary and long-term sampling phases, field arsenic
speciation was conducted once every 4 weeks for Plants
A and B and once every 8 weeks for Plants C and D.
Starting from March 1999, backwash and spent brine
samples were collected from Plant A when regeneration
was performed once every 4 weeks. Spent AA samples
also were collected during the media change-out at
Plant C in December 1998 and at Plant D on May 25,
1999.
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All sample containers and arsenic speciation kits were
prepared and sent in coolers on a weekly or biweekly
basis from Battelle to each plant via Federal Express.
The coolers were returned to Battelle immediately after
the sample collection had been completed. Analyses of
arsenic, aluminum, iron, and manganese in water were
conducted by Battelle's ICP-MS laboratory. Wilson Envi-
ronmental Laboratories of Westerville, OH, was subcon-
tracted to perform all other chemical analyses. Battelle
coordinated all sampling logistics.
3.2 Preparation of Sampling Kits
and Sample Coolers
All arsenic speciation kits and sample coolers were
prepared at Battelle. The following sections describe the
relevant preparation procedures.
3.2.7 Preparation of Arsenic
Speciation Kits
The arsenic field speciation method used an anion
exchange resin column to separate the soluble arsenic
species, As(V) and As(lll). A 250-mL bottle (identified as
bottle A) was used to contain an unfiltered sample,
which was analyzed to determine the total arsefiic con-
centration (both soluble and particulate). The soluble
portion of the sample was obtained by passing the unfil-
tered sample through a 0.45-um screw-on disc filter to
remove any particulate arsenic and collecting the filtrate
in a 125-mL bottle (identified as bottle B). Bottle B con-
tained 0.05% (volume/volume) ultra-pure sulfuric acid to
acidify the sample to about pH 2. At this pH, As(III) was
completely protonated as H3AsO3, and As(V) was pres-
ent in both ionic (i.e., H2AsO4~) and protonated forms (i.e.,
H3AsO4) (see Figure 1-1). A portion of the acidified sam-
ple in bottle B was run through the resin column. The
resin retained As(V) and allowed As(lll) (i.e., H3AsO3) to
pass through the column. (Note that the resin will retain
only H2AsO4~ and that H3AsO4, when passing though the
column, will be ionized to H2AsO4~ due to elevated pH
values in the column caused by the buffer capacity of
acetate exchanged from the resin.) The eluate from the
column was collected in another 125-mL bottle (identi-
fied as bottle C). Samples in bottles A, B, and C were
analyzed for total arsenic using ICP-MS. As(lll) concen-
tration was the total arsenic concentration of the resin-
treated sample in bottle C. The As(V) concentration was
calculated by subtracting As(lll) from the total soluble
arsenic concentration of the sample in bottle B.
Arsenic speciation kits were prepared in batch at Battelle
based on a method modified from Edwards et al. (1998).
Each arsenic speciation kit contained the following:
One anion exchange resin column
Primary and duplicate A, B, and C bottles
One 400-mL disposable beaker
Two 60-mL disposable syringes
Several 0.45-um syringe-adapted disc filters.
Each speciation kit was packed in a plastic zip-lock bag
along with latex gloves and a step-by-step speciation
sampling instruction sheet. All chemicals used for pre-
paring the kits were of analytical grade or higher. The
arsenic speciation kits were prepared according to the
following procedures:
Resin Preparation. Before packing into columns,
the anion exchange resin (Dowex 1-X8, 50-100
mesh) was converted from the chloride form (as
supplied by Supelco) to the acetate form according
to the method used by Edwards et al. (1998). First,
1 kg of the resin was placed in a 3-L beaker. One
liter of 1 N NaOH was then added to the resin,
stirred for an hour using an overhead stirrer, and
drained. This NaOH rinse was repeated sequen-
tially for three times. The NaOH-treated resin then
was rinsed with two 1-L batches of reagent-grade
water, followed by three acetic acid rinses. Each
acetic acid rinse consisted of adding 1 L of 1 N
reagent grade acetic acid to the resin, stirring for
5 minutes, and draining the spent acid. The acetic
acid-treated resin was subsequently rinsed with
3-L batches of reagent-grade water. The resin
slurry was stored in a 2-L bottle and kept moist
until use.
Anion Exchange Column Preparation. The resin
columns used were 12 cm x 15 mm in size and
made of polypropylene (Bio-Rad Laboratories,
CA). Each column was slurry packed with about
20 g (drained weight) of the prepared resin, yield-
ing a resin depth of approximately 10.5 cm. The
column was sealed with two plastic caps (one each
on top and bottom) to prevent contamination and
retain moisture prior to use.
Sample Bottles. VWRbrand TraceClean high-
density polyethylene (HOPE) sample bottles (250
and 125 mL) were used to prepare bottles A, B,
and C. Bottles A and C were spiked with 500 and
250 uL of concentrated ultra-pure nitric acid
(HNO3), respectively; and bottle B was spiked with
1.25 mL of 5% (volume/volume) ultra-pure sulfuric
acid (H2SO4). H2SO4 was used to acidify the sample
in bottle B because chloride (Cl~) in HCI could inter-
fere with the ICP-MS arsenic detection and HNO3
(an oxidizing agent) could damage the resin or
form nitric acid-arsenic redox couples (Edwards et
al., 1998).
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Beaker, Syringes, and Filters. One 400-mL
disposable plastic beaker was used to collect a
water sample. Samples were filtered using 60-mL
disposable plastic syringes with 0.45-um screw-on
disc filters. All disposable beakers, syringes, and
filters were rinsed with Dl water and air-dried
before being packed into the sampling kits.
3.2.2 Preparation of Sample Coolers
Sample containers for analysis of all water quality
parameters except for total As, Al, Fe, and Mn were pro-
vided by Wilson Environmental Laboratories. These con-
tainers were new, rinsed with Dl water, allowed to air dry,
and contained appropriate preservatives before being
delivered to Battelle. These bottles were labeled with the
letter D, E, F, or G, designating the specific analysis to
be performed. Table 3-1 lists the sample container size
and type (for water and solid samples), 'sample preser-
vation used, analysis to be performed, and holding time.
All sample containers were labeled prior to shipment.
Figure 3-1 presents an example sample bottle label. The
sample identification (ID) consisted of five parts, includ-
ing a two-letter code for a water treatment plant, the
sampling date (mm/dd/yy), a two-letter code for a spe-
cific sampling location (e.g., IN for inlet water, TA for
after the first tank, TB for after the second tank, and OU
for outlet water), a one-letter code (A through G) desig-
nating the analyses to be performed (see Table 3-1),
and a code indicating whether the sample was a primary
sample or a field duplicate sample. A field duplicate was
identified by adding a "dup" to the label and a primary
sample used no additional coding.
After the sample bottles were labeled, they were placed in
coolers subdivided into two or four compartments, each
corresponding to a specific sampling location at each
plant. Color coding was used to identify sampling loca-
tions and all associated sample bottles. For example, red,
blue, green, and yellow were used to designate sample
locations for inlet, TA, TB, and outlet locations, respective-
ly. Other sampling and shipping-related materials, includ-
ing latex gloves, chain-of-custody forms, prepaid Federal
Express air bills, sampling instructions, ice packs, and
bubble wrap, also were packed into coolers. When arse-
nic speciation or residual samples were to be collected,
arsenic speciation kits or bottles for residual samples also
were included in the cooler. After preparation, sample
coolers were sent to all plants every Thursday via Federal
Table 3-1. Sample Containers and Preservation Methods
Container Size Container Type
Arsenic Speciation Samples
- . ,., certified clean HOPE
250 mL (A) bott,es
,,. . ,m certified clean HOPE
125 ml (B) boffles
HOC i m certified clean HOPE
125mL(C) bottles
Backwash/Spent Brine Samples
250 mL (D) plastic
or.n . /A> certified clean HOPE
250mL(A) bottles
Water Quality Parameter Samples
250 mL (D) plastic
250 mL (D) plastic
250 mL (E) plastic
250 mL (F) plastic
500 mL (G) glass
Spent AA Samples
8oz(AA1) glass jar
4 oz (AA2) glass jar
4 oz (AA2) glass jar
Preservation Method
4ฐC
HNO3 for pH <2
4ฐC
0.05 % H2SO<
4ฐC
HNO3 for pH <2
4ฐC
4ฐC
HNO3 for pH <2
4ฐC
4ฐC
4ฐC
HNO3 for pH<2
4ฐC
H,, SO, for pH <2
4ฐC
H2SO4 for pH<2
4ฐC
4ฐC
4ฐC
Analyte
Total As, Al, Fe, Mn
Dissolved As, Al, Fe, Mn
Dissolved As, Al, Fe, Mn
PH
TSS
Total As, Al, Fe, Mn
Alkalinity
pH
Turbidity
Sulfate
Fluoride
Hardness
NO37NO2-
TOC
Total As, Al, Fe, Mn
Water content, pH,
TCLP metals
Water content, pH,
TCLP metals
Hold Time
6 months
6 months
6 months
immediate
7 days
6 months
14 days
immediate
48 hours
28 days
28 days
6 months
28 days
14 days
6 months
14 days
14 days
TOC = total organic carbon.
TSS = total suspended solids.
10
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AP-09/15/98-IN-B-DUP
Date: 09/15/98 Time: 11a.m.
Collector's Name: Sample Collector
Location: Any Plant
Sample ID: AP-02/15/98-PF-B-DUP
Send to: Battelle
Analysis Required: Total As, Al, Fe, and Mn
Preservative: 0.05% sulfuric acid
Figure 3-1. Example of Sample Bottle Label
Express for the following week's sampling activity. Fig-
ure 3-2 shows photographs of a sample cooler with four
sample compartments and a color-coded instruction
sheet placed under the lid of the cooler.
3.3 Sampling Procedures
3.3.1 General Approach and
Sampling Schedules
One Battelle staff member and the EPA WAM traveled to
each plant to collect source water samples, meet plant
operators, solicit interest in participating in this year-long
sampling program, and obtain system design and oper-
ating information and historical water quality data. After
the plant selection, two Battelle staff members returned
to each plant to collect samples at selected sampling
locations and train the plant operator or a designated
POC to perform sampling and field arsenic speciation.
The remaining three preliminary sampling events and
long-term sampling events then were conducted by the
trained plant personnel. Residuals sampling, including
monthly collection of backwash and spent brine samples
during the resin regeneration at Plant A and a single
spent AA sampling event at Plants C and D also were col-
lected by the designated plant employees with detailed
instructions provided by Battelle over the telephone.
Table 3-2 summarizes the sampling activities conducted
at each plant.
During the preliminary and long-term sampling, sample
collection was conducted on a 4- or 8-week cycle, with
each week having unique sampling requirements.
Tables 3-3 (for Plants A and B) and 3-4 (for Plants C and
D) summarize the schedules for the initial source water,
the preliminary, the long-term, and the residual sampling.
After receipt of the weekly sample coolers, plant person-
nel began sampling activities at the selected locations on
the scheduled dates. Upon completion, all sample bot-
tles were sealed with tape and placed in the same cool-
ers for return shipment to Battelle by Federal Express.
Upon receipt of the samples, the designated Battelle
sample custodian immediately examined and compared
the conditions of all sample bottles with those indicated
in the chain-of-custody forms. Samples then were dis-
tributed to Battelle's ICP-MS laboratory and Wilson Envi-
ronmental Laboratories for chemical analyses.
Throughout the duration of the study, Battelle staff main-
tained frequent telephone contact with each plant to
ensure that all sampling activities were carried out as
planned. For example, after the scheduled arrival of
sample coolers, one Battelle staff member would call to
confirm the receipt of the coolers, answer any questions,
discuss irregular plant operations and unusual observa-
tions, and propose/suggest corrective actions. When
available, results of the chemical analyses also were dis-
cussed over the telephone and data sheets were sent
quarterly to the plants for review. Also, water usage and
historic water quality data were sent along with sample
coolers or transmitted via facsimile to Battelle for infor-
mation/evaluation.
3.3.2 Arsenic Field Speciation Procedure
The procedures for performing the field arsenic specia-
tion are shown in Figure 3-3 and are described as fol-
lows ("steps" refer to Figure 3-3):
Bottle A: A 400-mL disposable plastic beaker was
rinsed thoroughly with the water to be sampled.
The beaker then was used to collect a water sam-
ple and to fill bottle A with an aliquot of that sample
(step 3). If necessary, additional sample water was
added to the beaker after bottle A was filled to
complete arsenic speciation sampling.
Bottle B: A 60-mL disposable plastic syringe was
rinsed thoroughly with the water in the plastic
beaker by completely filling and emptying the
syringe (step 4). After attaching a 0.45-um disc
filter and wasting about 10 drops of the filtrate, the
syringe was used to filter the water sample from
the beaker and fill bottle B. Bottle B then was
tightly capped and vigorously shaken for about
15 seconds to allow thorough mixing of the filtered
water and sulfuric acid (step 5).
Bottle C: The protective caps on the top and bot-
tom of a resin column were removed and approx-
imately 40 mL of the water in bottle B was wasted
through the column. This initial 40 mL was used to
displace the water in the resin column and to
ensure attainability of a representative sample from
the column. The resin column then was positioned
11
-------
WARNING
Do not rinse or overflew bottles. Bซides
Figure 3-2. Photographs of a Typical Sample Cooler (with Four Sample Compartments) and a
Color-Coded Instruction Sheet
over bottle C, and the water from bottle B was
passed through the column until approximately
20 mL of the resin-treated sample had been
collected in bottle C (step 6).
The procedures described under the above three
bullets were repeated to obtain duplicate bottles A,
B, and C.
Upon completion, the individual performing the
speciation signed a chain-of-custody form (step 7).
All sample bottles (for arsenic speciation and other
water quality parameters), along with the signed
chain-of-custody form, were placed in the original
cooler with ice packs and shipped via Federal
Express to Battelle (step 8).
12
-------
Table 3-2. Summary of Sampling Activities at Plants A, B, C, and D
Sampling Activities
Initial source water sampling
Preliminary sampling
Long-term sampling
Spent AA sampling
Backwash and spent brine
sampling
Sampling
Frequency
Once
Weekly or
biweekly
Weekly1" or
biweekly
Once
4-week
Plants A and B
06/10/98
08/06/98 through 08/26/98
09/01/98 through 06/17/99
Not applicable
03/21/99 through 06/13/99
(Plant A only)
Plant C
06/1 1/98
08/05/98 through 09/16/98
09/30/98 through 06/09/99
12/29/98
Not applicable
Plant D
06/11/98
08/05/98 through 09/16/98
09/30/98 through 09/01/99
05/25/99
Not applicable
(a) Except for the holiday weeks of 11/23/98,12/21/98, and 12/28/98.
3.3.3 Backwash, Spent Brine, and
Spent AA Sampling Procedure
Backwash and spent brine samples were collected at
Plant A on a monthly basis starting on March 21, 1999.
When the IX tank was regenerated, eluate from each of
the four regeneration steps (i.e., backwash, brine regen-
eration, slow rinse, and fast rinse) was collected alter-
nately in two 32-gal buckets through a garden hose. A
stopwatch was used to measure the time elapsed to
assist in determining the start and end points of each
regeneration step. At the end of each regeneration step,
the content in the. bucket was thoroughly mixed, and a
portion of the water was transferred to sample bottles for
pH, TSS, total As, Al, Fe, and Mn,analyses.
Spent AA samples were collected from Plants C and D
during the medium replacement. At Plant C, AA samples
were collected from roughing tanks, TA1 and TA2. At
Plant D, AA samples were collected from the top, mid-
dle, and bottom sections of the roughing tank in train 1
(TB1). With a bed depth of 3.2 ft, the top, middle, and
bottom sections were defined as 0-0.5, 1.1-1.6, and 2.2-
2.7 ft from the top of the bed. The AA was vacuumed
from each section, placed in a container, and mixed thor-
oughly before a representative sample was collected.
The sample collection was performed by the plant POC
with assistance from a certified operator. When the sam-
ples arrived at Battelle, subsamples were sent to Wilson
Environmental Laboratories for TCLP testing. Another
portion of the AA samples were regenerated with caustic
Table 3-3. Summary of Sampling Schedule for Plants A and B
Water Sampling
Analvte
As (total)
As (total soluble)
As (particulate)
As(lll)
As(V)
Al (total)
Fe (total)
Mn (total)
Al (dissolved)
Fe (dissolved)
Mn (dissolved)
Alkalinity
Sulfate
NO3-NO2 (N)
TOG
Turbidity
Hardness
Ca Hardness
Mg Hardness
pH
TSS
Initial Source
Water Sampling
(Once)
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
Preliminary Sampling Cycle
Week
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W
W
W
W
W
W
W
W
1 Week 2
W
W
W
W
W'
W*
W*
W*
W*
W*
W*
W*
Week 3 Week 4
W
W
W
W
W
W
W
W
W
W
W
W
W
W
W
Long-Term
Sampling Cycle
Weekl Week 2 Weeks Week 4
W*
W*
W*
W*
W*
w*
W*
W*
W*
W*
W*
W
W
W
W
W
W
W
W
W
W
W
W
W*
W*
W*
W, RG
W, RG
W, RG
W, RG
W
W
W, RG
RG
W
W
W
W
W
W
W
: Duplicate samples collected and analyzed.
W = Water samples collected from the inlet and outlet locations.
RG = Regeneration wastewater samples collected at Plant A.
Empty cells indicate no samples taken.
13
-------
Table 3-4. Summary of Sampling Schedule for Plants C and D
Water Sampling
Analyte
As (total)
As (total soluble)
As (participate)
As (III)
As(V)
At (total)
Fe (total)
Mn (total)
Al (dissolved)
Fe (dissolved)
Mn (dissolved)
Alkalinity
Fluoride
Sulfate
NOyNO, (N)
TOG
Turbidity
PH
Hardness
Ca Hardness
Mg Hardness
TCLP Metals
Percent moisture
As (total)
Initial Source
Water Sampling
(Once)
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
Preliminary
Sampling Cycle
Week"! WeekS Weeks Week?
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W
W
W
W
W
W
W
W
W
W
W
W
W
W*
W*
W*
W*
W*
W
W
W
W
W
W
W
W
W
W
W
W
W
W
W
W
Long-Term
Sampling Cycle
Week"! Week3 Weeks Week 7
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W*
W
W
W
W
W
W
W
W
W
W
W
W
W
W*
W*
W*
W*
W
W
W
W
W
W
W
W
W
W
W
W
W
W
W
W
Spent AA
Sampling
(Once)
AA
AA
AA
= Duplicate samples collected and analyzed.
W a Water samples collected from the inlet, after Tank A, after Tank B, and outlet locations.
AA ซ Spent AA samples collected at Plants C and D.
Empty cells indicate no samples taken.
solutions to remove the adsorbed arsenic from AA.
Detailed experimental procedures are described in Sec-
tion 3.4.2.
3.3.4 Sampling Procedure for Other Water
Quality Parameters
All other water quality parameters identified in Tables
3-3 and 3-4 were analyzed using samples either in bot-
tles A, B, and C or in bottles provided by Wilson Environ-
mental Laboratories (i.e., bottles D, E, F, and G). All bot-
tles D, E, F, and G were filled directly from sample taps
and preserved according to the respective analytical
methods. These sample bottles along with bottles A, B,
and C were placed in the original coolers with ice packs
and shipped via Federal Express to Battelle.
3.4 Technical Approaches for
Special Studies
During the long-term evaluation studies, several obser-
vations were made on the performance of the treatment
processes at Plants A and D that suggested a need for
short-term special studies. At Plant A, arsenic break-
through was detected in the effluent before the IX resin
was regenerated; therefore, a revisit of the system,
especially its regeneration process, was made to en-
hance the understanding of the IX system performance.
At Plant D, a laboratory study using the spent and virgin
AA was designed to assist in evaluating the performance
of the AA system.
The following sections discuss the technical approaches
used for the special studies at Plants A and D, respec-
tively, including experimental setup, test procedures, and
sampling procedures.
3.4.1 Short-Term Special Study at Plant A
During June 12 to 14, 1999, Battelle staff performed a
resin regeneration study to evaluate the effectiveness of
the renegeration process and determine the quantities and
chemical characteristics of the regeneration residuals.
The fiowrate and duration of each regeneration step
were measured by continuously monitoring the eluate's
fiowrate and TDS levels using an Omega ACCUM-U-
FLO totalizer and a Hanna HI 9635 conductivity/TDS
meter (Hanna Instruments, Inc., Woonsockett, Rl), re-
spectively. The pH of the eluate also was monitored
using a VWR Model 2000 pH meter and a nonrefillable
combination pH electrode. All meters and probes were
14
-------
Step 1:
Go to sampling point
(Inlet, Pre-Filtration, or Outlet)
Step 2:
Put on gloves
Sfep 3;
Collect water sample
Preservative
(HNOs)
a) Avoid agitation
b) Fill bottle A
Important Note;
DO NOT RINSE ANY BOTTLES!!
THEY CONTAIN PRESERVATIVES!!
Step 4:
Prepare the syringe
Fill and empty syringe to rinse
Sfep 5;
Collect filtered sample
Preservative
(H2S04)
B
a) Refill syringe
b) Attach filter to syringe c) Fill bottle B
and waste 10 drops
d) Cap tightly; shake (about 15 seconds)
Step 6;
Collect resin-treated sample
a) Fill resin column from bottle B;
drain column to rinse; repeat
(waste approx. 40 mil)
A
c
minium!
Preservative
/
f
b) Drain column into bottle C;
repeat (collect approx. 20 ml)
Sfep 7:
Fill in all blanks on chain-of-custody form
Step 8:
Pack and ship samples
a) Tighten caps of all bottles b) Tape cooler before shipping
Figure 3-3. Instruction Sheet for Arsenic Field Speciation
15
-------
calibrated prior to use according to the manufacturers'
instruction manuals.
The test apparatus was set up as follows: (a) The eluate
from the resin column was directed through a garden
hose and the totalizer to a 250-mL plastic beaker holding
the TDS and pH probes, (b) The beaker was placed just
inside the rim of a 32-gal plastic bucket, allowing the
eluate to overflow, after measurements, into the bucket.
(c) Two 32-gal plastic buckets were used alternately dur-
ing the sampling, (d) A stopwatch was used to measure
the time elapsed.
The following test procedures were used for sampling
during the regeneration:
Collect one influent and one effluent sample.
Turn on the power and start the stopwatch after
water had entered the resin column.
Record the time elapsed, TDS, pH, temperature,
volume, and flowrate on a datalogger every 30 to
60 seconds.
Collect grab samples once every 4 to 6 minutes by
filling up sample bottles with the overflow from the
beaker.
Collect a composite sample from the bucket at the
end of each regeneration step.
Collect two influent and two effluent samples after
regeneration was complete and the system
returned to service.
Collect two influent and two effluent samples each
day on Day 2 and Day 3.
Place sample bottles in a cooler with ice packs and
have the cooler shipped via Federal Express to
Battelle at the end of the test.
The number of samples collected at each step is listed in
Table 3-5. All samples were analyzed for total As and
sulfate. Because the IX resins prefer sulfate ions to arse-
nic ions, and because sulfate was present in the water
(up to 25 mg/L), the sulfate content in the influent, efflu-
ent, spent regenerant, and rinse water was determined.
The percent recovery of arsenic from the regeneration
was calculated using Equation 3-1:
(3-1)
where: %R = percent recovery j
= the amount of arsenic recovered from
the resin column, g
= the amount of arsenic removed from
the source water, g.
Table 3-5. Sampling Schedule for the Special Study
at Plant A
Preregeneration
Regeneration
Post-
regeneration
Total
Tank
Activities
Service
Backwash
Brine
regeneration
Slow rinse
Fast Rinse
Service
Service
Service
Sampling
Time
Day 1
Day 1:
0-1 8 min
Day 1:
18-42 min
Day 1:
42-68 min
Day 1:
68-78 min
Day 1
Day 2
Day 3""
Number of Samples
Grab Composite
2
3
6
5
2
4
4
2
28
0
1
1
1
1
0
0
0
4
(a) The Day 3 samples were collected by the plant POC.
M.
was calculated using the arsenic concentration
and the volume of the eluate from each regeneration step;
^removed was estimated based on the water usage data
and arsenic concentrations in the inlet and outlet water.
3.4.2 Short-Term Special Study at Plant D
A special study was conducted on the AA system at
Plant D to determine AA's capacity for arsenic removal
under the field and laboratory conditions. The spent AA
sampling has been described in Section 3.3.3. A virgin
AA sample and five gallons of raw water were collected
and shipped to Battelle. Upon receiving these samples,
the following tests were performed by Battelle:
Test 1: Characteristics of the Spent AA
A subsample of each spent AA sample was sent to
Wilson Environmental Laboratories for TCLP testing.
Another subsample was digested with nitric acid and
analyzed for total arsenic. The resulting concentration
was compared with the concentration desorbed from the
spent AA using caustic solutions.
Prior to use, the spent AA samples were air-dried in
clean glass trays for several days and stored and
homogenized in glass bottles. A subsample of each air-
dried sample was analyzed for moisture content accord-
ing to Standard Method ASTM D2216.
Three subsamples of each air-dried AA sample (from the
top, middle, and bottom of the column) were weighed
(approximately 2.00 g) and digested using 100 mL each
of concentrated nitric acid according to EPA Method
3051. The digestate was analyzed for total arsenic. The
amount of arsenic recovered per unit dry weight from
each AA sample was calculated using Equation3-2:
16
-------
(3-2)
where: qe = Arsenic recovered, mg/g dry AA
C^ = arsenic concentration in digestate, mg/L
V = digestive fluid volume, L
Wdry = dry weight of AA, g.
Test 2: Regeneration of Spent AA Using
Caustic Solutions
Caustic solutions of 1-2% (by weight) NaOH have been
reported to be effective in stripping inorganic ions such
as fluoride, arsenic, and phosphate from spent AA (Chen
and Snoeyink, 1987). Higher NaOH concentrations (i.e.,
4%) have also been suggested for stripping arsenic
because arsenic is much more difficult to remove from
AA than fluoride (Clifford, 1999), thus a 4% NaOH solu-
tion was used in this study. Studies have also showed
that comparable regeneration results have been ob-
tained with 30 minutes to 3 days of contact time (Chen et
al., 1989). Therefore, the regeneration test was run for
approximately 16 hours.
Spent AA samples collected from the top, middle, and
bottom sections of the column were stripped with a 4%
NaOH solution to determine the amount of arsenic that
might be desorbed from each sample. The experiment
was conducted in duplicate at room temperature (about
22ฐC) according to the following procedures:
Weigh approximately 70 g of a wet spent AA
sample into one of six 250-mL plastic bottles
containing 150 mL of 4% NaOH solution.
Cap the bottles and place them on a tumbler for
overnight mixing (approximately 16 hrs).
Remove the contents from each bottle and filter
them through a ZAPCAP-S 0.45-um disposable
cellulose acetate membrane filter (Schleicher &
Schuell, Keene, NH).
Rinse the residual AA three times with a total of
200 mL Millipore Dl water and filter the rinsate.
Combine and mix the filtrate from each bottle and
analyze the sample for total arsenic (preserved with
nitric acid) and fluoride and sulfate (unpreserved).
The amount of arsenic, fluoride, and sulfate recovered
from the caustic wash was calculated using Equation 3-2
except that the digestive fluid volume was replaced by
the total volume of the NaOH solution and the rinse
water used in the experiment.
Test 3: Adsorption Isotherm Experiment
Isotherm tests were conducted to determine the capacity
of the virgin AA (Alcoa CPN type granular AA, 28 x 48
mesh) used at Plant D. To increase the initial As(V) con-
centration in the raw water from 50 ug/L to approx-
imately 500 ug/L, 450 uL of 1.0-ug/uL As(V) standard
solution was spiked to 1 L of raw water. A kinetic study
was performed to determine the time required to reach
equilibrium. A series of 250 mg of virgin AA was accu-
rately weighed, placed in a 250-mL plastic bottle con-
taining 200 mL of the spiked raw water, and adjusted to
the raw water pH of 7.7 ฑ 0.2. The bottles were placed
on a tumbler for 7 days at room temperature (-22 ฐC).
During the test period, the pH values of all test solutions
were periodically checked and adjusted to 7.7 ฑ0.2. After
1, 2, 5, 6, and 7 days, one bottle each was removed
from the tumbler and its content was decanted and
filtered through a ZAPCAP-S 0.45-um disposable cellu-
lose acetate membrane filter. The filtrate was collected
in a plastic bottle preserved with nitric acid for total arse-
nic analysis.
For the isotherm experiment, identical volumes of an
arsenic solution were exposed to different quantities of
AA. The control contained only arsenic solution, without
alumina. During the test period, the pH values of all test
solutions were periodically checked and adjusted to 7.7
ฑ0.2. Final arsenic concentrations were determined, and
the difference between test and control final concentra-
tions was attributed to adsorption onto AA. The proce-
dure for batch tests is as follows:
Pour 200-mL aliquots of arsenic-spiked raw water
into 250-mL plastic bottles with measured
quantities (100 to 1,000 mg) of granular AA.
Adjust the pH of solution in each bottle to 7.7 ฑ0.2.
Cap bottles and place them on the tumbler.
Remove bottles from the tumbler after 6 days and
filter their contents as described above.
Analyze filtrate samples for total arsenic
concentration.
3.5 Analytical Procedures
The analytical procedures used for this project were
described in Section 4.0 of the QAPP prepared by
Battelle (1998). Table 3-6 presents a summary of all
analytical methods used. All of the methods used are
standard EPA methods. Analyses of As, Al, Fe, and Mn
in water samples were accomplished by ICP-MS using
EPA Method 200.8. ICP-MS was chosen as the method
for As, Al, Fe, and Mn analyses because it has a low
method detection limit (MDL) and was a relatively low-
cost method (about $35/sample). ICP-MS analyses were
conducted on a Perkin Elmer Sciex Model 6000 equipped
with a crossflow pneumatic nebulizer and an automatic
17
-------
Table 3-6. Summary of Analytical Methods for Arsenic Treatment Study
Sample Matrix
Aqueous
Spent AA
Analyte
As (total)
Total Al
Total Fe
Total Mn
Alkalinity
PH
Turbidity'"'
Hardness
so4*-
F-
TOC
NO,-/NO2-
Moisture content
pH
TCLP metals
Total As
Total Fe
Method
EPA 200.8
EPA 200.8
EPA 200.8
EPA 200.8
EPA 310.1
EPA 150.1
EPA 180.1
EPA 215.1/242.1
EPA 375.4
EPA 340.2
EPA 415.1
EPA 353.2
ASTMD2216
SW-846 9045
SW-8461311
SW-846 3051, 6020
SW-846 3051, 6020
Analytical Laboratory
Battelle ICP-MS
Battelle ICP-MS
Battelle ICP-MS
Battelle ICP-MS
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
Wilson Environmental
(a) Turbidity was analyzed in the laboratory, not on site.
sampler. Yttrium (88'9Y) was added to all samples as an
internal standard to correct for instrument drift. Because
arsenic is monoisotopic, all measurements were made at
a mass/charge ratio of 75. To eliminate an appreciable
interference from a chloride molecular species (40Ar3SCI),
all ion current data at m/e 75 were corrected using
chloride measurements in all samples, and the MDL
was 0.1 ug/L As. All the unfiltered water samples (i.e., in
bottle A) were digested using EPA Method 200.8 prior to
analysis. Filtered water samples (i.e., in bottles B and C)
were analyzed directly without digestion. Wilson Environ-
mental Laboratories was subcontracted to perform all
other chemical analyses. QA/QC of all methods followed
the guidelines provided in the QAPP (Battelle, 1998) and
the data quality in terms of precision, accuracy, MDL, and
completeness is discussed in Section 5.0 of this report.
18
-------
4.0 Results and Discussion
This section presents the results of the treatment plant
selection process, which resulted in the selection of two
IX plants, referred to as Plants A and B, and two AA
plants, referred to as Plants C and D. In addition, results
from water and residuals sampling and analysis at
Plants A, B, C, and D are summarized and discussed.
Complete analytical results from long-term water sam-
pling at Plants A, B, C, and D are presented in Appen-
dices A.1, B.1, C.1, and D.1, respectively.
4.1 Plant Selection
The plant selection process consisted of identifying po-
tential treatment facilities, contacting these facilities via
telephone, and conducting initial site visits during which
source water samples were collected and analyzed. Ini-
tially, a list was prepared consisting of two potential IX
treatment facilities and three AA facilities (Plants A, B, C,
D, and E; see Table 4-1 for plant details). Staff at these
potential candidate facilities were contacted to discuss
the study and determine details of plant operation.
All plants except Plant E were selected for the sub-
sequent phases of the study. Results from source water
sampling at each of these four facilities are presented in
the following subsections.
4.2 Plant A
Water and residual samples were collected and ana-
lyzed at Plant A, an IX plant, during three phases of the
study.
The first phase consisted of source water sampling used
to help determine if the plant should be considered for
subsequent phases. Source water sampling at Plant A
was performed in June 1998. Following source water
sampling, the second phase of the study was initiated.
This second phase consisted of weekly water sampling
over a 4-week period in August 1998 and was designed
to determine if the sampling locations and proposed
water quality analyses were appropriate for the third
phase, long-term evaluation. The third phase was ini-
tiated in September 1998 and continued through June
1999. This long-term evaluation consisted of weekly
sampling and analysis of raw and finished water. Also,
arsenic speciation sampling was conducted every fourth
week. The third phase of the study also included sam-
pling and analysis of residuals. Backwash and spent
brine samples were collected monthly beginning in March
1999.
4.2.1 Plant A Description
The IX system in Plant A supplies treated water to a
school and is used by approximately 350 students and
teachers. The IX system was installed by Lowry Engi-
neering at Unity, ME in August 1990 and was designed
based on an average daily demand (ADD) of 1,200
gallons per day (gpd) of water. The system is operated
intermittently and the treated water is stored in a storage
tank to supply daily demand. This system consists of a
Filox oxidizing filter followed by an A300X IX resin
system. Figure 4-1 is a schematic diagram of the treat-
ment process, which consists of the following major
components:
Table 4-1. Initial List of Treatment Facilities Identified for the Study
Plant ID
A
B
C
D
E
Process
IX
IX
AA
AA
AA
Source Water Arsenic
Concentration (ug/L)
23-34 (effluent)
52
42
40-80
51-63
Sampling
Date
July 1995 -March 1997
November 12,1995
December 30, 1 994
NA
1988
Population
Served
350
35
600
200
97 families
Historical Data
Limited
NA
Yes
Yes
Yes
Source
Water Type
GW
GW
GW
GW
GW
NA = not available; GW = groundwater.
19
-------
From well
MONTHLY
As (total), As (III), As (V),
Hardness, Turbidity, NO3/NO2
Flow Totalizer
Plant A
Anion Exchange
Design Flow: 4 gpm
SEPTIC TANK
FILOX FILTER
i
i
i
i
As (total), pH,TSS
i
i
i
i
Regeneration
IX System
Note:
The outlet samples were planned to be
collected at the DC system outlet, however,
were actually collected after the storage tank.
STORAGE TANK
(2,400 GAL)
WEEKLY
As (total), Alkalinity, pH,
Total ALTotal Fe, Total Mn, SO4
0
LEGEND
Water Sampling
Location
Regeneration/Backwash
Sampling Location
Unit Process
Disinfectant Addition
Point
Proposed sampling location
As (total), As (III), As (V),
Hardness, Turbidity, NO3/NO2
To the distribution system
Figure 4-1. Process Flow Diagram and Sampling Locations at Plant A
r Actual sampling location
As (total), Alkalinity, pH,
Total Al/Total Fe, Total Mn, SO4
20
-------
Intake. The raw water is pumped from an 800-ft-
deep bedrock well located in the eastern vicinity of
the school building (Well 1) and flows directly into
the Filox filter. Well 1 was drilled in 1987-88 and
has a 6-inch steel casing. Another well, Well 2, is
located about 125-150 ft northeast of Well 1. Well 2
was drilled in 1957 with a depth of 250 ft and an
8-inch steel casing, but is not currently in use.
Oxidizing Filter. The Filox filter was installed to
oxidize possible arsenite [As(lll)] in water to arse-
nate [As(V)J. As shown in Figure 4-2, the Filox
filter is a 65-inch-long by 14-inch-diameter Poly-
glassฎ vessel filled with a 22.5-inch-deep MnO2-
based medium. Because the source water contains
primarily As(V) and almost no As(lll), the oxidizing
filter has functioned only as a prefiltration unit to
remove particulate from the raw water. The Filox
filter is backwashed every 3 days with treated
water from the storage tank. The backwash lasts
for 15 to 20 minutes at a flowrate of 11 gallons per
minute (gpm).
Anion Exchange System. After passing through
the Filox filter, water flows into the A300X resin
column. The A300X column has the same dimen-
sions and configuration as the Filox column
except that it is filled with a 22.5-inch-deep Purolite
A-300 anionic resin bed (Figure 4-2). The Purolite
A-300 anionic resin (The Purolite Company, Bala
Cynwyd, PA) is a strongly basic gel IX resin in
chloride form. Typical physical and chemical
properties of this resin are presented in Table 4-2.
Detailed technical data on the resin can be found
in Appendix A.2. At a design flowrate of 4 gpm, the
hydraulic loading rate to the filter is 4 gpm/ft2 and
the EBCT is 3.7 minutes.
Resin Regeneration. The original design called
for a regeneration frequency of every 3 months
using a brine solution at 10 Ib salt/ft3 resin. Because
early arsenic breakthrough was detected during this
study, a more frequent (once every 4 weeks) regen-
eration schedule was recommended to the plant
personnel and has been implemented since March
1999. Discussion on the resin regeneration is pro-
vided in Section 4.2.4.4. The brine solution is stored
in a 35-inch-tall by 18-inch-diameter tank. The
regeneration of the A300X resin column consists of
four steps: upflow backwash, downflow brine,
downflow slow rinse, and downflow fast rinse. The
approximate flowrate and duration of each regener-
ation step are listed in Table 4-3 and were verified
during the special study at Plant A.
Chlorination. To disinfect the water, chlorine is
added to the treated water through a conventional
chemical feed pump.
Storage Tank. The treated, chlorinated water is
stored in a 2,400-gallon steel tank, and is pressur-
ized through two booster pumps and two pressure
tanks before it enters the school distribution
system.
The cost of the system at the time of installation was
$6,886 with an additional $2,000 installation fee.
4.2.2 Initial Source Water Sampling
Source water sampling was conducted during the initial
site visit on June 9, 1998. Table 4-4 presents the analyt-
ical results from the source water sampling. The average
total arsenic concentration was 23.1 ug/L. Particulate
arsenic was less than detection; thus, soluble arsenic,
primarily As(V), accounted for the majority of the total
arsenic. The average As(III) concentration was 0.5 ug/L.
4.2.3 Preliminary Sampling
During the preliminary sampling phase of this study,
water samples were collected only at the inlet and the
outlet of the system because of the lack of a sampling
tap after the oxidizing filter. The inlet samples were col-
lected from a tap located on the pipe connecting to the
well. The outlet samples, originally planned to be col-
lected between the resin tank and the storage tank, were
actually collected after the storage tank. The outlet sam-
pling location was changed because it was difficult to
draw water samples from the resin tank outlet when the
system was turned off. The sampling locations and the
associated sample analyses performed at each location
are shown on Figure 4-1.
Alkalinity, sulfate, turbidity, pH, total hardness, nitrate-
nitrite, total Al, total Fe, total Mn, and total arsenic were
analyzed on samples collected every week at both sam-
pling locations. Arsenic speciation was conducted once
during the preliminary study on samples collected from
both sampling locations. Soluble and particulate arsenic
were determined as part of the arsenic speciation, as
were the species (arsenite and arsenate) making up the
soluble fraction of the total arsenic. Dissolved Al, Fe, and
Mn concentrations at each sampling location were deter-
mined using a sample from bottle B of the arsenic spe-
ciation kits. Table 4-5 presents the results of the 4-week
preliminary sampling period.
As shown on Table 4-5, inlet total arsenic concentrations
ranged from 17.8 to 26.6 ug/L. Arsenic in the source
water was primarily As(V) and contained almost no As(lll)
and particulate arsenic, consistent with the results of the
initial source water sampling (Table 4-4). On August 6,
1998, the total arsenic concentration in the finished water
21
-------
Use 18x35 Brine Tank with Fleck 2300
Brining Valve Assembly for Both Resin Filters
Fleck 2900 Control
15 gpm backwash only
14x65 Polyglass
FILOX bed
22 J" deep
Gravel
Fleck 2900 Control
3 gpm backwash
03 gpm brine
14x65 Polyglass
Anion Resin Bed
22 J" deep
Gravel
FILOX Filter Unit
Anion Exchange Unit
Figure 4-2. Cross Section of Filox Filter and A300X IX Filter at Plant A (Source: Lowry Engineering,
Inc., 1990)
22
-------
Table 4-2. Typical Chemical and Physical
Characteristics of Purolite A-300
Anion Exchange Resin
Polymer Structure
Functional Groups
Physical Appearance
Ionic Form
Screen Size, U.S. Std.Mesh
(Wet)
Particle Size Range
Uniformity Coefficient
Water Retention
Swelling
pH Limitations
Temperature Limitations
Chemical Resistance
Whole Clear Beads
Shipping Weight
Total Capacity
Polystyrene crosslinked with
divinylbenzene
R(CH3)2(C,H4OH)N*
Clear spherical beads
Chloride
16-50
+16 mesh < 5%; -50 mesh < 1%
1.7 maximum
40-45%
Salt-OH, 10%
None
185BF maximum
Unaffected by dilute acids, alkalis,
and most solvents
92% minimum
44 Ib/ff (705 g/L)
1.45-1.6 meq/mL min. Volumetric;
3.5-3.7 meq/gm min. Weight
Table 4-3. Regeneration Schedule of the A300X
Resin Column at Plant A
Regeneration
Step
Backwash
Brine
Slow Rinse
Fast Rinse
Flow
Direction
Upflow
Downflow
Downflow
Downflow
Duration
(min)
18
24
18
10
Flowrate
(gpm)
5.0
1.0
1.0
3.2
exceeded the concentration in the raw water, indicat-
ing arsenic breakthrough. Therefore, the IX column was
regenerated immediately after the samples had been col-
lected. Over the following 3 weeks, the arsenic concen-
trations in the finished water decreased slowly from 7.2 to
0.6 ug/L, corresponding to 62% to 98% arsenic removal.
At the time, it was not clear why the IX column continued
to leak even about 2 weeks after the resin regeneration.
Further study revealed that this "leakage" actually was
due to an artifact caused by the arsenic already present
in the 2,400-gal storage tank located just upstream from
the sampling point. The storage tank contained relatively
high arsenic water before the regeneration and was
replenished by the low arsenic water produced after the
regeneration. Therefore, the arsenic concentrations in the
effluent samples gradually decreased to low levels de-
pending on how quickly the storage tank was replenished.
It is expected that the water at the resin tank outlet imme-
diately after the resin regeneration contained even lower
arsenic concentrations (i.e., <1.0 ug/L). This hypothesis is
being verified by a short-term special study.
During the preliminary sampling period, the inlet alka-
linity concentrations ranged from 69 to 92 mg/L (as
CaCO3), and the inlet sulfate concentrations ranged from
23 to 25 mg/L. According to the selectivity sequence dis-
cussed in Section 1.1.3.1, an SBA resin prefers sulfate
over HAsO42~ and H2AsO4~; HCO3~ is less preferred than
HAsO/~ but has a similar affinity to the resin as H2AsO4~.
Clifford and Rosenblum (1982) found that the presence
of 720 mg/L sulfate reduced arsenic removal by more
than 50%. When arsenic broke through the IX column on
August 6, 1998, both sulfate and alkalinity (mainly HCO3"
at a neutral pH) showed little removal (20-25%). After
resin regeneration, sulfate was consistently reduced to
Table 4-4. Source Water Analytical Results at Plant A (June 9, 1998)
Parameter
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Total Al
Total Fe
Total Mn
NO3-N02(N)
TOC
As (total)
As (total soluble)
As (particulate)
As(lll)
As(V)
Unit
mg/L*"
mg/L
NTU
mg/Lw
mg/L(a!
mg/L1"
Mg/L
Mg/L
ug/L
mg/Llbl
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Primary
Sample
84
20
0.06
7.6
100
88.9
10.9
<400
<30
<20
0.75
1.1
22.5
24.6
<0.1
0.4
24.2
Duplicate
Sample
84
20
0.06
7.6
98
87.4
10.7
<400
40
30
0.78
1.1
23.6
24.4
<0.1
0.6
23.8
Average
84
20
0.06
7.6
99
88.2
10.8
<400
30
20
0.77
1.1
23.1
24.5
<0.1
0.5
24.0
(a) As CaCO3.
(b) Combined NO3-N and NO2-N.
NTU = nephelometric turbidity units.
23
-------
Table 4-5. Analytical Results from Preliminary Sampling at Plant A (August 6,1998 to August 26,1998).
Sampling Date/Location
Parameter
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (paniculate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
Units
mg/Lm
mg/L
NTU
mg/L""
mg/L""
mg/L'1"
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
IN
92
25
0.3
7.7
82.1
72.7
9.5
0.5
17.8
20,0
18.8
19:1
0.9
ND
ND
18.8
19.1
9.7
13.9
42.8
68.1
2,9
2.7
1.7
0.7
ND
ND
3.0
2.5
8/6/98""
OU
71
20
<0.1
7.5
62.2
54.4
7.7
0.8
23.2
21.3
22.1
22.7
ND
ND
ND
22.1
22.7
9.8
16.6
0.3
4.8
0.3
0.4
2.4
ND
ND
0.2
0.2
8/11/98
IN
69
24
22
<0.1
<0.1
7.3
7.3
68.0
68.0
60.4
60.4
7.5
7.3
0.7
0.7
19.0
NS
NS
NS
NS
30.8
31.8
1.5
NS
NS
NS
OU
23
<5
<5
<0.'l
7.0
6.9
69.0
71.0
61.7
62.9
7.5
7.6
0.5
0.6
7.2
NS
NS
NS
NS
18.2
1.0
1.6
NS
NS
NS
8/18/98
IN
72
23
<0.1
7.5
NS
NS
NS
NS
26.0
NS
NS
NS
NS
158
37.0
2.6
NS
NS
NS
OU
41
<5
<0.1
7.4
NS
NS
NS
NS
1.9
NS
NS
NS
NS
19.7
16.0
1.3
NS
NS
NS
8/26/98
IN
76
24
NS
7.3
NS
NS
NS
NS
26.6
NS
NS
NS
NS
64.5
47.0
6.0
NS
NS
NS
OU
67
<5
NS
7.4
NS
NS
NS
NS
0.6
NS
NS
NS
NS
25.0
ND
0.4
NS
NS
NS
(a) Samples were taken prior to resin regeneration.
(b) As CaCO,.
IN = inlet.
OU = outlet.
NS = not sampled.
ND = not detected.
<5 mg/L throughout the subsequent 3 weeks. However,
the alkalinity was reduced by 67%, 43%, and 12%, re-
spectively, showing a decreasing trend with time. This
decreasing trend probably was caused by the fact that
the less-preferred bicarbonate was replaced from the
resin by the more preferred sulfate and arsenic ions. The
pH values ranged from 7.3 to 7.7 in the inlet and 7.0 to
7.5 in the outlet. Because the IX process is not pH
sensitive in the range of pH 6.5 to 9.0 (Section 1.1.3.1),
the effect of inlet pH on the IX process is insignificant.
The slightly lower pH value at the outlet presumably was
caused by the removal of alkalinity.
Iron compounds can clog and foul IX resins, thereby
lowering the arsenic removal capacities and reducing the
water throughput. However, at Plant A, both total and
dissolved Fe and Mn concentrations were very low.
Therefore, the effects of Fe and Mn on the process were
insignificant.
Based on the results of the preliminary sampling effort,
no changes were made to the approach for the long-term
evaluation. Sampling locations and primary analytes re-
mained unchanged.
24
-------
4.2.4 Long-Term Sampling
Long-term sampling and analysis consisted of a total of
37 weeks of sampling and included 10 arsenic speciation
sampling events. During the long-term sampling phase,
water samples were collected at the same two locations
that were used during the preliminary sampling phase:
inlet and outlet (Figure 4-1). Alkalinity, sulfate, turbidity,
pH, total aluminum, total iron, total manganese, and total
arsenic analyses were performed on samples collected
each week. Arsenic speciation sampling was conducted
10 times during the long-term sampling phase on samples
collected from each sampling location. Dissolved alum-
inum, iron, and manganese concentrations at each sam-
pling location were determined monthly using a sample
from bottle B of the arsenic speciation kits. Additionally,
residual sampling was performed during this phase and
consisted of collection and analysis of backwash waste-
water and spent brine from the regeneration of the A300X
column. The following subsections summarize the ana-
lytical results for arsenic, other water quality parameters,
and backwash/regeneration wastewater.
4.2.4.1 Arsenic
Table 4-6 provides a summary of the arsenic analytical re-
sults collected from the inlet and outlet locations at Plant A.
Total arsenic concentrations at the inlet varied widely from
23.3 ug/L to 59.2 ug/L and averaged 40.6 ug/L. Consistent
with previous phases of the study, particulate arsenic con-
centrations were low, averaging 0.4 ug/L and 0.5 ug/L at
the inlet and outlet sampling locations, respectively. As(lll)
concentrations averaged 0.7 ug/L at the inlet and 0.2 ug/L
at the outlet, indicating that As(V) made up the majority of
the soluble arsenic.
The effluent arsenic concentration ranged from 0.7 to as
high as 82 ug/L, which exceeded the corresponding inlet
arsenic concentration and the current 0.050 mg/L MCL
level. This chromatographic peaking, most likely was
caused by the sulfate in the source water. After two
3-month regeneration cycles and one 6-week regener-
ation cycle, it was determined that the system should be
regenerated more frequently. The effluent data collected
since April 18, 1999 indicated that if the system was
regenerated every 4 weeks or less, the system would be
able to achieve arsenic effluent levels of less than 5 ug/L.
Again, the column leak, which was observed during the
preliminary sampling, still existed, as indicated by the data
collected on March 23, May 18, and June 14 through 17,
1999. Because the effluent sampling location did not
change throughout the study, the reason for the column
leak was again attributed to the storage tank (see Sec-
tion 4,2.3). Figure 4-3 is a graph showing the total arse-
nic concentrations at the inlet and outlet of the IX column
and removal percentages during the long-term sampling.
Based on the water usage data recorded at each regen-
eration event since 1994 (see Appendix A.4), the run
length of each regeneration cycle is calculated and plotted
in Figure 4-4 both in gallons and in BV. Bed volume was
calculated by dividing the volume of water processed by
the volume of the resin bed (2 ft3 or 14.96 gal). With the
3-month regeneration schedule (before March 1999), the
run length varied from 5,760 to 9,670 BV with an average
of 7,890 BV. With the 4-week regeneration schedule, the
run length was significantly shortened, ranging from 2,220
to 3,780 BV with an average of approximately 3,000 BV.
This run length is reasonable compared with the 4,200
BV and 2,800 BV reported by Clifford and Lin (1986) and
Hathaway and Rubel (1987), respectively.
Assuming an average daily demand of 1,200 gpd, a
3000-BV cycle (equivalent to 44,880 gal) would last for
37 days. However, due to variations in water demand
with the school schedule (e.g., low water demand during
summer when school is dismissed), the regeneration
frequency based on total flow rather than time of oper-
ation was recommended in place of a time schedule.
Table 4-6. Summary of Arsenic Analytical Results at Plant A (September 1, 1998 to June 17, 1999)
Parameter Sampling Location
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Units
ug/L
Mg/L
Mg/L
ug/L
Mg/L
ug/L
ug/L
ug/L
ug/L
ug/L
Number of
Samples
47
47
20
20
20
20
20
20
20
20
Minimum
Concentration
23.3
0.7
30.8
0.9
0
0
0.1
0
30.2
0.8
Maximum
Concentration
55.4
81.5
60.9
97
3.4
5.9
1.4
0.5
60.2
96.7
Average
Concentration
40.6 '
19.0
45.9
18.0
0.4
0.5
0.7
0.2
45.2
17.8
Standard
Deviation
8.0
20.3
9.0
29.1
1.0
1.5
0.3
0.2
9.1
29.1
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
25
-------
100%
50%
-50%
rt
-100%
-150%
-200%
08/01/98 08/31/98 09/30/98 10/30/98 11/29/98 12/29/98 01/28/99 02/27/99 03/29/99 04/28/99 05/28/99 06/27/99 07/27/99
-<> --Inlet As
Reg 3/21/99
Outlet As
Reg 4/1 8/99
Reg 8/20/98
Reg 5/1 6/99
Reg 11/10/98
Reg 6/13/99
- Reg 2/6/99
X % Removal
Figure 4-3. Total Arsenic Analytical Results during Long-Term Sampling at Plant A
160
140-
120
BO
I 10ฐ
o
o
1 80
|
1 ซ0
B
40
20-
Anion exchange resin regenerated every three months
before March 1999 and every 4-6 weeks afterwards
10,000
8,000
6,000
53
4,000 |
--2,000
09/23/94 09/23/95 09/22/96 09/22/97 09/22/98 09/22/99
Regeneration Date
Figure 4-4. Water Treated between Regenerations of the IX System at Plant A
26
-------
4.2.4.2 Other Water Quality Parameters
In addition to arsenic analysis, other water quality param-
eters were analyzed to provide possible insight into the
chemical processes occurring at the treatment facility.
Table 4-7 summarizes the analytical results for several
water quality parameters obtained during the long-term
sampling.
Inlet sulfate concentrations ranged from 19 to 28 mg/L
with an average of 23.7 mg/L. As shown on Figure 4-5,
sulfate concentrations were reduced to <5 mg/L at the
outlet after the column was properly regenerated. Just
after the arsenic breakthrough, the effluent sulfate con-
centrations increased rapidly, approaching but never
exceeding their influent levels. This sharp breakthrough
is typical for a most preferred species like sulfate (Clifford,
1999). Because sulfate is more preferred than arsenate
by the resin, it can elute arsenate from the resin, causing
chromatographic peaking, as observed during the long-
term sampling.
Figure 4-6 plots the inlet and outlet alkalinity concentra-
tions and pH throughout the long-term sampling. Alkalin-
ity concentrations ranged from 61 to 93 mg/L (as CaCO3)
in the inlet with an average of 84.7 mg/L. The alkalinity
was partially removed by the treatment, resulting in its
outlet concentrations ranging from 21 to 92 mg/L with an
average of 74.6 mg/L. Because bicarbonate is a less-
preferred ion, it broke through earlier than sulfate and
arsenic. The pH values ranged from 7.2 to 7.8 in the inlet
with an average of 7.5. After the treatment, the pH val-
ues were slightly reduced, ranging from 7.0 to 7.7, pre-
sumably due to the removal of some alkalinity.
During the long-term sampling, the turbidity was low,
averaging 0.1 NTU at both the inlet and the outlet. Total
hardness also was low, ranging from 64 to 83.9 mg/L (as
CaCO3). As expected, the hardness was not removed by
the IX column and remained constant at the inlet and the
outlet. Nitrate-nitrite concentrations of the inlet water were
very low and thus did not have any significant impact on
arsenic removal.
The maximum total Al, Fe, and Mn concentrations were
105, 80.2, and 3.1 ug/L, respectively, at the inlet, and 60,
117, and 1.4 ug/L, respectively, at the outlet. As ex-
pected, the low metal concentrations of these cations did
not have any effects on arsenic removal.
4.2.4.3 Backwash/Regeneration Wastewater
Backwash wastewater and spent brine were sampled on
August 6, 1998 and on March 21, April 18, May 16, and
June 13, 1999. Composite samples were collected from
each of the four regeneration steps (i.e., backwash, brine
Table 4-7. Summary of Water Quality Parameter Analytical Results at Plant A (September 1, 1998 to June 17, 1999)
Parameter
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Nitrate-Nitrite
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
Sampling
Location
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Units
mg/L
mg/L
mg/L
mg/L
NTU
NTU
z
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Number of
Samples
47
47
47
47
20
20
47
47
20
20
20
20
47
47
47
47
47
47
20
20
20
20
20
20
Minimum
Concentration
61
21
19
2.5
0.05
0.1
7.2
7.0
64
61
0.3
0.1
5.5
5.5
15
15
0.3
0.3
3.9
5.5
11.5
15
0.3
0.3
Maximum
Concentration
93
92
28
25
0.3
0.1
7.8
7.7
83.9
79.0
0.8
3.3
105
60
80.2
117
3.1
1.4
12.9
19.5
15.6
15
1.2
2.7
Average
Concentration
84.7
74.6
23.7
9.5
0.1
0.1
7.5
7.5
69.5
67.3
0.5
0.7
16.7
10.5
21.3
19.4
0.9
0.5
5.8
6.2
14.9
15
0.5
0.5
Standard
Deviation
7.4
16.9
1.8
9.0
0.1
0
: 0.1
0.2
6.7
5.0
0.1
0.9
15.7
8.4
14.2
15.9
0.7
0.3
1.7
3.1
0.8
0
0.3
0.6
One-half of the detection limit was used for calculating concentrations of nondetect samples.
Primary and duplicate samples were averaged for calculations.
27
-------
2
SO
40
30
I 20 J
10
100%
08/01/98 08/31/98 09/30/98 10/30/98 11/29/98 12/29/98 01/28/99 02/27/99 03/29/99 04/28/99 05/28/99 06/27/99
Date
-20%
-40%
-60%
-80%
-100%
07/27/99
--O---Inlet Sulfate *Outlet Sulfate Reg8/6/98 Reg 11/10/98 Reg2/6/99
Reg3/21/99 Reg4/18/99 Reg5/16/99 Reg6/13/99 *%Removal
Figure 4-5. Inlet and Outlet Sulfate Concentrations and Percent Removal at Plant A
200
160
1
U 120
80
0 J
6.5
6.0
08/01/98 08/31/98 09/30/98 10/30/98 11/29/98 12/29/98 01/28/99 02/27/99 03/29/99 04/28/99 05/28/99 06/27/99 07/27/99
Date
--ซ- -Inlet alkalinity *Outlet alkalinity Reg 8/6/98 Reg 11/10/98
Reg 2/6/99 Reg 3/21/99 Reg 4/18/99 Reg 5/16/99
Reg 6/13/99 - - A Inlet pH A Outlet pH
Figure 4-6. Inlet and Outlet pH and Alkalinity Analytical Results at Plant A
28
-------
regeneration, slow rinse, and fast rinse). Analytical results
of these sampling events are summarized in Table 4-8.
As expected, the majority of arsenic was eluted from the
column during the brine regeneration; the arsenic concen-
trations ranged from 1.83 to 38.5 mg/L with an average of
15.6 mg/L. The arsenic concentrations in the elutes from
the backwash, slow rinse, and fast rinse averaged 59.4,
1,332, and 108 ug/L, respectively. The arsenic concentra-
tions along with the respective volumes were used to
calculate the mass of arsenic recovered from the regen-
eration to determine the regeneration efficiency (to be
discussed in Section 4.2.4.4). The elevated pH value ob-
served during the brine regeneration is presumably due
to the elution of bicarbonate ions from the resin column.
4.2.5 Special Study at Plant A
During June 12 to 14, 1999, a special study was per-
formed to evaluate the regeneration efficiency and to
determine the quantity and chemical characteristics of
the regeneration residuals.
Figure 4-7 plots total arsenic, TDS, and sulfate concen-
trations vs. time during the regeneration process. For the
first 24 minutes during backwash and the initial stage of
brining, all three parameters stayed at low levels. After-
wards, TDS concentrations increased sharply and reached
a maximum level of 26.1 mg/L. Meanwhile, sulfate con-
centrations jumped from about 20 mg/L to as high as
24 g/L. Arsenic also was eluted with sulfate; arsenic
concentrations increased sharply from less than 1 mg/L
to more than 77 mg/L. Figure 4-7 also seems to indicate
that arsenic was easier to elute than sulfate, most likely
due to the selectivity reversal in the high-ionic strength
(>1 M) environment (Clifford, 1999). The ease of regen-
eration is a strong point in favor of IX as compared to
AA.
Figure 4-8 indicates that a flowrate of 3.0 gpm was ap-
plied to the backwash and fast rinse, which is lower than
the 5 gpm specified in the service manual, and that
approximately 1 gpm was maintained during the brine
regeneration and slow rinse. The pH of the eluate was
close to neutral (-7.5) during backwash, increased to up
to pH 9.0 after the introduction of the brine solution, and
returned to neutral by the end of the process. Again, the
change in the pH value is probably related to bicarbon-
ate desorption from the column.
Table 4-8, Summary of Analytical Results from Backwash/Regeneration Samples at Plant A
(August 6, 1998 to June 13, 1999)
Parameter
Backwash
pH
TSS
Total As
Total Al
Total Fe
Total Mn
Brine Rinse
PH
TSS
Total As
Total Al
Total Fe
Total Mn
Stow Rinse
PH
TSS
Total As
Total Al
Total Fe
Total Mn
Fast Rinse
PH
TSS
Total As
Total Al
Total Fe
Total Mn
Units
mg/L
ug/L
ug/L
Pg/L
Pg/L
mg/L
M9/L
Pg/L
Pg/L
M9/L
mg/L
yg/L
pg/L
pg/L
Pg/L
mg/L
pg/L
P9/L
pg/L
pg/L
Number of
Sample Events
5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
5
5
5
5
5
5
Minimum
Concentration
7.2
6.0
28.9
86.4
264
15.3
8.1
6.0
1,830
5.5
43.5
2.3
7.6
0.5
253
13.5
15.0
1.6
7.0
0.5
6.9
5.5
3.7
1.3
Maximum
Concentration
7.6
24.0
74.4
847
1,982
59.8
8.9
13.0
38,522
28.0
445
3.4
8.7
22.0
3,060
236
1,567
42.0
8.4
4.0
356
30.3
15.0
9.5
Average
Concentration
7.4
14.0
59.4
432
1,102
40.2
8.5
9.0
15,623
20.5
207
3.0
8.1
9.6
1,332
65.2
336
12.6
7.7
1.2
108
13.5
11.8
4.7
Standard
Deviation
0.1
8.5
18.5
325
733
19.4
0.3
2.9
15,109
8.9
153
0.5
0.4
10.2
1,084
96.3
688
16.6
0.5
1.6
141
10.0
5.0
3.8
29
-------
100.00
90.00 -
80.00 -
70.00 -
g> eo.oo -
^ j3 50.00 -
% 40.00
30.00 -
20.00 -
10.00 -
0.00-
Backwash
Brine and slow rinse
Fast rinse
30.00
-- 25.00
- - 20.00
-- 15.00 s
- - 10.00
- - 5.00
0.00
10 20 30 40 50 60
Time elapsed, minutes
70 80
90
Figure 4-7. TDS, Total Arsenic, and Sulfate during the IX System Regeneration at Plant A (June 13,1999)
en
of
50.00
40.00 -
30.00 -
20.00 -
10.00 -
0.00-
10 20
30 40 50 60
Time elapsed, minutes
80 90
Figure 4-8. TDS, TSS, pH, and Flowrate during the IX System Regeneration at Plant A (June 13, 1999)
30
-------
Based on the water usage data and arsenic concentra-
tions in the inlet and outlet, the mass of arsenic removed
from the raw water was estimated and is presented in
Table 4-9 (see data listed under June 13,1999). Further-
more, the amount of arsenic recovered from the regener-
ation also was calculated using the arsenic concentrations
and the volume of the eluate from each regeneration step.
The percent recoveries of arsenic calculated by Equation
3-1 were 71.9-78.5%. Substituting the arsenic for sulfate,
the percent recovery of sulfate was 78.7%.
Table 4-9 also presents the percent recoveries of arse-
nic from previous regeneration events. Excluding the data
of March 21, 1999, the percent recoveries ranged from
66.5% to 85.5% with an average of approximately 75%.
This average value is somehow lower than the reported
values (85-100%) (Clifford, 1999), which could be due to
aged resin or the grab sampling.
4.3 PlantB
Water samples were collected and analyzed at Plant B,
an IX plant, during the following three phases of the
study: source water sampling, preliminary sampling, and
long-term evaluation. Source water sampling at Plant B
was performed in June 1998. Preliminary sampling con-
sisted of weekly water sampling for a 4-week period in
August 1998 and was designed to determine if the sam-
pling locations and proposed water quality analysis were
appropriate for the third phase, long-term evaluation.
The third phase was initiated in September 1998 and con-
tinued through June 1999. Arsenic speciation sampling
was conducted every fourth week. Backwash/regenera-
tion sample collection and analysis were not performed
at Plant B due to lack of information on the automatic
regeneration schedule.
4.3.1 Plant B Description
Plant B supplies water to approximately 35 employees of
a medical facility. The water source is a 260-ft-deep bed-
rock well drilled in October 1995. The capacity of this
well is 2 gpm based on a 48-hr pump test. The water
treatment system treats approximately 800 gpd.
During this test, arsenic and gross alpha radiation levels
in the well water were found to exceed maximum regu-
latory levels required by the EPA (Table 4-10). Gross
alpha in source water was remeasured at 31.00 pCi/L on
December 28, 1995, and the concentration of total urani-
um (U-234 and U-238) was measured at 27.72 pCi/L.
Subtracting the concentration of total uranium from the
concentration of gross alpha leaves a level of 3.28 pCi/L,
which falls under the 5 pCi/L MCL for gross alpha radi-
ation. Although treatment for gross alpha radiation was
determined to be unnecessary, a system capable of treat-
ing both the arsenic and gross alpha was installed by
Norlen's Water Treatment Service at Orrington, ME, in
March 1996.
Plant B uses an oxidizing filter followed by a cation-anion
mixed-bed filtration system. Figure 4-9 is a schematic
diagram of the treatment process used, which consists
of the following major elements:
Intake. Raw water is pumped from a 260-ft-deep
bedrock well and flows through a pressure tank.
ซ Oxidizing Filter. An MN1054AF oxidizing filter
tank was installed after the pressure tank to oxidize
possible As(lll) to As(V). The oxidizing filter tank is
a 54-inch-long and 10-inch-diameter fiberglass
tank with automatic control valves. An MnO2-based
material is used as the oxidizing medium and is
regenerated by potassium permanganate solution.
Ion Exchange System. After passing through the
oxidizing filter, water flows into an LAT-32 IX tank
filled with both cation and anion exchange resins.
The IX tank has the same size as the oxidizing
filter and the resin bed is 1.5 ft3 (containing both
cation and anion resins). At a design flow of 2 gpm,
the hydraulic loading rate to the filter is 3.7 gpm/ft2
Table 4-9. Percent Recoveries of Arsenic during the Resin Regeneration at Plant A
Date
3/21/99
4/18/99
5/16/99
6/13/99
Average
Volume of Water
Treated
(gai)
49,000
42,600
49,500
53,500
48,650
Volume of Water
Treated
(BV)
3,275
2,848
3,309
3,576
3,250
As Removed from
Raw Water*"
(mg)
6,200
5,260
6,099
5,931
As Recovered from
Regeneration1"'
(mg)
1,091
3,496
5,212
4,262
4,654""
Percent Recovery
(%)
17.6
66.5
85.5
71.9
78.5
74.6(dl
(a) Expressed as Mr.movod in Equation 3-1.
(b) Expressed as Mrrav.rod in Equation 3-1
(c) Calculation was based on grab sample data.
(d) Excluded data of 3/21/99.
31
-------
Table 4-10. Typical Source Water Quality Data
at Plant B (November 12,1995)
Parameter
Unit
Concentration
Turbidity
Fluoride
pH
Hardness
Sodium
Iron
Arsenic
Gross alpha
NTU
mg/L
mg/L(a>
mg/L
mg/L
ug/L
pCi/L
0.85
1.77
: 8.2
39.9
13.9
0.16
52
, 36.02
(a) Measured as CaCO3.
and the EBCT is 5.6 min. Information on the type
and volume of anionic resin was not available at
the time of study. Figure 4-10 shows a photograph
of the IX system.
Regeneration/Backwash. The oxidizing filter is
regenerated with potassium permanganate stored
in a 1.5-ft3 canister. The IX filter is regenerated with
Softouch, a potassium chloride-based regener-
ant, stored in a brine tank. Regeneration and back-
wash of both filters take place automatically once
every 6 days. Detailed information on fiowrates
and durations of regeneration and backwash were
unavailable. The spent regenerant and backwash
wastewater are disposed of to the facility's septic
tank.
The arsenic removal system (shown in Figure 4-10) is
fully automatic. The total cost of the system, including in-
stallation, piping and fittings, 1-year supply of Softouch,
and 1-year service warranty, was $2,975.80 at the time
of installation.
4.3.2 Initial Source Water Sampling
Plant B influent water is supplied by a 260-ft-deep bed-
rock well drilled in October 1995. Table 4-10 presents
the source water quality data on samples collected after
the well installation. As can be seen, the arsenic concen-
tration in the source water exceeded the 0.05 mg/L arse-
nic MCL The source water arsenic was not speciated.
A site visit to Plant B was conducted on June 9, 1998 to
collect source water samples. During this sampling event,
samples were collected for arsenic [total, paniculate, sol-
uble, As(lll), As(V)] and various other water quality pa-
rameters that may affect arsenic removal. Table 4-11
presents the analytical results from the source water
sampling. These results are similar to those of the previ-
ous sampling events shown in Table 4-10. The total
arsenic concentration in the source water averaged
55.0 ug/L; of this, approximately 0.8 ug/L was particulate
arsenic and 0.8 ug/L was As(lll). The majority of the sol-
uble arsenic was As(V). This speciation information sug-
gests that the oxidizing step of the Plant B treatment
system is unnecessary. The inlet total iron concentra-
tions averaged 150 ug/L. Aluminum concentrations were
less than the detection limit, and manganese concentra-
tions averaged 20 ug/L.
Alkalinity concentrations averaged 62.5 mg/L (as CaCO3)
and total hardness concentrations averaged 36 mg/L (as
CaCO3). This low hardness concentration suggests that
the softening function of the cation resin seems unnec-
essary. Turbidity concentration was relatively low, aver-
aging 0.45 NTU and the pH averaged 8.3. Sulfate con-
centrations averaged 45.5 mg/L, which was higher than
the sulfate level in the raw water at Plant A.
4.3.3 Preliminary Sampling
During the preliminary sampling phase, only the inlet and
outlet samples were collected because of the lack of a
sampling tap between the oxidizing filter and the IX filter.
The inlet sample was collected from a tubing connecting
to the inlet piping to the system. A sink faucet was used
for the outlet sampling. The sampling locations and the
associated sample analyses are shown on Figure 4-9.
Alkalinity, sulfate, turbidity, pH, total hardness, nitrate-
nitrite, total Al, total Fe, total Mn, and total arsenic analy-
ses were performed on all water samples collected.
Arsenic speciation sampling was conducted at the two
sampling locations once during the preliminary study.
Arsenic form (soluble and particulate) and species
(arsenate and arsenite) were determined as part of the
arsenic speciation. Table 4-12 presents the results of the
4-week preliminary sampling period.
Results from the preliminary sampling events indicated
that inlet total arsenic concentrations ranged from 53.2
to 57.1 ug/L, and were consistently higher than the arse-
nic MCL. As found during the source water sampling, the
total arsenic in the source water was primarily As(V),
and contained only little or no As(lll) or particulate arse-
nic. Except for the week of August 11,1998, the average
total arsenic removal was more than 95%, leaving less
than 1.0 ug/L arsenic in the finished water. The finished
water in August 11, 1998 had an abnormally high total
arsenic concentration (16.8 ug/L), hardness concentra-
tion (24 mg/L as CaCO3), pH (10.1), and turbidity
(1.9 mg/L). The reason for these abnormal results was
not clear. It was suspected that the samples might have
been contaminated.
_
32
-------
MONTHLY
As (total), As (III), As (V),
Hardness, Turbidity, NO3/NO2
SEPTIC TANK
As (total), As (IE), As (V),
Hardness, Turbidity, NO3/NO2
INFLUENT
PRESSURE TANK
OXIDIZING FILTER
IX FILTER
m
DISTRIBUTION
SYSTEM
Figure 4-9. Process Flow Diagrams and Sampling Locations at Plant B
Plant B
Ion Exchange
Design Flow: 2 gpm
WEEKLY
As (total), Alkalinity, pH,
Total Al,Total Fe, Total Mn, SO4
0
LEGEND
n Water Sampling
Location
Regeneration/Backwash
Sampling Location
Unit Process
Regeneration
..As (total), Alkalinity, pH,
Total Al,Total Fe, Total Mn, SO4
33
-------
Figure 4-10. Photograph of the IX System at Plant B
Table 4-11. Source Water Analytical Results at Plant B (June 9,1998)
Parameter
Alkalinity
Sulfate
Turbidity
pH
Hardness
Ca Hardness
Mg Hardness
Total Al
Total Fe
Total Mn
NO3-NO2 (N)
TOO
As(total)
As(total soluble)
As(particulate)
As(lll)
As(V)
(a) AsCaCO3.
(b) Combined NO3-N and
Unit
mg/Lซ"
mg/L
NTU
'
mg/L""
mg/L"ป
mg/Lw
Mg/L
M9/L
Mg/L
mg/LP"
mg/L
MI3/L
MS/L
M9/L
Mg/L
ug/L
NO2-N.
Primary
Sample
63
46
0.45
8.3
36
29.7
5.9
<400
200
30
<0.02
<1.0
53.8
53.5
0.3
0.8
52.7
Duplicate
Sample
62
45
0.44
8.3
36
30
5.8
<400
100
<20
<0.02
<1.0
56.2
54.9
1.3
0.8
54.1
Average
Concentration
62.5
45.5
0.45
8.3
36
29.9
5.9
<400
150
20
<0.02
<1.0
55.0
54.2
0.8
0.8
53.4
34
-------
Table 4-12. Analytical Results from Preliminary Sampling at Plant B (August 6 through 25, 1998)
Sampling Date/Location
Parameter
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total AI
Total Fe
Total Mn
Dissolved AI
Dissolved Fe
Dissolved Mn
Units
mg/L'"
mg/L
NTU
-
mg/L""
mg/L'"
mg/L"1
mg/L
M9/L
pg/L
van.
ug/L
M9/L
mg/L
pg/L
ug/L
Mg/L
Mg/L
pg/L
IN
63
44
0.3
8.4
33.8
28.0
5.8
<0.02
53.2
56.6
59.6
59.1
ND
ND
0.7
0.8
58.9
58.3
23.1
14.6
120
100
2.1
1.8
1.7
2.7
ND
ND
1.2
1.2
8/6/98
OU
27
<5
<0.1
7.2
<2.0
0.5
0.8
<0.02
0.8
1.1
1.0
0.7
ND
0.4
ND
ND
0.9
0.7
3.2
9.1
ND
2.5
0.1
0.2
1.5
1.7
ND
ND
0.1
0.1
8/11/98
IN
64
64
47
48
0.2
0.2
8.2
8.4
32.0
32.0
26.2
26.2
5.6
5.6
0.02
0.02
57.1
NS
NS
NS
NS
31.2
88.2
3.9
NS
NS
NS
OU
34
34
<5
<5
1.8
1.9
10.1
10.1
28.0
20.0
26.7
18.7
<0.8
<0.8
0.04
0.02
16.8
NS
NS
NS
NS
28.2
78.8
0.7
NS
NS
NS
8/18/98
IN
65
44
0.5
8.2
NS
NS
NS
NS
54.7
NS
NS
NS
NS
17.8
105
2.5
NS
NS
NS
OU
12
<5
<0.1
8.5
NS
NS
NS
NS
0.8
NS
NS
NS
NS
25.1
9.4
0.3
NS
NS
NS
8/25/98
IN
64
47
-
8.4
NS
NS
NS
NS
54.1
NS
NS
NS
NS
OU
17
<5
-
7.9
NS
NS
NS
NS
0.9
NS
NS
NS
NS
24.2 21.9
98.6
2.7
NS
NS
NS
2.4
0.2
NS
NS
NS
(a) AsCaCO3.
Because Plant B uses a mixed resin bed, it removes
both cations and anions from the source water. Total
hardness was reduced to nondetect level. Alkalinity
decreased from approximately 64 mg/L (as CaCO3) at
the inlet to 12-27 mg/L at the outlet, concurrent with the
decreased pH values of the outlet samples. The inlet
sulfate concentrations, ranging from 44 to 48 mg/L, were
significantly reduced to less than the detection limit
(5 mg/L) after treatment. Turbidity and nitrate-nitrite con-
centrations were extremely low in the raw water, so no
significant changes were observed after the treatment.
Total and dissolved AI, Fe, and Mn concentrations also
were low in the raw water, and therefore, their effects on
the process were insignificant.
4.3.4 Long-Term Sampling
Long-term sampling and analysis consisted of 36 weeks
of water sampling at the same two locations used during
the preliminary sampling phase (see Figure 4-9). All
weekly samples were analyzed for alkalinity, sulfate, pH,
total aluminum, total iron, total manganese, and total
35
-------
arsenic. Arsenic speciation sampling was conducted at
each sampling location nine times during the long-term
sampling phase on samples collected from each sam-
pling location. Analysis included determination of hard-
ness, nitrate-nitrite, and dissolved aluminum, iron, and
manganese concentrations. Backwash and regeneration
wastewater was not sampled due to lack of information
on the automatic regeneration schedule. The following
subsections summarize the analytical results of arsenic
and other water quality parameters.
4.3.4.1 Arsenic
Table 4-13 provides a summary of the arsenic analytical
results collected at the inlet and outlet sampling loca-
tions. Total arsenic concentrations at the inlet ranged
from 40.8 to 64.5 ug/L with an average of 56.7 ug/L,
which are comparable with the data collected during the
previous phases of the study. Total arsenic concentra-
tions at the outlet ranged from 0.8 to 4.5 ug/L with an
average of 1.6 ug/L. Therefore, an average removal rate
of 97% was achieved, corresponding well with the re-
moval rates observed during the preliminary sampling
phase. Figure 4-11 is a graph showing the total arsenic
concentrations at both sampling locations throughout the
study.
Particulate arsenic concentrations averaged 0.5 ug/L at
the inlet and 0.3 ug/L at the outlet. As(lll) concentrations
averaged 0.8 ug/L in the raw water and 0.2 ug/L in the
finished water. These results were consistent with those
of the source water and preliminary sampling. As(V) con-
centrations averaged 56.7 ug/L in the raw water and
1.4 ug/L in the finished water. Therefore, As(V) made up
the majority of the soluble arsenic, which suggests that the
oxidizing filter may not be necessary; however, the filter
can act as a safeguard against any occurrence of As(lll).
Throughout the study, the IX system was able to con-
sistently remove arsenic to <5 ug/L (or <2 ug/L at 90% of
the time). The satisfactory performance of this treatment
process is likely due to the frequent regeneration of the
system. The maximum run length of the system (in terms
of BV), however, might not have been reached before
each regeneration cycle. The maximum run length was
not estimated because of lack of information on the
anion resin bed volume and water usage data.
4.3.4.2 Other Water Quality Parameters
Several other water quality parameters also were ana-
lyzed to provide information on the performance of the
treatment plant. Table 4-14 summarizes the analytical
results for the other water quality parameters obtained
during the long-term sampling.
The inlet sulfate concentrations, ranging from 36 to 49
mg/L with an average of 44.5 mg/L, were consistently
reduced to <5 mg/L after the treatment process. Figure
4-12 shows the inlet and outlet sulfate concentrations as
well as removal percentages. Due to the frequent regen-
eration of the IX filter, the sulfate in the inlet water did
not seem to impact the system performance for arsenic
removal.
Figure 4-13 plots the inlet and outlet alkalinity and pH
values throughout the study. Inlet alkalinity concentra-
tions remained constant at levels of 62 to 65 mg/L (as
CaCO3). The alkalinity was removed through exchange
of bicarbonate ions with the chloride ions on the resin.
Inlet pH values were relatively constant throughout the
duration of the study. The outlet pH values varied from
6.1 to 8.8 and were below the inlet pH values most of the
time, presumably due to the removal of alkalinity. The
elevated outlet pH did not seem to impact arsenic
removal.
Turbidity and nitrate-nitrite concentrations were very low
in the raw and finished water, and no significant changes
were found after the treatment. Total and dissolved Al,
Table 4-13. Summary of Arsenic Analytical Results at Plant B (September 1,1998 to May 25,1999)
Parameter
As (total)
As (total soluble)
As (partlculate)
As(lll)
As(V)
Sampling Location
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Units
ug/L
ug/L .
ug/L
ug/L
ug/L
Mg/L
ug/L
ug/L
ug/L
ug/L
Number of
Samples
45
45
18
18
18
18
18
18
18
18
Minimum
Concentration
40.8
0.8
43.9
0.9
0.1
0.1
0.4
0.1
43.2
0.8
Maximum
Concentration
64.5
4.5
62.7
2.9
1.6
1.2
1.3
0.6
62.0
2.6
Average
Concentration
56.7
1.6
57.4
1.7
0.5
0.3
0.8
0.2
56.7
1.4
Standard
Deviation
4.6
0.7
5.5
0.7
0.6
0.4
0.3
0.2
5.6
0.6
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculation.
36
-------
100 -r
X *
.00
'
Sat
100%
90%
'Met As
Outlet As
"%Renr>val
08/06/98
10/05/98
12/0498
02/02/99
Date
04/03/99
06/02/99
08/01/99
Figure 4-11. Total Arsenic Analytical Results during Long-Term Sampling at Plant B
Table 4-14. Summary of Water Quality Parameter Analytical Results at Plant B (September 1, 1998 to May 25, 1999)
Parameter
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Nitrate-Nitrite
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
Sampling Location
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Units
mg/L
mg/L
mg/L
mg/L
NTU
NTU
mg/L
mg/L
mg/L
mg/L
ug/L
M9/L
ug/L.
pg/L
pg/L
ug/L
ug/L
wg/L
ug/L
ug/L
pg/L
ug/L
Number of
Samples
45
45
45
45
18
18
45
45
18
18
18
18
45
45
45
45
45
45
18
18
18
18
18
18
Minimum
Concentration
62
3
36
<5
<0.1
<0.1
7.8
6.1
33.0
<2.0
<0.02
<0.02
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
1.4
<0.5
Maximum
Concentration
65
17
49
<5
0.6
0.2
8.6
8.8
46.7
8.3
0.06
0.03
68.3
131
139
72.7
3.6
5.5
21.8
10.4
113.5
31.2
2.8
<0.5
Average
Concentration
63.8
8.2
44.5
<5
0.4
0.1
8.3
7.3
38.4
2.1
0.03
0.01
15.2
12.9
69.5
21.5
2.1
0.5
7.3
6.0
35.1
16.8
2.0
<0.5
Standard
Deviation
0.7
3.8
2.4
0
0.2
0.1
0.1
0.9
4.3
2.5
0.02
0.01
13.3
21.1
39.7
14.0
0.8
0.9
5.4
1.6
35.9
5.4
0.5
0
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
37
-------
100
I
&
e
o
S
%
ง
80-
60-
40
20
% Removal
-******* i
****-x+^++++++.
0000
'^
Detection limit of 5 mg/L
ปซซปซซปป ป<
Outlet
ป ป ปซปซปป
>ป>ปปปซ
100%
- - 80%
- - 60%
- - 40%
- - 20%
--ซ-- Met Sulfate
-i-ปOutlet Sulfate
* % Removal
o
a
0%
08/06/98 10/05/98 12/04/98 02/02/99 04/03/99 06/02/99 08/01/99
Date
Figure 4-12. Inlet and Outlet Sulfate Analytical Results and Percent Removal at Plant B
200
1ZO
OSW98
10/05/98
12/04/98 02/02/99
04/03/99
06/02/99
-- ฃ,-
- - o- - "Met alkalinity
*Outlet alkalinity
-Inlet pH
'Outlet pH
08/01/99
Date
Figure 4-13. Inlet and Outlet Alkalinity and pH Analytical Results at Plant B
38
-------
Fe, and Mn concentrations were low in the raw water, so
their effects on the arsenic removal process were mini-
mal.
4.4 Plant C
Water samples were collected and analyzed at Plant C,
an AA plant, during the following three phases of the
study: initial source water sampling (June 10,1998), pre-
liminary sampling (August 5 through September 16,1998),
and long-term sampling (September 30, 1998 through
June 9, 1999). Water sampling was performed biweekly
during the preliminary and long-term sampling. Arsenic
speciation sampling was conducted during the initial
source water sampling, once during preliminary sam-
pling, and once every 8 weeks during the long-term sam-
pling. Spent AA samples were collected once from two
roughing tanks during AA change-out on December 29,
1998.
4.4.1 Plant C Description
Plant C supplies water to a school used by approximate-
ly 600 students and teachers. The ADD of the school is
approximately 2,000-2,500 gpd. The AA system was
installed by Aqua Specialties of Northwood, NH, in August
27, 1997 with a design flowrate of 14gpm. Figure 4-14 is
a schematic of the AA system.
As shown on Figure 4-14, Plant C consists of four AA
tanks that are arranged as two parallel sets of two tanks
in series. Figure 4-15 shows a cross section of an AA
tank. The first set of the tanks (TA1 and TA2) are used
as roughing filters and the second set (TB1 and TB2) are
used as polishing filters. The major elements of the treat-
ment process are described as follows:
Intake. Raw water is supplied by a 700-ft-deep
well and flows through the water system control
room. A water flowmeter was installed to measure
the volume of water entering the treatment system.
* Cartridge Filters. Two Ametek "Big Blue"
cartridge filters were installed in parallel on the raw
water header to remove particles from the well
water. The cartridge filters are approximately
9% inches tall and 5 inches in diameter. The
nominal rating of the cartridge is 30 urn.
Activated Alumina Tanks. After passing through
the cartridge filters, the filtered water splits into the
two AA treatment trains. Gate valves exist to
isolate each train and control the split ratio; how-
ever, no water meter is available on either train to
confirm the exact split ratio. Each fiberglass min-
eral tank (52 inches tall by 16 inches in diameter)
contains approximately 4 ft3 of Alcoa DD-2 AA. The
depth of the AA bed is approximately 33 inches,
leaving a free board distance of approximately
9 inches between the top header and the top of the
medium. The AA medium/gravel support interface
material is approximately 6 inches above the floor.
The influent flows downward through the AA bed
and the treated water returns to the top of the tank
through a 1-inch polyvinyl chloride (PVC) riser
tube. The differential pressure across the medium
was approximately 3 psi.
Alcoa DD-2 (14 x 28 mesh) is a successor of F-1
AA. Typical physical and chemical properties of
this medium are presented in Table 4-15, and the
material safety data sheet (MSDS) is attached in
Appendix C.2. At a design flowrate of 7 gpm
(assuming water is split evenly into each train), the
hydraulic loading rate to each tank is 5.0 gpm/ft2
and the EBCT is 4.3 minutes.
Media Replacement. The AA system at Plant C is
operated on a media-throwaway basis. When the
AA medium in the roughing filters reaches its arse-
nic removal capacity, the spent AA is removed and
replaced with virgin medium. The polishing filters
are moved to the roughing filter position by phys-
ically repositioning the filters. The tanks with the
new virgin medium then are placed in the polishing
position. The AA in all four tanks was virgin in
September 1997. The AA in the two roughing tanks
(TA1 and TA2) was replaced with virgin AA on
December 29, 1998 due to arsenic breakthrough.
Also on that date, tanks TB1 and TB2 were moved
to the roughing positions and the recharged TA1
and TA2 were moved to the polishing positions.
Backwash. Backwash is not performed on a
routine basis. Since their installation, the AA tanks
have been backwashed only twice with the pres-
surized treated water. Backwash of TA1 was per-
formed during Battelle's visit on August 5,1998
and lasted for approximately 5 minutes at a flow-
rate of 3 gpm. Backwash wastewater was disposed
of to the school's leach field.
Storage Tank. The treated water from each train is
combined and flows to a 15,000-gal steel storage
tank buried outside the school building. The stor-
age tank invert is at an elevation of approximately
20 ft above the school's floor grade. Water in the
storage tank also serves the school's fire sprinkler
system. Before distribution, the treated water is
pressurized by two Flint & Walling 2-horsepower
(hp) centrifugal booster pumps buffered by four
119-gal pressure tanks.
Quarterly sampling for arsenic has been conducted by a
plant staff since March 1996 on raw water, between the
39
-------
From well
BIMONTHLY
As (total), As (III), As (V),
Hardness, Turbidity, NO3/NO2~^~
Plant C
Activated Alumina
Design Flow: 14 gpm
Flowmeter
BIWEEKLY
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
As (total), pH, TSS
i Water Content, Total As,' '
Storage Tank
(15,000 gal)
I
0
(BW)
(AA)
(CP]
@
.EGEND
Water Sampling
Location
Backwash Sampling
Location
Spent AA Sampling
Location
Cartridge Filter
AAtank
As (total), As (HI), As (V),
Hardness, Turbidity, NO3-/NO2-
As (total), As (HI), As (V),
Hardness, Turbidity, NO3/NO2
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
To the distribution system
Figure 4-14. Process Flow Diagrams and Sampling Locations at Plant C
40
-------
O-100
pressure
gauge
we//
Fiberglass mineral tank
Freeboard area
Packwashing control valve/tank manifold
(manual operation for occasional media "fluffing")
A secondary tank is not shown
Treated wafer to
atmospheric
storage
tank
Sample tap
4 cubic feet activated alumina
(28 x 48 mesh)
1" pvc riser tube with
strainer basket on
bottom (returns treated
water to top of unit)
50 # (appro*. 6" depth) support
gravel
NOTE:
The system consists of two
treatment trains (configured
in parallel) with two AA
tanks in series in each train.
Only one tank is shown in
this figure.
trainer basket
Not to scalg. Modified 5/5/97. C. Kofcr
Figure 4-15. Cross Section of AA Tank at Plant C (Source: Aqua Specialties, 1999)
41
-------
Table 4-15. Typical Characteristics of DD-2
Activated Alumina
Physical Characteristics
Appearance (color, shape)
Surface area, mVg
Total pore volume, cc/g
Total porosity, %
Bulk density, kg/nf
Abrasion loss, wt%
DD-2 AA (14x28 mesh)
White, granule
250
0.395
56.2
620-830
1.6
Chemical Composition (wt%)
AIA
Nap
Fep,
SiO,
Loss on ignition (Water)
Alumina XRD phase
Price, $/lb
92.2
0.90
0.08
0.09
6.5
Amorphors, boehmite, and gamma
1.01
roughing and the polishing tanks in each train, and from
treated water. The arsenic concentration data are sum-
marized in Table 4-16. The data show that the arsenic
concentrations in samples collected between TA2 and
TB2 on October 13, 1998 reached the 0.05 mg/L arsenic
MCL, indicating arsenic breakthrough in TA2. Water
usage data have been recorded since the AA system
installation and are attached in Appendix C.3.
Table 4-16. Arsenic Concentrations (ug/L) from
Quarterly Water Sampling at Plant C
Date
Raw Water A1B1W A2B2M Treated Water
03/11/96
06/13/96
9/18/96
11/12/96
02/11/97
06/11/97
08/12/97
08/14/97
08/27/97""
10/23/97
1/15/98
04/23/98
08/04/98
10/13/98
01/08/99
37
46
47
50
50
42
37
78
12
16
33
43 37
20
17
36
50
29
<5
13
<5
<10
<10
7
17
5
(a) Water collected from a tap between TA1 and TB1.
(b) Water collected from a tap between TA2 and TB2.
(c) The AA system was installed.
= No data collected.
4.4.2 Initial Source Water Sampling
Source water for Plant C is supplied by a 700-ft-deep
bedrock well (drilled in 1994) through a submersible
pump (Model No. 13GS20). The capacity of this well is
12-14 gpm based on a 48-hr continuous pump test.
Source water quality measurements on samples col-
lected on December 30, 1994 are presented in Table 4-
17. The historic quarterly sampling data shown in Table
4-16 indicate significant variation in raw water arsenic
concentrations, which ranged from 37 to 78 ug/L. These
concentrations were close to or exceeded the arsenic
MCL. Information on arsenic speciation was unknown
prior to this study.
Table 4-17. Source Water Quality Measurements at
Plant C (December 30,1994)
Parameter
Unit
Concentration
Alkalinity
Turbidity
Fluoride
Chloride
Sulfate
pH
Hardness
Sodium
Specific Conductance
Arsenic
mg/L!"
NTU
mg/L
mg/L
mg/L
mg/L<"
mg/L
umhos/cm
pg/L
105
<1.0
1.91
4.0
23
8.3
52.2
38.4
259
42
(a) Measured as CaCOj.
On June 10, 1998, an initial site visit to Plant C was con-
ducted and source water samples were collected. The
analytical results as presented in Table 4-18 are consist-
ent with previous plant sampling data shown in Table 4-
17. The total soluble arsenic concentration was relatively
high, averaging 61.9 ug/L. Approximately 30% of the sol-
uble arsenic existed as As(lll) (18.1 ug/L) and the rest was
As(V) (43.8 ug/L). Particulate arsenic was not detected
in the raw water.
4.4.3 Preliminary Sampling
During the preliminary sampling phase of this study,
water samples were collected at four locations: (1) at the
inlet; (2) after the roughing tank of train 1 (TA1); (3) after
the polishing tank of train 1 (TB1); and (4) at the com-
bined effluent of trains 1 and 2. Sampling taps were avail-
able at all four sampling locations. Sampling locations and
sample analyses are indicated on Figure 4-14.
Preliminary sampling consisted of biweekly sample col-
lection and analysis of various parameters (alkalinity, tur-
bidity, pH, hardness, fluoride, sulfate, total arsenic, total
42
-------
Table 4-18. Source Water Sampling Analytical Results
at Plant C (June 10,1998)
Parameter
Alkalinity
Fluoride
Sulfate
Turbidity
pH
Hardness
Ca Hardness
Mg Hardness
Total Al
Total Fe
Total Mn
NO3-NO2 (N)
TOC
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
(a) AsCaC03.
Units
mg/L"'
mg/L
mg/L
NTU
mg/L("
mg/Lซ"
mg/L"ฐ
IJg/L
ug/L
ug/L
mg/L0"
mg/L
ug/L
ug/i-
pg/L
pg/L
pg/L
(b) Combined NO3-N and
Primary
Sample
86
1.5
26
1.27
8.1
50.2
31.7
18.5
ND
110
100
0.06
1.3
60.0
61.4
ND
18.1
43.3
NO2-N.
Duplicate
Sample
82
1.5
26
0.28
8.1
53.7
35.2
18.5
ND
100
90
0.04
1.1
58.0
62.5
ND
18.2
44.3
Average
84
1.5
26
0.78
8.1
52.0
33.5
18.5
ND
105
95
0.05
1.2
59.0
61.9
ND
18.1
43.8
Al, total Fe, and total Mn analyses). Arsenic speciation
sampling was conducted once on samples collected
from inlet and TA1 locations. Table 4-19 presents the
results of the biweekly preliminary sampling events.
Similar to the results of historic quarterly sampling, inlet
total arsenic concentrations varied significantly, ranging
from 21.3 to 56.1 ug/L. During the arsenic speciation
sampling on August 5, 1998, the inlet water contained an
average of 5.9 ug/L As(lll), which is lower than the con-
centration measured during the source water sampling
(18.1 ug/L). Most As(lll) was removed by the roughing
filter, as indicated by the As(lll) concentrations (1.1 ug/L)
measured after the roughing filter. Particulate arsenic
was not measured at significant levels in any of the sam-
ples collected during preliminary sampling.
During the first sampling event on August 5, 1998, the
roughing filter removed close to 50% of the total arsenic
from the raw water. However, the total arsenic concen-
trations after the roughing filter approached or was over
the influent levels during two subsequent sampling events
(i.e., August 19 and September 16, 1998), which indicated
the exhaustion of the AA medium in the roughing filter.
Regardless of the arsenic breakthrough from the rough-
ing filter, the polishing filter still was able to reduce arse-
nic concentrations to low levels (e.g., 1.6 to 9.3 ug/L).
The combined treated water from both trains had total
arsenic concentrations ranging from 2.8 to 11.6 ug/L.
Fluoride concentrations ranged from 1.1 to 1.6 mg/L in
the raw water and 1.3 to 1.6 mg/L in the finished water.
Therefore, fluoride was not removed by the AA tanks.
Similarly, sulfate concentrations remained relatively con-
stant at 22 to 27 mg/L throughout the treatment process.
Fluoride is known to be a major competing ion with arse-
nate for adsorption sites on AA surface, especially in an
optimal pH range of 5.5-6.0. Sulfate also has some affin-
ity for the AA surface (see Section 1.1.3.2). Removal of
sulfate and fluoride by AA was not observed during these
sampling events, thus confirming AA's higher order of
preference for arsenate. Other factors such as high pH
values of the inlet water and near-exhaustion AA capac-
ity, also might have contributed to the low reduction of
sulfate and fluoride. Clifford et al. (1986) reported that
the addition of 360 mg/L sulfate and 1,000 mg/L TDS
decreased the As(V) adsorption on AA by almost 50%.
Vagliasindi et al. (1996) found that arsenate adsorption
was insensitive to sulfate concentrations in the range of
0 to 100 mg/L. Therefore, sulfate concentrations in raw
water were not high enough to significantly affect the
As(V) removal. Alkalinity, total hardness, and nitrate/
nitrite remained relatively constant after the treatment.
Total aluminum concentrations slightly increased after the
roughing and polishing tanks. The increase in aluminum
concentration might have resulted from the dissolution of
AA medium. Total iron and manganese concentrations in
the raw water were rather low and did not appear to
impact arsenic removal.
Based on the results of the preliminary sampling, only
minor changes were made to the approach for the long-
term evaluation. Sampling locations and analytes re-
mained unchanged. However, arsenic speciation was
performed at all four locations during the long-term eval-
uation instead of just at the inlet and TA1 locations.
4.4.4 Long-Term Sampling
Biweekly long-term sampling and analysis was per-
formed for 36 weeks (18 events) for alkalinity, fluoride,
sulfate, turbidity, pH, hardness, nitrate-nitrite, total alum-
inum, total iron, total manganese, and total arsenic.
Long-term sampling also included five arsenic speciation
sampling events at each sampling location. The four
sampling locations used during the preliminary sampling
also were used during long-term sampling. Additionally,
spent AA samples were collected once during AA re-
placement.
4.4.4.1 Arsenic
Table 4-20 summarizes the arsenic analytical results col-
lected at the four sampling locations. Total arsenic con-
centrations at the inlet ranged from 34.4 to 76.0 ug/L
with an average of 53.5 ug/L. These concentrations were
consistent with the historic arsenic data (Table 4-16).
43
-------
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< LL 2
CD ฃ CD O S
~
-------
Table 4-20. Summary of Arsenic Analytical Results at Plant C (September 30,1998 to June 9,1999)
Parameter
As (total)
As
(total soluble)
As
(particulate)
As (III)
As(V)
Sampling Location
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1 st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Units
ug/L
ug/L
ug/L
ug/L.
ug/L
ra/L
yg/L
ug/L
ug/L.
ug/L
M9/L
M9/L
ug/i-
ug/L
ra/L
yg/L
yg/L
ug/L.
M9/L
ug/L
Number of
Samples
23
22
23
23
10
10
10
10
10
9
10
10
10
10
10
10
10
10
10
10
Minimum
Concentration
34.4
14.2
0.4
1.3
42.3
33.9
0.4
1.8 .
<0.1
<0.1
<0.1
<0.1
<0.1
0.3
0.1
<0.1
34.4
33.6
<0.1
<0.1
Maximum
Concentration
76.0
50.4
26.7
21.8
63.6
50.1
26.0
18.6
13.4
<0.1
0.6
6.9
28.8
9.1
2.6
1.9
55.4
48.3
25.6
17.6
Average
Concentration
53.5
39.3
6.8
7.2
54.9
43.0
7.1 .
6.8
5.1
<0.1
0.2
0.8
7.9
3.0
0.6
0.7
45.2
39.9
6.6
6.0
Standard
Deviation
9.4
8.7
9.2
6.8
8.1
6.1
9.9
6.5
6.2
0
0.2
2.2
11.2
3.3
0.8
0.7
6.9
6.4
10.0
6.6
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
The first tank was TA1 before the medium change-out on December 29,1998 and TB1 after the medium change-out.
The second tank was TB1 before the medium change-out on December 29,1998 and TA1 after the medium change-out.
Samples collected after the roughing tank contained total
arsenic of 14.2 to 50.4 ug/L with an average of 39.3
ug/L. Samples collected after the polishing tank con-
tained total arsenic of 0.4 to 26.7 ug/L with an average of
6.8 ug/L. The combined treated water (i.e., outlet) had
total arsenic concentrations ranging from 1.3 to 21.8
ug/L with an average of 7.2 ug/L. The average removal
percentages were 26.5% and 87.3% by the roughing
and polishing tanks, respectively. The average overall
arsenic removal efficiency was 86.5% during the long-
term sampling.
Figure 4-16 provides charts showing the fractions of the
total arsenic concentration made up by particulate arse-
nic, As(III), and As(V) at each sampling location. The
inlet water contained primarily the oxidized species of
arsenic [i.e., As(V)] with various amounts of As(lll) (0 to
45%) and particulate arsenic (0 to 22%). Particulate arse-
nic was only detected in the inlet water on September 30,
1998 and May 26, 1999 with concentrations averaging
12.8 and 11.8 ug/L, respectively. Because total iron con-
centrations in the inlet samples also were abnormally
high, it was suspected that some arsenate might have
clung to some iron particles, resulting in high particulate
arsenic concentrations. Except for September 30, 1998,
most particulate arsenic was removed by the system.
As(lll) concentrations averaged 7.9 ug/L at the inlet,
3.0 ug/L after the roughing tank, 0.6 ug/L after the pol-
ishing tank, and 0.7 ug/L at the outlet location. There-
fore, As(III) was almost completely removed by AA.
Because no oxidative treatments were performed ahead
of the AA columns, conversion of As(lll) to As(V) was
rather unlikely. The removal of As(lll) would occur either
through a direct sorption of As(lll) or via some unex-
plained conversions of As(lll) to As(V) prior to adsorp-
tion. Clifford and Lin (1984; 1991) had observed some
unplanned oxidation of As (III) to As(V) within alumina
columns, which resulted in better-than-expected per-
formance for arsenic removal. Nonetheless, the adsorp-
tion of As(lll) onto AA has been reportedly far less than
that of As(V) (Vagliasindi, and Benjamin, 1997; Clifford,
1999). Therefore, arsenite should be oxidized to arse-
nate prior to AA treatment.
The average As(V) concentrations were 45.2 ug/L at the
inlet, 39.9 ug/L after the roughing tank, 6.6 ug/L after the
polishing tank, and 6.0 ug/L at the outlet location. The
arsenic in the finished water consists almost entirely of
As(V).
Figure 4-17 presents the total arsenic concentrations at
each sampling location and the overall removal per-
centages for each sampling event. The data were plotted
twice, with one graph showing the sampling date and the
other showing the BV of the water treated. BV was
calculated using the amount of water treated divided by
the AA volume in each tank (4 ft3 or 29.92 gallons).
45
-------
Ink!
70
60-
50
40
30-
20
10
0
y
/u
60
50
40
30
20
10 -
T
ป !
p
"
'
y,
I
1
IS
,J
n
?-
,
s
_
J
'*
ป
^-
09/30/98 12/02/98 02/03/99 03/31/99 05/26/99
09/30/98 12/02/98 02/03/99 03/31/99 05/26/99
TB1
Outlet
09/30/98 12/02/98 02/03/99 03/31/99 05/26/99
7U '
60
1 5ฐ-
J40-
1 20 -
10
n -
i 1 _
ElAs (paniculate)
As (III)
El As (V)
09/30/98 12/02/98 02/03/99 03/31/99 05/26/99
Figure 4-16. Arsenic Form and Species Analytical Results during Long-Term Sampling at Plant C
As shown in Figure 4-17, the AA capacity of TA1 (the
roughing tank of train 1) was nearly exhausted after treat-
ing 10,050 BV of water. The plant record also indicated
that arsenic breakthrough occurred in TA2 (the roughing
tank of train 2) on October 13, 1998 after treating 9,156
BV of water (see Table 4-16). Therefore, both TA1 and
TA2 were recharged with virgin AA and repositioned to
become polishing tanks. TB1 and TB2 then were moved
to the first position and used as roughing tanks. Within 1
to 2 weeks after the medium replacement and tank
rearrangement, the total arsenic concentrations dropped
to <20 ug/L after the roughing tank and <5 ug/L in the
system effluent. Afterwards, the arsenic concentrations
after the roughing tank gradually increased to inlet levels
again, indicating arsenic breakthrough from the roughing
tank (TB1). Nonetheless, the arsenic concentrations
measured after the polishing tank were consistently
below 5 ug/L.
To estimate the AA capacity for arsenic in TA1 and TA2,
the following assumptions were made: (1) 9,600 BV of
water were treated before arsenic breakthrough from
TA1 and TA2; (2) 53.5 ug/L total arsenic were in the raw
water (see Table 4-20); (3) 30.7 ug/L total arsenic were
in TA1 and TA2 effluent (calculated based on available
data from the plant record, preliminary sampling events,
and long-term evaluation); and (4) the density of the AA
was 730 kg/m3 (see Table 4-15). Using the above assump-
tions, 49.6 g of total arsenic was removed from the raw
water by the two roughing tanks prior to 50-jag/L arsenic
breakthrough, equivalent to an AA capacity of 0.30 g/kg
(219 g/m3). This value is comparable to the AA capacity
of 0.26 g/kg (to 50 ng/L arsenic breakthrough) reported
by Fox (1989) in his study with a source water of pH 8.3
and containing 50 to 350 ug/L As(V). Clifford (1999) esti-
mated the practically achievable column capacity based
on pH 6.0 operation with a source water containing 100
ug/L As(V) to be 1,400 g As(V)/m3 of alumina, which was
much higher than the capacity obtained for Plant C. Be-
cause Plant C operated under less ideal conditions (i.e.,
higher pH), it would not be expected to achieve the
same level of arsenic removal.
4.4.4.2 Other Water Quality Parameters
Sampling and analysis of other water quality parameters
were performed to provide insight into the arsenic re-
moval efficiency at the plant. Table 4-21 summarizes the
analytical results for several water quality parameters
obtained during long-term sampling at Plant C. Figure 4-18
46
-------
160.0
140.0
120.0
3 100.0'
ง
o
U
80.0 '
60.0 -
40.0"
20.0-
0.0
09/12/98
,.--0.
TA1 was used as the roughing tank and TB1 was used as
the polishing tank before medium change-out on December
29,1998; since then, TB1 was used as the roughing tank
and the recharged TA1 was used as the polishing tank.
11/01/98 12/21/98
02/09/99
Date
03/31/99 05/20/99
100
-80
-'60
-'40
-20
0
07/09/99
160.0
140.0
120.0-
i
o
I
o
U
100.0-
80.0-
60.0-
40.0-
20.0-
Arsenic broke through.TAI
after treating 10,050 BV of water / '.
o.
\ '; '-
V-o-V ,...<5
Roughing tanks replaced with virgin AA
after treating 11,071 BV of water
-80
100
--20
9.0 10.0
11.0 12.0 13.0
BV of water treated (xlOOO)
14.0 15.0
0
16.0
Figure 4-17. Total Arsenic Analytical Results during Long-Term Sampling at Plant C
47
-------
Table 4-21. Summary of Water Quality Parameter Analytical Results at Plant C (September 30,1998 to
June 9,1999)
Parameter
Alkalinity
Fluoride
Sulfate
Turbidity
oH
r* *
Total Hardness
N0a-N0s (N)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
, .....
Dissolved Mn
Sampling
Location
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Inlet
After 1st tank
- After-2nd tank
Outlet
Inlet
After 1st tank
After 2nd tank
Outlet
Units
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
NTU
NTU
NTU
NTU
_
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
pg/L
M9/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
pg/L
ug/L
Number of
Samples
23
23
23
23
23
23
23
23
23
23
23
23
5
5
5
5
23
23
23
23
5
5
5
5
5
5
5
5
23
23
23
23
23
23
23
23
23
23
23
23
10
10
10
10
10
10
10
10
10
10
10
10
Minimum
Concentration
67
73
73
72
1.2
0.9
0.3
0.2
22
23
18
19
<0."1
<0. i
<0,1
<0.1
7.8
7.8
7.6
7.6
47
49
48
48
0.01
0.01
0.05
0.02
<11
12.7
<11
12.6
<30
<30
<30
<30
48.9
30.4
1.9
6.4
<11
<11
<11
<11
<30
<30
<30
<30
52.2
30.2
16.0
10.3
Maximum
Concentration
90
89
89
87
1.6
1.7
1.6
1.6
27
27
35
29
0.3
<0.1
<0.1
0.15 .
8.1
8.1
8.6
8.7
57
53
52
53
0.1
0.3
0.6
1.3
97.4
59
109
112
178
60.5
25.6
125
90.7
88.7
87.9
86
<11
15.1
23.3
23.3
<30
<30
<30
<30
68.1
81.3
76.3
75.8
Average
Concentration
81.1
83.3
80.9
78.3
1.4
1.4
1.3
1.2
25.2
25.3
25.9
25.2
0.14
<0.1
<0.1
0.07
8.0
7.9
8.0
8.0
52.4
50.9
49.2
50.3
0.04
0.14
0.25
0.31
18.3
27.5
29.4
32.5
53.4
20.0
15.6
36.3
67.2
69.2
55.2
46.5
<11
10.5
12.6
13.4
15
15
15
22.6
63.1
67.2
56.2
45.7
Standard
Deviation
4.1
4.4
4.6
0.11
0.17
0.33
0.36
1.2
1.0
3.5
2.1
0.11
0
0.04
0.1
0.07
0.2
0.3
4.6
1.7
1.8
1.8
0.03
0.11
0.22
0.55
21.1
12.3
24.2
23.2
49.0
12.4
2.5
36.4
11.9
17.9
25.9
28.6
0
3.6
7.7
7.7
0
0
0
17.1
6.3
21.4
24.6
25.2
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
The 1st tank was TA1 before the medium change-out on December 29,1998 and TB1 after the medium change-out.
The 2nd tank was TB1 before the medium change-out on December 29,1998 and TA1 after the medium change-out.
48
-------
100.0
80.0-
<5
u
a
" 60.0
g 40.0 -
1
20.0-
Inlet alkalinity
Inlet pH
o-
Outlet alkalinity
change-out on December 29,1998
Outlet pH
12
-- 11
-- 10
--9
-- 8
--7
0.0
09/12/98 11/01/98 12/21/98 02/09/99 03/31/99 05/20/99 07/09/99
Date
-O- -Inlet alkalinity
-*~ Outlet alkalinity
" O " Inlet pH
Outlet pH
" AA change-out
50,0
I
I
45.0-
40.0 -
35.0-
30.0 -
a 20.0
15.0 -
10.0 -
5.0-
0.0
AAphange-out on December 29, 1998
Outlet sulfate
Inlet fluoridi
Outlet fluoride
10
Inlet sulfate
Outlet sulfate
""Inletfluoride
Outlet fluoride
AA change-out
+ 6 I
2
"S
1
+ 4 3
--2
0
09/12/98 11/01/98 12/21/98 02/09/99 03/31/99 05/20/99 07/09/99
Date
Figure 4-18. Inlet and Outlet Alkalinity, pH, Fluoride, and Sulfate Analytical Results at Plant C
49
-------
plots the inlet and outlet water alkalinity, pH, fluoride,
and sulfate at Plant C.
Inlet alkalinity concentrations were relatively constant,
ranging from 67 to 90 mg/L (as CaCO3) with an average
of 81.1 mg/L. Alkalinity remained relatively constant
across all four sampling locations. Inlet pH values
ranged from 7.8 to 8.1 with an average of 8.0. This pH
was higher than the optimal pH for the AA process,
which ranges from 5.5 to 6.0. Because pH adjustment
was not applied, the AA system was not operated for an
optimal run length (or an AA adsorption capacity). There-
fore, the run length of 9,600 BV (219 g/m3) achieved at
Plant C was shorter than the 15,536 BV (1,242 g/m3)
reported by Hathaway and Rubel (1987) who operated the
AA columns at pH 5.5. Nonetheless, the performance of
the AA system demonstrated that a throwaway AA treat-
ment system operating without pH adjustments is able to
consistently remove arsenic to low levels (i.e., <5 ug/L).
The ease of operation and low O&M cost of such a throw-
away system make this AA system an appealing option
for small water treatment plants and POE systems.
Fluoride and sulfate in the raw water are the major com-
peting ions for adsorption on AA. As shown on Figure 4-
18, inlet fluoride and sulfate concentrations were rela-
tively constant, ranging from 1.2 to 1.6 mg/L for fluoride
and 22 to 27 mg/L for sulfate. Removal of either ion
through the treatment process was insignificant most of
the time, except for several weeks immediately after the
medium replacement. For example, during the first week
after medium replacement, fluoride concentrations de-
creased from 1.2 to 0.9, 0.3, and 0.2 mg/L across the
treatment process. The same trend lasted for subse-
quent sampling events until the fluoride removal capacity
was reached. Sulfate removal appeared to be less sig-
nificant than that of fluoride.
Turbidity, hardness, NO3-NO2 (N), total Al, Fe, and Mn
contents in the inlet water were relatively low. Therefore,
their effects on the arsenic removal efficiency were insig-
nificant. In some cases, turbid source water, which can be
caused by iron precipitates if iron concentration is high,
may clog the AA filter and reduce the treatment efficiency.
Therefore, a cartridge filter often is installed prior to the
AA bed to prevent medium clogging and fouling.
After the media replacement, total Al concentrations in-
creased significantly in the tank effluent and combined
finished water, indicating alumina dissolution. An exam-
ple can be found from the data of January 6, 1999, when
total Al concentrations increased from nondetect levels
to 42, 109 and 112 ug/L at the TA1, TB1, and outlet
locations, respectively.
4.4.4.3 Spent AA Samples
Spent AA samples were collected from two roughing tanks
(TA1 and TA2) during AA replacement on December 29,
1998. Subsamples were analyzed for TCLP metals
(arsenic, barium, cadmium, chromium, lead, mercury,
selenium, and silver) and percent moisture. As shown in
Table 4-22, arsenic was not detected in leachate of the
spent AA sample from TA1, and slightly above the
detection limit in leachate of the spent AA sample from
TA2. None of the results from analyses of spent AA from
Plant C indicate exceedances of TCLP limits.
Table 4-22. Analytical Results of Spent AA Samples at Plant C
Parameter
Unit
MDL
Tank A1
Tank A2
TCLP Metals
As-TCLP
Ba-TCLP
Cd-TCLP
Cr-TCLP
Pb-TCLP
Hg-TCLP
Se-TCLP
Ag-TCLP
TCLP extraction
Percent moisture
Parameter
Caustic Waslf"
Total As
Total Al
Fluoride
Sulfate
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
NA
%
Unit
g/kg, dry
g/kg, dry
g/kg, dry
g/kg, dry
0.05
1.0
0.020
0.030
0.20
0.0002
0.05
.0.020
NA
0.1
MDL
0.1ซ
11'"
0.1 w
50
<0.05
1.2
<0.02
<0.03
<0.2
<0.0002
<0.05
<0.02
Complete
36
30 minutes
0.09
0.20
0.27
3.16
0.066
1.2
<0.02
<0.03
<0.2
<0.0002
<0.05
<0.02
Complete
24
NaOH Rinse Time (min)
120 minutes 30 minutes
0.11 . 0.07
0.23 0.35
0.31 0.39
3.17 NA
120 minutes
0.10
0.40
0.47
NA
(a) MDL is in units of ug/L for digestate.
(b) Spent AA was washed with 1% NaOH solution for 30 and 120 minutes, respectively.
50
-------
Spent AA subsamples were rinsed with 1 % NaOH solu-
tion for 30 and 120 minutes, respectively, to strip arse-
nic, fluoride, and sulfate from the AA surface. The waste
solution was analyzed for total arsenic, total aluminum,
fluoride, and sulfate. As shown in Table 4-22, the contact
time of 120 minutes yielded higher arsenic concentra-
tions than the contact time of 30 minutes, suggesting
that it might take longer than 30 minutes to reach de-
sorption equilibrium. For the contact time of 120 minutes,
the arsenic loading was 0.11 and 0.10 g/kg dry AA for
TA1 and TA2, respectively. Compared with the 0.30 g/kg
adsorption capacity estimated in Section 4.4.4.1, only
one-third of the arsenic was recovered by the caustic
wash. Clifford and Lin (1986) found that 50 to 70% of
arsenic could be recovered from the AA columns during
regeneration. Hathway and Rubel (1987) recovered 80-
82% of the arsenic during their pilot studies. In both
studies, a 4% NaOH solution was used to regenerate the
AA media. Therefore, a 4% NaOH solution and a 16-hr
contact time were used in a similar test performed on
spent AA samples collected from Plant D.
4.5 Plant D
Water samples were collected and analyzed at Plant D,
an AA plant, during the following three phases of the
study: initial source water sampling (June 10,1998), pre-
liminary sampling (August 5 through September 16,
1998), and long-term sampling (September 30, 1998
through September 1, 1999). Similar to Plant C, water
sampling was performed biweekly during the preliminary
and long-term sampling. Arsenic speciation sampling
was conducted during the initial source water sampling,
once during preliminary sampling, and every 8 weeks
during the long-term sampling. Spent AA samples were
collected once from one roughing tank in Plant D during
medium replacement on May 25,1999.
4.5.1 Plant D Description
Plant D serves approximately 200 employees in a manu-
facturer's warehouse. The ADD is approximately 3,000
gpd The AA system was installed by Secondwind Envi-
ronmental of Manchester, NH, in February 1996 with a
design flowrate of 20 gpm. The plant consists of four AA
tanks, which are positioned as two parallel sets of two
tanks in series. The first set of tanks are used as rough-
ing filters and the second set of tanks as polishing filters
(Figure 4-19).
The treatment process at Plant D consists of the follow-
ing major elements:
Intake. Raw water is supplied from a 500-ft-deep
well by a submersible pump at a flowrate of
20 gpm. Influent water is pressurized in a WX 205
captive-air hydropneumatic tank.
Chlorination. Approximately 1 mg/L chlorine is
added to the water through a single conventional
LMI chemical feed pump. The purposes of
chlorination are to convert all arsenite [As(lll)] to
arsenate [As(V)] and to disinfect the water.
Cartridge Filter. One Harmsco cartridge filter was
installed on the raw water header to remove parti-
cles from the well water. The filter is approximately
21 inches long and 13 inches in diameter, and is
reusable. The nominal rating of the cartridge is
20 urn.
Activated Alumina Tanks. The effluent from the
cartridge filter splits into two AA treatment trains of
two tanks in series. Gate valves exist to isolate
each train and control the split ratio. A flowmeter is
available on each train to confirm the exact split
ratio. Each fiberglass mineral tank (6-ft-tall by 2-ft-
diameter) contains approximately 10 ft3 of Alcoa
CPN AA (28 by 48 mesh). Table 4-23 lists typical
physical and chemical properties of this medium.
The influent flows downward through the AA bed
and the effluent is collected at the bottom of the
tank. At a design flowrate of 10 gpm (assuming
water is split evenly into each train), the hydraulic
loading rate to each tank is 3.18 gpm/ft2 and the
EBCT is 7.5 min. The differential pressure across
the medium was approximately 3 psi.
Medium Replacement. Same as Plant C, the AA
system at Plant D is operated on a throwaway basis
without pH adjustments. When the AA medium in
the roughing filters reaches its total arsenic removal
capacity, the spent AA is removed and replaced
with a virgin medium. The polishing filters are
moved to the roughing filter position, and the tanks
with the new virgin medium then are placed in the
polishing position. The tank rearrangement is
accomplished by changing the water flow through
valving, which is different from Plant C where the
medium tanks need to be physically repositioned.
A diagram of the system plumbing is provided in
Appendix D.2.
All four tanks contained virgin AA in February 1996
when the system was installed. The roughing
tanks, TA1 and TA2, were replaced with virgin AA
in November 1997 due to arsenic breakthrough.
Approximately 1 month later, TB1 and TB2 were
recharged with virgin AA because the medium had
cemented. The spent AA passed the TCLP test
and was disposed of as a nonhazardous waste.
From November 11, 1997 to May 25, 1999, TB1 .
51
-------
From well
BIMONTHLY
As (total), As (HI), As (V),
Hardness, Turbidity,
captive-air
hydropneumatic
tank
Septic Tank
As (total), As (in), As (V),
Hardness, Turbidity, NO3/NO2
As (total), As (III), As (V),
Hardness, Turbidity,
Plant D
Activated Alumina
Design How: 20 gpm
BIWEEKLY
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
Water Content, Total As / ^^^^^
pH,TCLP metals / X >
/ (Tank Al*
LEGEND
ฉWater Sampling
Location
Backwash Sampling
Location
Spent AA Sampling
Location
AAtank
Disinfectant
TJA.Q JJisintectant
.lJ Addition Point
BW)
AA]
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
As (total), Alkalinity,
pH, Total Al, Total Fe,
Total Mn, F, SO4
Note:
* The system plumbing can be reconfigured to place
Tanks Al and A2 into the lead positions and Tanks
Bl and B2 into the polishing positions.
To the distribution system
Figure 4-19. Process Flow Diagrams and Sampling Locations at Plant D
52
-------
Table 4-23. Typical Characteristics of CRN
Activated Alumina
Physical Characteristics
Appearance (color, shape)
Surface area, mVg
Total pore volume, cc/g
Total porosity, %
Bulk density, Ib/ft3 (kg/ma)
Abrasion loss, wt%
CPN AA (28x48 mesh)
White, granule
300 -340
0.5
60.6
47 (752)
0.2
Chemical Composition (wt%)
Na2O
Fe,0.
SiO2
Loss on ignition (Water)
Alumina XRD phase
Price, $/lb
94.1
0.3
0.03
0.02
5.5
Amorphors, chi, and gamma
1.98
and TB2 were operated in the roughing position
and TA1 and TA2 operated in the polishing posi-
tion. TB1 and TB2 were recharged again on May
25,1999 due to arsenic breakthrough. TA1 was
recharged on July 23,1999. Since May 25,1999,
TA1 and TA2 have been used as roughing filters
and TB1 and TB2 used as polishing filters.
Backwash. Backwash of each AA filter was origi-
nally scheduled every 4 months using untreated
water. The last two backwashes occurred in
January and May 1998. Backwash wastewater was
disposed of to a septic tank. Currently, backwash
is not performed on a routine basis.
Granular Activated Carbon Tank. Water from the
two AA treatment trains combines and flows into a
granular activated carbon (GAC) tank to be
dechlorinated. The GAC tank is 66 inches tall and
18 inches in diameter, and is rebedded every
2 years. Based on the plant record, residual CI2
was not detected in effluent after dechlorination.
Storage Tank. The treated water from the GAC
tank is stored in a 3,000-gal atmosphere tank
located inside the building. The water is pressur-
ized through two booster pumps buffered by two
pressure tanks before release to the distribution
system.
Water samples are collected monthly by a certified oper-
ator from the raw water, between the roughing and the
polishing tanks in each train, and from treated water.
Table 4-24 summarizes arsenic concentration results
from the monthly sampling events. The data show that
the arsenic concentrations in water samples collected at
A2B2 and A1B1 locations (i.e., after tanks TA2 and TA1,
respectively, which both serve as roughing tanks)
approached the 0.05 mg/L arsenic MCL on June 12 and
August 15, 1997, again respectively, which indicated
arsenic breakthrough. Therefore, both tanks were re-
bedded with virgin AA in November 1997. Water meter
readings were recorded during monthly sampling at
Plant D and are attached in Appendix D.3.
4.5.2 Initial Source Water Sampling
Source water for Plant D is supplied by a 500-ft-deep
bedrock well drilled in 1975 through a submersible pump.
The historic sampling data listed in Table 4-24 show that
the raw water arsenic concentrations ranged from 39 to
81 ug/L since March 1992. Arsenic speciation was not
conducted prior to this study. Typical source water qual-
ity measurements made at Plant D are presented in
Table 4-25.
On June 10,1998, an initial site visit to Plant D was con-
ducted during which time source water samples were
collected. Table 4-26 presents the analytical results from
the source water sampling. Consistent with plant records
(Table 4-25), the total soluble arsenic concentration was
relatively high, averaging 61.1 ug/L. Almost all of the
soluble arsenic existed as As(V) (60.6 ug/L). Particulate
arsenic was not detected in the raw water.
4.5.3 Preliminary Sampling
During the preliminary sampling phase of this study, water
samples were collected at four locations: (1) at the inlet;
(2) after the roughing tank TB1; (3) after the polishing tank
TA1; and (4) after the GAC tank. Sampling taps were
available at all four sampling locations. Sampling locations
and sample analyses are indicated on Figure 4-19.
Preliminary sampling consisted of biweekly sample col-
lection and analysis of various parameters (alkalinity, tur-
bidity, pH, hardness, fluoride, sulfate, total arsenic, total
Al, total Fe, and total Mn analysis). Arsenic speciation
sampling was conducted once on samples collected from
the inlet and after TB1. Speciation was not performed on
samples collected after TA1 and GAC tank because
As(V) is the dominant species in the source water based
on source-water sampling results. Table 4-27 presents
the results of the biweekly preliminary sampling.
As shown on Table 4-27, the inlet total arsenic con-
centrations were relatively constant, ranging from 56.0 to
62.1 ug/L. During the first week of speciation sampling,
the raw water contained an average of 61.6 ug/L As(V),
0.2 ug/L As(III), and no paniculate arsenic, which is con-
sistent with the source water sampling results.
The roughing AA filter removed 55 to 70% of the total
arsenic from the raw water. The polishing filter further
53
-------
Table 4-24. Arsenic Concentrations (pg/L) from Monthly Water Sampling at Plant D
(March 6,1992 to December 29,1999)
Date
03/06/92
03/16/95
03/21/96
04/16/96
05/08/96
06/19/96
07/22/96
08/20/96
09/06/96
10/15/96
11/13/96
12/20/96
01/09/97
02/21/97
03/21/97
04/17/97
05/15/97
06/12/97
07/14/97
08/15/97
09/12/97
10/15/97
11/18/97
12/23/97
01/19/98
02/24/98
03/25/98
04/15/98
05/19/98
06/15/98
07/23/98
08/27/98
09/16/98
10/15/98
11/12/98
01/19/99
02/16/99
03/18/99
04/28/99
06/22/99
07/14/99
08/25/99
09/17/99
10/29/99
11/22/99
12/29/99
Raw water
54
62
45
40
46
39
51
50
52
45
48
77
58
60
70
61
77
61
60
81
60
58
62
54
71
57
63
62
61
61
72
60
68
67
54
47
46
50
66
61
61
68
66
57
47
54
A1B1-
-
-
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5.
-
36
<5
24
32
38
36
47
42
45
-
_
-
_
-
-
-
_
_
-
_
_
-
-
-
_
<5
<5
<5
<5
<5
<5
<5
A2B2""
-
-
<5
<5
<5
<5
1 <5
<5
<5
<5
<5
<5
<5
<5
<5
42
43
: 50
. 65
57
48
44
; _
_
-
_
-
-
_
-
_
-
_
_
-
-
-
_
<5
1 <5
5
7
12
11
17
B1A1(C)
-
-
-
-
-
-
-
-
-
-
- ,
-
-
-
-
-
-
-
-
^
-
_
<5
26
<5
<5
<5
<5
<5
15
17
23
39
34
39
41
30
40
48
_
-
-
-
_
_
-
B2A2(d)
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
_
7
13
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
6
17
23
-
-
-
_
_
-
Treated
Water
-
-
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
5
Remarks
AA system installed in 2/96;
TA1 and TA2 were roughing
tanks; TB1 and TB2 were
polishing tanks
Arsenic breakthrough TA2 (50 jjg/L)
Arsenic breakthrough TA1 (50 |ig/L)
TA1 and TA2 rebedded and moved
to polishing positions in 11/97;
TBIand TB2 moved to roughing
positions
TBIand TB2 rebedded in 12/97 and
stayed in roughing positions
TB1 and TB2 rebedded and moved
to polishing positions on 5/25/99;
TAIand TA2 moved to roughing
positions
TA1 rebedded on 7/23/99, remained
at roughing position
(a) Water collected from a tap between the roughing tank TA1 and the polishing tank TB1.
(b) Water collected from a tap between the roughing tank TA2 and the polishing tank TB2.
(c) Water collected from a tap between the roughing tank TB1 and the polishing tank TA1.
(d) Water collected from a tap between the roughing tank TB2 and the polishing tank TA2.
- = Not sampled.
54
-------
Table 4-25. Typical Source Water Quality
Measurements at Plant D
Parameter
Alkalinity
Fluoride
Chloride
Sulfate
pH
Hardness
Sodium
Specific Conductance
Arsenic
Unit
mg/L"1
mg/L
mg/L
mg/L
mg/L(1)
mg/L
umhos/cm
M9/L
Concentration
56.8
1.15
8.0
10
8.3
55
13.9
166
40-80
(a) Measured as CaCO3
Table 4-26. Source Water Sampling Analytical Results
at Plant D (June 10,1998)
Parameter
Alkalinity
Fluoride
Sulfate
Turbidity
PH
Hardness
Ca Hardness
Mg Hardness
Total Al
Total Fe
Total Mn
NO3-NO2 (N)
TOC
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Units
mg/L("
mg/L
mg/L
NTU
mg/Lw
mg/Lw
mg/L("
Mg/L
Mg/L
ug/i.
mg/L0"
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Primary
Sample
56
1.13
15
0.31
8.3
49
42.2
7.1
<400
50
<20
0.36
1.0
60.0
60.8
ND
0.5
60.3
Duplicate
Sample
55
1.13
15
0.3
8.3
46
39
7.1
<400
60
<20
0.37
ND
58.1
61.4
ND
0.5
60.9
Average
55.5
1.13
15
0.31
8.3
47.5
40.6
7.1
<400
55
<20
0.37
ND
59.0
61.1
ND
0.5
60.6
(a) As CaCO3.
(b) Combined NO3-N and NO2-N.
reduced the total arsenic concentrations to 0.6-1.1 ug/L.
The combined treated water after the GAG tank con-
tained concentrations of total arsenic ranging from 0.7 to
1.1 ug/L, corresponding to an overall removal efficiency
of greater than 98%.
Fluoride concentrations were constant throughout the
treatment process, with 1.1 mg/L in the raw water and
1.2 mg/L in the finished water. Therefore, fluoride was
not removed by the AA filters. Similarly, sulfate concen-
trations remained at constant levels of 11 to 14 mg/L
throughout the treatment process, except for one sample
collected on August 5, 1998 with 30 mg/L of sulfate de-
tected after TB1. The reason for this anomaly is un-
known. Although both fluoride and sulfate have certain
affinities for the AA surface, their removal by AA was not
observed here; this result is most likely due to the nearly
exhausted AA arsenic removal capacity (similar results
observed at Plant C, as discussed in Section 4.4.3).
Alkalinity, total hardness, and nitrate/nitrite remained
relatively constant after the AA tanks because these ions
hardly reacted with the AA surface. Total aluminum con-
centrations in the water slightly increased after the treat-
ment, presumably due to the dissolution of AA medium.
Total iron and manganese concentrations in the raw
water were less than detection limit.
The preliminary sampling effort at Plant D resulted in no
changes to the long-term sampling approach.
4.5.4 Long-Term Sampling
Long-term sampling and analysis consisted of 24 bi-
weekly sampling events, including six arsenic speciation
sampling events. The four sampling locations used dur-
ing the preliminary sampling also were used during long-
term sampling. Additionally, spent AA samples were
collected once during medium replacement on May 25,
1999. A special short-term study was conducted using
the spent and a virgin medium. The following sub-
sections summarize the analytical results for arsenic,
other water quality parameters, spent AA, and the spe-
cial study.
4.5.4.1 Arsenic
Table 4-28 provides a summary of the arsenic analytical
results at different sampling locations. Total arsenic con-
centrations at the inlet ranged from 53.3 to 87.0 ug/L
with an average of 63.0 ug/L, exceeding the 0.05 mg/L
arsenic MCL. The inlet water contained primarily As(V)
with only minor concentrations of As(lll) and particulate
arsenic. Particulate arsenic was detected at the inlet only
on September 30, 1998 with a highest concentration of
12.7 ug/L. An abnormally high total Fe concentration
also was detected in the same samples. The maximum
As(III) concentrations were 0.5 ug/L at the inlet and 0.4
ug/L after the first tank. Should the As(lll) concentration
in the source water increase, As(lll) would be oxidized to
As(V) by chlorination before the AA adsorption.
Figure 4-20 presents the total arsenic concentrations at
each sampling location and the corresponding overall
removal percentages throughout the long-term sampling.
The figures were plotted against both sampling date and
BV of treated water, respectively. As shown on these
plots, the total arsenic concentrations after the roughing
tank (TB1) gradually approached influent levels, indi-
cating breakthrough. Based on the water usage data,
roughing tank TB1 treated approximately 4,350 BV of
water before arsenic breakthrough occurred on March 3,
1999. The medium was replaced with virgin AA on May
55
-------
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IO to IO to
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IN = inlet; TB1
CD
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- = No analysi
56
-------
Table 4-28. Summary of Arsenic Analytical Results at Plant D (September 30,1998 to September 1,1999)
Parameter
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Sampling Location
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
Inlet
After 1st Tank
Inlet
After 1st Tank
Inlet
After 1st Tank
Units
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
Number of
Samples
30
30
30
30
10
10
10
9
10
10
10
10
Minimum
Concentration
53.3
1.3
0.6
0.4
61.1
1.4
<0.1
<0.1
<0.1
0.1
61.1
1.3
Maximum
Concentration
87.0
60.8
3.2
9.6
70.4
60.6
12.7
0.7
0.5
0.4
70.1
60.4
Average
Concentration
63.0
31.6
1.3
1.2
66.3
38.2
2.1
0.1
0.2
0.2
66.1
37.9
Standard
Deviation
6.8
21.8
0.7
1.8
2.8
21.5
4.2
0.2
0.1
2.8
21.4
0.0
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
The 1 st tank was TB1 before the medium change-out on May 25,1999 and TA1 after the medium change-out.
The 2nd tank was TA1 before the medium change-out on May 25,1999 and TB1 after the medium change-out.
medium change-out) consistently contained <5 ug/L
arsenic. Except for one spike (9.6 ug/L) on May 26,
1999, the combined treated water had total arsenic con-
centrations similar to those in samples collected after the
second tank, indicating that the other treatment train per-
formed in similarly effective fashion. During the entire
study, the system arsenic effluent was consistently below
5 ug/L, corresponding to an average arsenic removal of
greater than 98%.
Using an average 5,260 BV of water treated prior to 50-
jag/L arsenic breakthrough, an inlet arsenic concentration
of 62.1 ug/L, an arsenic concentration of 26.5 ug/L after
the roughing tanks, and a density of 752 kg/m3, it was
estimated that approximately 106 g of arsenic was
removed from the raw water by the roughing filters,
corresponding to an arsenic loading of 0.25 g/kg (155
g/m3). This value is comparable to that obtained from
Plant C (0.30 g/kg or 219 g/m3) and to reported values
(Fox, 1989).
4.5.4.2 Other Water Quality Parameters
As with Plant C, sampling and analysis of other water
quality parameters were performed to provide insight
into the arsenic removal efficiency at the plant. Table 4-
29 summarizes the analytical results of the water quality
parameters measured during long-term sampling at
Plant D. Figure 4-21 plots the inlet and outlet alkalinity,
pH, fluoride, and sulfate concentrations.
Inlet alkalinity concentrations were relatively constant,
ranging from 44 to 59 mg/L (as CaCO3) with an average
of 56.9 mg/L. Alkalinity also remained constant through-
out all four sampling locations. Inlet pH values ranged
from 7.8 to 8.4 with an average of 8.2. This pH was
higher than the reported optimal pH for the AA process.
Even though the pH of the inlet water was not adjusted to
the optimal value', the system consistently removed arse-
nic to below 5 ug/L before the medium was exhausted.
Fluoride and sulfate in the raw water are the major com-
peting ions for adsorption on AA. As shown on Table 4-29
and Figure 4-21, inlet fluoride and sulfate concentrations
were relatively constant, ranging from 0.9 to 1.4 mg/L
and 11 to 15 mg/L, respectively. Removal of either ion
through the treatment process was not significant before
the medium replacement on May 25, 1999. However,
both fluoride and sulfate were removed to nondetect
levels by the freshly recharged tank on June 6, 1999.
Afterwards, the removal of fluoride lasted until the end of
this study; however, the sulfate removal capacity was
quickly exhausted.
Turbidity, hardness, NO3-NO2 (N), total Al, Fe, and Mn
contents in the inlet water were relatively low, so their
effects on the arsenic removal efficiency were deter-
mined insignificant. Similar to Plant C, after the medium
replacement, total Al concentrations increased signifi-
cantly at the second tank and effluent sampling loca-
tions, indicating medium dissolution. For example, total
Al concentration was as high as 7.5 mg/L at the second
tank and effluent sampling locations.
4.5.4.3 Spent AA Samples
Spent AA samples were collected from the roughing tank
TB1 during the medium replacement on May 25, 1999.
Subsamples were analyzed for TCLP metals and per-
cent moisture. Analytical results are presented in Table
4-30. All three samples had arsenic TCLP testing results
of less thafi 0.05 mg/L, far below the arsenic TCLP limit
of 5.0 mg/L. Only minor concentrations of barium were
detected in the leachates of samples from the middle
57
-------
100.0
80.0-
:xx-xx
TB1 was used as the roughing tank and TA1
was used as the polishing tank before medium
change-out on May 25,1999; since then, TA1
was used as the roughing tank and the recharged
TB1 was used as the polishing tank.
100.0
- 90.0
80.0 ~
I
70.0
- ' 60.0
09/02/98 10/22/98 12/11/98 01/30/99 03/21/99 05/10/99 06/29/99 08/18/99 10/07/99 11/26/99
Date
100.0
100.0
AA replacement and
tank switch on May 25,1999
50.0
3,000 , 3,500 4,000 4,500 5,000 5,500 6,000 6,500
BV of water treated
Figure 4-20. Total Arsenic Analytical Results during Long-Term Sampling at Plant D
58
-------
Table 4-29. Summary of Water Quality Parameter Analytical Results at Plant D (September 30,1998 to
September 1,1999)
Parameter
Alkalinity
Fluoride
Sulfate
Turbidity
PH
Total Hardness
NCyNO2 (N)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
Sampling Location
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1 st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
After 2nd Tank
Effluent
Inlet
After 1st Tank
Inlet
After 1st Tank
Inlet
After 1st Tank
Units
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
NTU
NTU
NTU
NTU
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
ug/L
van-
.ug/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/i-
pg/L
Number of
Samples
30
30
30
30
30
30
30
30
30
30
30
30
6
6
6
6
30
30
30
30
6
6
6
6
6
6
6
6
30
30
30
30
30
30
30
30
30
30
30
30
10
9
10
10
10
10
Minimum
Concentration
44
47.5
52
40
0.9
<0.1
<0.1
<0.1
11
7.5
<5
<5
0.2
<0.1
<0.1
<0.1
7.8
7.8
7.0
7.7
46
47
<2
<2
0.3
0.3
0.3
0.3
<11
<11
<11
<11
<30
<30
<30
<30
<0.5
<0.5
<0.5
<0.5
<11
13.3
<30
<30
<0.5
<0.5
Maximum
Concentration
59
63
65
62
1.4
1.4
1.5
1.6
15
17
16
15
0.4
0.2
<0.1
<0.1
8.4
8.4
9.9
9.5
51
51
50
50
0.8
1.3
1.4
0.5
44.7
471
148(=)
190""
483
127
53.7
54.3
11.2
0.7
<0.5
<0.5
<11
19.2
<30
<30
<0.5
1.5
Average
Concentration
56.9
56.8
56.8
55.2
1.1
1.1
1.0
1.0
13.5
13.5
12.3
12.2
0.3
0.1
0.05
0.05
8.2
8.1
8.1
8.0
48.8
49.7
39.8
40.2
0.4
0.6
0.6
0.4
14.1
55.1
54.9!"
55.5<"
44.4
21.1
18.1
17.1
0.9
0.3
0.3
0.3
<11
15.5
<30
<30
<0.5
0.4
Standard
Deviation
' 2.9
2.6
2.6
4.1
0.1
0.3
0.5
0.5
1.0
1.8
3.9
3.9
0.1
0.1
0.0
0.0
0.2
0.1
0.5
0.4
1.8
1.5
19.1
19.2
0.2
0.4
0.4
0.1
10.2
103
47.5"1
51 .7'"
97.7
23.1
9.5
8.2
2.3
0.1
0.0
0.1
0.0
2.1
0.0
0.0
0.0
0.4
One-half of the detection limit was used for nondetect samples for calculations.
Primary and duplicate samples were averaged for calculations.
The 1 st tank was TB1 before the medium change-out on May 25,1999 and TA1 after the medium change-out.
The 2nd tank was TA1 before the medium change-out on May 25,1999 and TB1 after the medium change-out.
(a) High total Al concentrations measured on May 26,1999 after the polishing tank and at the outlet due to medium dissolution were not included
for calculations.
59
-------
80.0
60.0
40.0-
20.0-
0.0
AA change-out on May 25,1999
Met pH
- - o- -o- o- -o- -o. .o- o- -o
12.0
-- 11.0
10.0
-9.0
--8.0
-7.0
->- inlet alkalinity
* Outlet alkalinity
AA change-Out
--O'-InletpH
* Outlet pH
6.0
09/12/98 11/01/98 12/21/98 02/09/99 03/31/99 05/20/99 07/09/99 08/28/99 10/17/99
Date
20.0
15.0
10.0
o
I
5.0
0.0
AA change-out on May 25,1999
--5.0
Inlet fluoride
6.0
* 'Inlet sulfate
*Outlet sulfate
AA change-out
-o - "inletfluoride
Outlet fluoride
4.0 a
E
I
- 3.0 3
I
2.0 a
--1.0
0.0
09/12/98 11/01/98 12/21/98 02/09/99 03/31/99 05/20/99 07/09/99 08/28/99 10/17/99
Date
Figure 4-21. Inlet and Outlet Alkalinity, pH, Fluoride, and Sulfate Analytical Results at Plant D
60
-------
Table 4-30. Analytical Results of Spent AA Samples at Plant D
Parameter
Unit
MDL
TB1-Top
TB1-Middle
TB1-Bottom
TCLP Metals
As-TCLP
Ba-TCLP
Cd-TCLP
Cr-TCLP
Pb-TCLP
Hg-TCLP
Se-TCLP
Ag-TCLP
TCLP extraction
Percent moisture
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
NA
%
0.05
1.0
0.020
0.030
0.20
0.0002
0.05
0.020
NA
0.1
<0.05
<1.0
<0.02
<0.03
<0.2
<0.0002
<0.05
<0.02
Complete
31.6
<0.05
1.1
<0.02
<0.03
<0.2
<0.0002
<0.05
<0.02
Complete
31.3
<0.05
1.4
<0.02
<0.03
<0.2
<0.0002
<0.05
<0.02
Complete
32.0
and bottom sections of TB1. None of the spent AA ana-
lytical results indicate exceedances of regulatory levels.
Therefore, the spent alumina could be disposed of as a
nonhazardous waste material.
4.5.5 Special Study at Plant D
4.5.5.1 Regeneration of Spent AA Using
Caustic Solution
Spent AA samples collected from the top, middle, and
bottom sections of TB1 were mixed with caustic solution
(4% NaOH) overnight to strip arsenic, fluoride, and sul-
fate from the AA surface. The rinsates were analyzed for
total arsenic, fluoride and sulfate. The amounts of arse-
nic, fluoride, and sulfate desorbed from the AA medium
were calculated as described in Section 3.4.2, and the
results are presented in Table 4-31. The same samples
also were digested with concentrated nitric acid and the
digestates were analyzed for total arsenic. As shown on
Table 4-31, the amounts of arsenic and fluoride recov-
ered from the spent AA showed a slightly increasing
trend from the top to the bottom sections of the tank. The
data based on the acid digestion are higher, but showing
a similar increasing trend. The average arsenic removal
capacity based on acid digestion is 0.41 g/kg, higher than
the one estimated based on column operation (0.25 g/kg
AA) (Section 4.5.4.1). Therefore, the arsenic removal
capacity based on column operation might have been
underestimated. The arsenic removal capacities can be
placed in the following order:
caustic wash (0.21 g/kg)
< column operation (0.25 g/kg)
< acid digestion (0.41 g/kg)
Based on the capacities from the column operation and
acid digestion, approximately 84% and 50% of arsenic
were recovered by the caustic wash respectively, which
fell in the ranges reported by Hathway and Rubel (1987)
and Clifford and Lin (1986).
Table 4-31. Analytical Results of Caustic Wash
and Acid Digestion of Spent AA Samples
at Plant D
Parameter
Unit
TB1-
Top
TB1-
Middle
TB1-
Bottom
Average
Caustic Wash with 4% NaOH
Total As
Fluoride
Sulfate
g/kg
g/kg
g/kg
0.19
0.19
0.36
0.40
0.40
0.48
0.21
0.21
0.42
0.42
0.56
0.59
0.23
0.23
0.43
0.43
0.39
0.36
0.21
0.41
0.46
Acid Digestion with HNO3
Total As g/kg
0.38
0.39
0.50
0.41
4.5.5.2 Adsorption of Arsenic onto AA
The results of the kinetic study as shown on Figure 4-22
indicated that arsenic adsorption on AA had reached equi-
librium within 2 days, consistent with previous studies by
Rosenblum and Clifford (1984). As a result, all subse-
quent isotherm batch tests were maintained for 6 days to
ensure equilibrium had been reached.
The As(V) adsorption isotherm on AA at pH 7.7 ฑ0.2 is
presented in Figure 4-23. The following data were fitted
with both Freundlich and Langmuir models and the
resulting equations are shown:
Freundlich model:
qe = 0.1679 x Ce(0452>, r*= 0.9632 (4-1).
Langmuir model:
qe = 0.6778 x 0.2957 x (4-2)
C,/(1+0.2957 x Ce), r*= 0.9677
where qa and Ce are the solid (mg/g AA) and liquid phase
(ug/L) equilibrium As(V) concentrations, respectively.
61
-------
600.0
345
Time elapsed (days)
Figure 4-22. Kinetics of Arsenic Adsorption on AA Media
1.00
3
ฃ?
3
0.10
Freundlich model:
K = 0.1679
l/n = 0.452
0.1
Figure 4-23. Arsenic Adsorption Isotherm on AA Media
10
100
Ce
62
-------
Because qe did not reach plateau under the experimental
conditions, the Freundlich model seemed to fit the data
better than the Langmuir model. The significance of the
Freundlich model with respect to As(V) adsorption onto
AA lies primarily in the assumption of heterogeneous ad-
sorption site energies and multilayer adsorption. In batch
tests performed by Rosenblum and Clifford (1984), a
similar relation between the solid and liquid phase arse-
nic concentrations was established; however, at much
higher aqueous equilibrium As(V) concentrations (i.e., up
to 4 mg/L).
Based on the Freundlich model, at an inlet arsenic con-
centration of 63.0 ug/L, the AA adsorption capacity is
predicted to be 1.09 g As(V)/kg AA. This value is higher
than the capacities obtained from the column operation
(0.25 g/kg), caustic wash (average of 0.21 g/kg), or acid
digestion (0.41 g/kg). Because the column operated at
an average pH of 8.3, higher than the pH of the isotherm
study (pH 7.7), the pH most likely affected the adsorption
capacity. In actual column operation, the arsenic capacity
obtainable should be far less than the equilibrium values
obtained from the adsorption isotherm. The competing
anions and the nonequilibrium mass transfer limitations
are some of the reasons for the low column capacities.
An additional reason for the low capacity is the possible
fouling of the porous alumina by particulate and colloidal
constituents such as colloidal silica and mica (Clifford
and Lin, 1986), which were not monitored during this
study.
63
-------
5.0 Quality Assurance/Quality Control
5.1 Quality Assurance Objectives
The precision, accuracy, MDL, and completeness for
each of the analytical measurements required for this
study were established in the QAPP (Battelle, 1998) and
are listed in Table 1 of the QA/QC Summary Report
(Battelle, 2000b), which was prepared under separate
cover. These terms serve as indicators of data quality
and were calculated in accordance with the formulas
provided in the QAPP. The precision, accuracy, and
MDL of each of the measurements performed during the
present study are presented in the summary report.
These quality assurance (QA) data are organized ac-
cording to the date of sample receipt or sample analysis
and are not site-specific. Therefore, the QA/QC section
of this report shares the same QA data with other water
treatment plants that have been included in the study.
5.2 Overall Assessment of Data Quality
Quantitative QA objectives listed in the QA/QC Summary
Report include precision as relative percent difference
(RPD), accuracy as percent recovery (%R), MDL, and
completeness. The precision, accuracy, and MDL or re-
porting limit of each of the measurements performed
during this study are presented in the QA/QC Summary
Report. Total arsenic, aluminum, iron, and manganese
analyses on water samples were conducted in Battelle's
ICP-MS laboratory. The QA data associated with these
metal analyses also are presented in the QA/QC Sum-
mary Report. Other water quality parameters including
alkalinity, pH, turbidity, hardness, nitrate-nitrite, sulfate,
fluoride, TDS, and TSS were analyzed by Wilson Envi-
ronmental Laboratories, and their QA data were summa-
rized in the QA/QC Summary Report. QA data for TOG
analysis performed by CT&E Environmental Laboratory
are presented in the QA/QC Summary Report. The
TCLP metal analysis on sludge samples also was con-
ducted by Wilson Environmental Laboratories and its
associated QA data are summarized in the QA/QC
Summary Report. Overall, the QA objectives of preci-
sion, accuracy, MDL, and completeness were achieved
by all laboratories. Therefore, all the valid data were
used to evaluate the effectiveness of the treatment pro-
cesses and support conclusions.
5.2.1 Total Arsenic, Aluminum, Iron,
and Manganese
At the early phase of the study, total As analysis was
performed by Battelle's ICP-MS laboratory, and total Al,
Fe, and Mn were analyzed by Wilson Environmental
Laboratories. Starting from June 1998, all four metals
were analyzed by Battelle's ICP-MS laboratory. There-
fore, QA data for only the total arsenic analysis before
June 16,1998 and QA data for all four metals afterwards
are presented.
The laboratory duplicate and matrix spike (MS) analyses
were performed every 10 samples (instead of 20 sam-
ples as required by the QAPP [Battelle, 1998]). All the
samples were analyzed for four metals although metals
other than arsenic may not be required for every sample.
Therefore, Battelle's ICP-MS laboratory performed more
QA/QC analyses than what were specified in the QAPP.
Greater than 99% of the precision results for all metals
met the QA objective of ฑ25% (with only two Fe outliers:
27% on August 8, 1998 and 74% on December 22,
1998; three As outliers: 27% on August 18, 1998, 182%
on October 1, 1998, and 27% on July 30, 1999; and four
Al outliers: 26% and 33% on August 18, 1998, 48% on
December 15, 1998, and 48% on January 25, 1999).
The majority of the accuracy data associated with matrix
spike analysis on August 31, 1998 exceeded the QA
limits of 75 to 125%. It is suspected that MS analyses
were not performed correctly on that day. After this
problem had been identified, Battelle's Work Assignment
Leader, laboratory QA officer, and Battelle's task leaders
met to discuss the cause of the deviation. Corrective
64
-------
actions were taken including re-analyzing samples and
adjusting the amount of spike added to samples (i.e., the
Fe spike was increased from 50 to 100, 200, 225, or
even as high as 2,000 ug/L because most of samples
contain much more than 50 ug/L of Fe). As indicated in
the QA/QC Summary Report, the MS data quality was
significantly improved since November 3, 1998. Exclud-
ing the data on August 31, 1998, only five arsenic data
were outside the acceptable range for accuracy. How-
ever, 15 Al, 26 Fe, and 14 Mn accuracy data did not
meet the QA objective. With exceptions of one 23% and
one 38% of accuracy, the Al accuracy data range from
65 to 125%. The Mn accuracy data range from 67 to
106% with the exception of one 37%. The Fe accuracy
data range from 55 to 142% with exceptions of one 14%,
one 23%, and one 38%.
All laboratory control samples showed %R within the
acceptable QA limit of 75 to 125% except for six outliers
for total Fe with %R ranging from 73 to 143%. Al was not
spiked to laboratory control samples until November 3,
1998 after corrective actions were taken. The MDL of Fe
is the same as target MDL; however, MDLs of other
three metals were far below the target levels as specified
in the QAPP (Battelle, 1998).
5.2.2 Water Quality Parameters
Water quality parameters include alkalinity, pH, turbidity,
hardness (Ca and Mg), nitrate-nitrite, sulfate, fluoride,
TDS, TSS and TOG. As shown in Table 3 of the QA/QC
Summary Report, all the precision data were within the
acceptable QA limit of ฑ25% except for two Mn analyses
with a 29% RPD (April 10 and 17, 1998) and three
nitrate-nitrite analyses with 40% RPD (August 6, 1998,
January 13, 1999, and February 11, 1999). The high
RPDs of these analyses might have been caused by the
low measured concentrations in the samples that were
close to the detection limits for Mn and nitrate-nitrite. The
accuracy data indicate that only one Al (70% on March 2,
1998), two Mn (66% and 64% on May 12, 1998), and
one Mg (126% on August 7, 1998) %R slightly exceeded
the QA objectives of 75 to 125%. Although the matrix
spike duplicate (MSD) analysis was not required by the
QAPP, the accuracy and the precision data relating to
MSD also were presented. The MS/MSD analyses are not
applicable to pH and turbidity measurements, though. The
laboratory did not perform MS/MSD analyses on Ca and
Mg hardness analyses until October 15, 1998 upon
Battelle's request. All laboratory control samples showed
%R within the acceptable QA limit of 75 to 125%. Re-
porting limits were below the required levels for all the
analytes except for sulfate. The reporting limits of sulfate
was 5 mg/L, exceeding the required MDL of 3.66 mg/L.
All precision, accuracy, and %R values for the TOC
analysis were within acceptable QA limits with the ex-
ception of one accuracy value, which was slightly below
the 75 to 125% range at 72% (February 21,1999).
5.2.3 TCLP Metals
The TCLP metals analyzed in the spent AA samples in-
cluded As, Se, Hg, Ba, Cd, Cr, Pb, and Ag. The preci-
sion data were within QA limits of ฑ25%. The accuracy
of matrix spikes and percent recovery of laboratory con-
trol samples were all within QA limits of 75 to 125%
except for one slightly elevated RPD for TCLP Se MS/
MSD at 26% (November 17,1998).
\
65
-------
6.0 References
Andreae, M. 1977. "Determination of Arsenic Species in
Natural Waters." Anal. Chem., 4&. 820-823.
Aqua Specialties. 1999. Personal communication with
Chris Kofer, Owner, by Battelle.
Battelle. 1998. Quality Assurance Project Plan for Evalu-
ation of Treatment Technologies for the Removal of
Arsenic from Drinking Water. Prepared for EPA's
NRMRL, Cincinnati, OH.
Battelie. 1999. Evaluation of Treatment Technologies for
the Removal of Arsenic from Drinking Water: Conven-
tional Coagulation/Filtration and Lime Softening. Pre-
pared for EPA's NRMRL, Cincinnati, OH. September.
Batteile. 2000a. Evaluation of Treatment Technologies
for the Removal of Arsenic from Drinking Water: Con-
ventional Iron Removal. Being prepared for EPA's
NRMRL, Cincinnati, OH.
Chen, A.S.C., and V.L. Snoeyink. 1987. "Activated Alum-
ina Adsorption of Dissolved Organic Compounds be-
fore and after Ozonation." ES&T, 21 (January): 83-90.
Chen, A.S.C., V.L. Snoeyink, J. Mallevialle, and F.
Fiessinger. 1989. "Activated Alumina for Removing
Dissolved Organic Compounds." J. AWWA: 53-60.
Chen, S.L., S.R. Dzeng, M. Yang, K. Chiu, G. Shieh, and
C.M. Wai. 1994a. "Arsenic Species in Groundwaters of
the Blackfoot Disease Area, Taiwan." ES&T: 877-881.
Chen, R.C., S. Liang, H.C. Wang, and M.D. Beuhler.
1994b. "Enhanced Coagulation for Arsenic Removal."
J. AWWA (September): 79-90. .
Clifford, D. 1999. "Ion Exchange and Inorganic Adsorp-
tion." In American Water Works Association (Eds.),
Water Quality and Treatment: A Handbook of Commun-
ity Water Supplies. 5th ed. New York: McGraw-Hill.
Clifford, D., and C. C. Lin. 1986. "Arsenic Removal from
Groundwater in Hanford, California-A Preliminary Re-
port." University of Houston, Department of Civil/Envi-
ronmental Engineering.
Clifford, D., and C. C. Lin, 1991. "Arsenic HI and Arsenic V
Removal from Drinking Water in San Ysidro, New
Mexico." EPA/600/2-91/011. U.S. EPA, Cincinnati, OH.
Clifford, D., and E. Rosenblum. 1982, 'The Equilibrium
Arsenic Capacity of Activated Alumina." U.S. EPA,
Cincinnati, Cooperative Agreement CR-807939-02.
Clifford, D., L. Ceber, and S. Chow. 1983. "Arsenic(lll)/
Arsenic(V) Separation by Chloride-Form Ion-Exchange
Resins." Proceedings of the XI AWWA WQTC.
Clifford, D., G. Ghurye, and A. Tripp. 1998. "Arsenic
Removal by Ion Exchange with and without Brine
Reuse." Proceedings of AWWA Inorganic Contami-
nants Workshop, San Antonio, TX.
Driehaus, W., M. Jekel, and U. Hildebrand. 1998.
"Granular Ferric Hydroxide-A New Adsorbent for the
Removal of Arsenic from Natural Water. J. Water SRT-
Aqua 47(1): 30-35.
Eaton, A.D., H.C. Wang, and J. Northington. 1997.
"Analytical Chemistry of Arsenic in Drinking Water."
AWWARF Project 914.
Edwards, M., S. Patel, L. McNeill, H. Chen, M. Frey,
A.D. Eaton, R.C. Antweiler, and H.E. Taylor. 1998.
"Considerations in As Analysis and Speciation."
J. AWWA (March): 103-113.
EPA, see United States Environmental Protection Agency.
Ficklin, W.H. 1983. "Separation of Arsenic (III) and Arse-
nic(V) in Groundwaters by Ion Exchange." Talanta,
30(5): 371-373.
66
-------
Fox, K. 1989. "Field Experience with Point-of-Use Treat-
ment Systems for Arsenic Removal." J. AWWA: 94-
101.
Frank, P., and D. Clifford. 1986. "Arsenic (111) Oxidation
and Removal from Drinking Water." EPA-600-52-
86/021.
Hathaway, S.W., and F. Rubel. 1987. "Removing Arsen-
ic from Drinking Water." J. AWWA, 79(8), 61 -5.
Hering, J.G., P.Y. Chen, J.A. Wilkie, M. Elimelech, and
S. Lung. 1996. "Arsenic Removal by Ferric Chloride."
J.AWWA (April): 155-167.
Joshi, A., and Chaudhuri, M. 1996. "Removal of Arsenic
from Groundwater by Iron Oxide-Coated Sand." J.
Env. Eng., Am. Soc. Civ. Engrs., 122: 769-771.
Lowry Engineering, Inc. 1990. Personal communication
with Battelle.
McNeill, L.S., and M. Edwards. 1997. "Arsenic Removal
During Precipitative Softening." Journal of Environ-
mental Engineering (May): 453-460.
Rosenblum, E., and D. Clifford. 1984. 'The Equilibrium
Arsenic Capacity of Activated Alumina." EPA-600/52-
83-107. U.S. EPA, Cincinnati, OH.
Scott, K.N., J.F. Green, H.D. Do, and S.J. McLean.
1995. "Arsenic Removal by Coagulation." J. AWWA
(April): 114-126.
Secondwind Environmental. 1999. Personal communica-
tion with Jodie Pepin, Commercial/Public Water Man-
ager, by Battelle.
Simms, J., and F. Azizian. 1997. "Pilot-Plant Trials on
the Removal of Arsenic from Potable Water Using
Activated Alumina." Proc. Water. Qua/. Technol. Conf.:
P6I/1-P6I/14.
Singh, G., and D. Clifford. 1981. 'The Equilibrium Fluo-
ride Capacity of Activated Alumina." EPA- 600/52-81-
082. U.S. EPA, Cincinnati, OH.
Sorg, T.J. 1993. "Removal of Arsenic From Drinking
Water by Conventional Treatment Methods." Proceed-
ings of the 1993 AWWA WQTC.
Tate, C.H., and K.F. Arnold. 1990. "Health and Aesthetic
Aspects of Water Quality." In American Water Works
Association (Eds.), Water Quality and Treatment: A
Handbook of Community Water Supplies. New York:
McGraw-Hill.
United States Environmental Protection Agency. 1998.
Research Plan for Arsenic in Drinking Water. EPA/
600/4-98/042. Office of Research and Development,
Washington, D.C. February.
Vagliasindi, F.G.A., M. Henley, N. Schulz, and M.M.
Benjamin. 1996. "Adsorption of Arsenic by Ion Ex-
change Resins, Activated Alumina, and Iron-Oxide
Coated Sands." Proc. Water Qua/. Technol. Conf.,
1829-1853.
Vagliasindi, F.G.A., and M.M. Benjamin. 1997. "Arsenic
Behavior in Packed Bed Adsorption Reactors: Media
Performance vs. Water Quality Composition." Proc.
Water Works Assoc. Conf., 443-456.
67
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APPENDIX A - D
-68-
-------
APPENDIX A
Plant A Data
A.1 Complete Analytical Results from Long-Term Sampling at Plant A
A.2 Technical Data on Puroliteฎ A-300
A.3 Water Usage Report
69
-------
A.1 Complete Analytical Results from Long-Term Sampling at Plant A
70
-------
Table A-1. Analytical Results from Long-Term Sampling, Plant A (September 1 to 22,1998)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/L("
mg/L""
mg/Lซ"
mg/Lw
pg/L
ug/L
ug/L
ug/L
ug/t
yg/L
Mg/L
Mg/L
M9/L
pg/L
ug/L
9/1/98
IN-
89
28
<0.1
7.6
64.7
57.4
7.3
0.3
43.9
39.1
45.4
47.9
<0.1
<0.1
0.4
0.4
45.0
47.5 .
16.4
21.5
<30
<30
2.1
1.8
<11
<11
<30
<30
-1.2
1.0
OU
68
<5
<0.1
7.3
63.7
56.7
7.0
0.2
0.7
0.7
1.2
1.2
<0.1
<0.1
<0.1
<0.1
1.2
1.2
<11
13.4
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
9/8/98
IN
85
84
25
24
7.5
7.5
41.9
23.9
<30
0.9
OU "
83
83
<5
<5
7.5
7.5
0.9
13.4
<30
<0.5
--.. 9/15/98
. "JN
85
25
7.6
44.9
32.2
<30
2.8
I OU
92
<5
7.7
3.2
21.7
<30
<0.5
9/2"2/98 "
'' IN
89
24
7.6
49.3
23.8
<30
0.8
OU
88
<5{*
7.6
54.0
19.4
<30
<0.5
(a) Measured as CaCO3.
(b) Combined NO3-N and NO2-N.
(c) Confirmed by sample re-analysis.
IN = inlet; OU = outlet.
71
-------
Table A-2. Analytical Results from Long-Term Sampling, Plant A (September 29 to October 20, i 998)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L"1
mg/L
NTU
mg/Lw
mg/L<"
mg/L("
mg/L""
PS/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
Pg/L
pg/L
pg/L
pg/L
9/29/98
IN
92
26
0.1
7.6
83.9
75.4
8.4
0.5
51.6
59.2
60.9
59.9
<0.1
<0.1
0.7
0.6
60.2
59.3
14.4
15.8
<30
<30
0.6
0.5
<11
<11
<30
<30
<0.5
<0.5
OU
85
20
<0.1
7.5
79.0
70.4
8.6
0.8
81 .0""
82.0
95.5
1 97.0
<0.1
<0.1
0.3
0.3
95.2
96.7
15.6
16.0
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
10/6/98" / '
IN
89
89
25
25
7.7
7.7
52.5
24.3
<30
1.0
qu
89
88
25
24
7.6
7.6
43.4
<11
<30
<0.5
10/13/98
'-IN
86
24
7.6
35.1
26.4
<30
1.3
, -OU, '-
72
16
7.5
27.2
13.9
<30
<0.5
10/20/98
'"'# -*,
92
26
7.6
50.4
15.7
<30
0.7
pu 1.
78
22
7.4
28.9
11.7
<30
<0.5
(a) Measured as CaCO,.
(b) Combined NOa-N and NO2-N.
(c) Confirmed by sample re-anaiysis.
IN ซinlet; OU = outlet.
72
-------
Table A-3. Analytical Results from Long-Term Sampling, Plant A (October 27 to November 17,1998)
Sampling Date
Sampling Location
Parameter 'Unit..
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (paniculate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L""
mg/L
NTU
mg/L!a)
mg/L("
mg/L<"
mg/L(b)
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
110/27/98
j ฃ
IN*
92
26
<0.1
7.5
75.6
67.7
7.9
0.6
48.9
47.2
59.8
59.5
<0.1
<0.1
0.2
0.1
59.6
59.4
19.0
<11
<30
<30
0.6
0.5
<11
<11
<30
<30
0.5
<0.5
OU
79
21
<0.1
7.4
70.7
62.9
7.8
0.8
27.9
27.0
32.3
32.5
<0.1
<0.1
<0.1
<0.1
32.3
32.5
<11
11.9
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
1 1/3/98
TN
-^i. _
90
90
27
25
7.5
7.5
49.7
<11
<30
0.8
OU
82
82
23
22
7.5
7.5
34.4
<11
<30
<0.5
* /S"11/10/98W -^
1
91
24
7.5
48.6
12.0
<30
0.6
* ouf.
ป
49
14
7.3
20.5
<11
<30
<0.5
4 1/1*7/9,8 _ ' ' "
- IN ,
86
23
7.6
37.6
<11
<30
0.5
^x ~ x
' OU -
t* * f
70
<5
7.4
1.2
<11
<30
<0.5
(a) Measured as CaCO3.
(b) Combined NO3-N and NO2-N.
(c) Samples were collected after the AX300 tank was regenerated on 11/10/98.
IN = inlet; OU = outlet.
73
-------
Table A-4. Analytical Results from Long-Term Sampling, Plant A (Nov. 24 to Dec. 15,1998)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (participate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/Lw
mg/L
NTU
mg/L*1
mg/L("
mg/L"1
mg/Lw
ug/L
Mg/L
Mg/L
ug/L
ug/L
ug/L
ug/L
Mg/L
van.
ug/L
pg/L
1 1/24/98(c)
IN
OU
-
-"
12/01/98 '''"
IN
90
23
<0.1
7.2
70
61.7
7.9
0.5
37.3
38.7
42.0
43.6
<0.1
<0.1
0.7
0.7
41.3
42.9
14.4
17.3
32.1
31.2
0.8
0.9
2.9
3.9
15.6
11.5
0.8
0.6
. OU
90
<5
<0.1
7.3
67
59.7
7.7
0.1
0.9
0.9
0.9
1.0
<0.1
<0.1
0.1
0.1
'0.8
0.9
11.6
11.1
34.8
33.4
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
12/08/98
IN" ~
87
88
26
26
7.6
7.6
42.5
13.6
<30
1.4
" 'oU
90
90
<5
<5
7.6
7.6
3.8
11.5
<30
<0.5
12/15/98
IN "
78
22
7.4
28.6
<11
<30
<0.5
OU
87
<5
7.6
33.6
<11
<30
<0.5
(a) Measured as CaCO3.
(b) Combined NO,-N and NO2-N.
(c) No sampling due to Thanksgiving holiday.
IN = inlet; OU = outlet.
74
-------
Table A-5. Analytical Results from Long-Term Sampling, Plant A (Dec. 22,1998 to Jan. 12,1999)
- 'Sampling Date
Sampling tbcation
Parameter ' Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Ai
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L<"
mg/L
NTU
mg/L"'
mg/L0"
mg/Lw
mg/L*'
ug/L
yg/L
ug/L
pg/L
pg/L
Mg/L
ug/L
ug/L
ug/L
pg/L
pg/L
12/22798fe!
- * -IN
%.
f
*
,/'
_-
," J
v,.
^
j r ' ' ~-
,- i^
,-
-
^ -?*
"* 3> J " '*
; *
"
6u
a* "* "
j--."
^~
S ' ' ,
V'- *L'
^7^"
r*
k r
_
/
*," x
f-. i1'**'"
.
12/29/98 ^
_ -
f "
ou
' -
, " ,
J &*
'
"
.*
* "*#"'
1 ^. ซ^
^
, --
X ^
'
_-,
01/05/99,
_, IN
89
23
7.6
37.7
<11
40.1
<0.5
qu
82
21
7.5
45.1
<11
40.3
<0.5
. 01/12/99
IN
91
23
<0.1
7.6
70
62.4
7.6
0.5
39.4
38.7
41.5
42.1
<0.1
<0.1
0.8
0.7
40.7
41.4
22.1
20.3
80.2
74.1
<0.5
0.8
<11
<11
<30
<30
1.0
0.7
oU
81
21
<0.1
7.5
67
59.4
7.2
0.7
34.9
- 32.2
29.0
28.7
5.9
3.5
0.3
0.4
28.7
28.3
13.6
12.2
<30
<30
0.8
1.4
<11
<11
<30
<30
2.7
<0.5
(a) Measured as CaCO3.
(b) Combined NO3-N and NO2-N.
(c) No sampling due to Christmas holiday.
IN = inlet; OU = outlet.
75
-------
Table A-6. Analytical Results from Long-Term Sampling, Plant A (Jan 19 to Feb 9,1999)
Sampling Date
Sampling Location
Parameter - Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/Lw
mg/L
NTU
mg/Lw
mg/L<"
mg/Lw
mg/L0"
ug/L
ug/L
ug/L
ug/L
ug/L
M9/L
pg/L
ug/L
pg/L
MS/L
pg/L
01/19/99
IN
86
85
23
23
7.4
7.4
34.7
14.0
<30
1.2
OU
73
. 73
22
21
7.4
7.4
28.1
<11
<30
0.7
01/26/99
IN
77
20
7.5
31.9
<11
41.3
0.6
ouX
70
20
7.5
22.8
<11
48.3
<0.5
'-; "Q2/02/99^
IN
88
23
7.6
42.1
34.1
<30
<0.5
OU
74
20
7.4
22.2
60.0
<30
<0.5
02/09/99tc);
IN'
*..! ? ^
83
23
<0.1
7.5
74
65.7
8.0
0.5
39.1
39.3
39.7
41.9
<0.1
<0.1
0.7
0.8
39.0
41.1
27.4
19.9
41.9
<30
3.1
2.0
<11
<11
<30
<30
<0.5
<0.5
OU
41
<5
<0.1
7.2
69
61.9
7.2
0.4
3.7
3.4
3.6
3.5
0.1
<0.1
<0.1
<0.1
3.6
3.5
<11
11.8
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
(a) Measured as CaCO,.
(b) Combined NO3-N and NO2-N.
(c) The AX300 tank was regenerated on 2/6/99.
IN = inlet; OU = outlet.
76
-------
Table A-7. Analytical Results from Long-Term Sampling, Plant A (Feb 16 to Mar 9,1999)
Sampling Date
Sampling Location
Parameter Unit.
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/L"1
mg/L">
mg/Lw
mg/L1"
Mg/L
Mg/L
M9/1-
MQ/L
pg/L
|jg/L
Mg/L
Mg/L
Mg/L
Mg/L
M9/L
- -02/16/99""
IN
.
- -.
,4
^" '
'
>
-
-
-
j
_
OU
*; ^
~
^
^ '
^ ^j, ^
. *
-
'
, 02/23/99,^ es*"
IN
77
77
23
23
7.5
7.5
33.3
<11
36.6
0.6
OU
82
82
<5
<5
7.5
7.5
1.2
<11
36.5
0.5
OS/2/99"'
IN '
> - i
if-- i
&.- - ;
V
>#r ";
>"/- __- .
r
-
,,
- ou -*_"
v.
f*' .'
- _ ซ*
y
'
.
v*
'"
j-.
...
' -
'
- ^03K
:*,m
79
25
<0.1
7.6
64
56.2
7.5
0.8
42.5
41.5
39.4
38.1
3.1
3.4
0.6
0.5
38.8
37.6
-------
Table A-8. Analytical Results from Long-Term Sampling, Plant A (Mar 16 to Apr 6,1999)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (111)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L""
mg/L
NTU
mg/L""
mg/L<"
mg/L("
mg/L""
P9/L
Pg/L
PS/L
Mg/L
pg/L
Mg/L
ug/L
pg/L
Pg/L
PS/L
PS/L
03/16/99'4'
IN
63
61
21
20
7.2
7.2
23.3
14.2
<30
1.3
OU
65
64
18
18
7.4
7.4
47.6
<11
<30
0.8
^ " 03/23/99
IN
93
26
7.7
46.4
18.0
<30
1.5
OU
21
<5
7.0
7.8
<11
<30
1.4
- 03/30/99
IN
66
21
7.5
25.3
19.4
<30
<0.5
OU
71
<5
7.6
1.2
<11
<30
<0.5
04/06/99 ~-
* - IN.
73
19
0.3
7.5
65
57.9
7.4
0.6
31.1
31.9
31.4
30.8
<0.1
1.1
0.6
0.6
30.8
30.2
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
. OU -
82
<5
<0.1
7.7
63
55.7
7.2
0.1
1.2
1.2
1.2
1.2
<0.1
<0.1
0.2
0.1
1.0
1.1
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
(a) Measured as CaCO,.
(b) Combined NO3-N and NO..-N.
(c) The AX300 tank was regenerated on 3/21/99 after samples were collected.
IN = Inlet; OU = outlet. ;
78
-------
Table A-9. Analytical Results from Long-Term Sampling, Plant A (Apr 13 to May 4,1999)
Sampling Date ''"
. ^Sampling Legation
Parameter ' Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L(a)
mg/L
NTU
mg/Lw
mg/L("
mg/L<"
mg/L0"
pg/L
pg/t
pg/L
Mg/L
ug/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
* ' "04/13/99-
":IN
87
87
25
24
7.7
7.6
43.9
13.2
<30
0.6
"U0M .
84
85
<5
<5
7.7
7.7
6.4
<11
<30
0.6
~04/20/99<
-------
Table A-10. Analytical Results from Long-Term Sampling, Plant A (May 11, to Jun 1,1999)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L"1
mg/L
NTU
mg/L<"
mg/Lw
mg/Lw
mg/Lฐ"
M9/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
pg/L
ug/L
ug/L
P9/L
05/11/99
IN
83
84
24
23
7.5
7.5
43.9
18.3
<30
1.1
OU
87
86
. <5
<5
7.6
7.6
1.9
13.4
<30
0.5
05/18/99(C> ""
IN
83
23
7.6
42.7
12.0
<30
3.1
OU, -
44
<5
7.3
10.1
<11
<30
0.8
,05/25/99
IN -^
92
24
7.7
45.9
16.3
31.7
0.6
, OU
82
<5
7.5
1.7
13.5
<30
0.8
06/01/9'9 '
IN
88
24
<0.1
7.6
64
56.7
7.0
0.3
44.1
43.9
44.9
44.7
<0.1
<0.1
1.1
1.1
43.7
43.6
<11
<11
<30
<30
0.7
0.8
<11
<11
<30
<30
0.5
0.5
OU
62
25
<0.1
7.6
65
58.2
7.1
0.2
1.6
1.5
1.5
1.5
0.1
<0.1
0.4
0.2
1.0
1.3
<11
<11
<30
<30
0.7
0.7
<11
<11
<30
<30
0.7
0.8
(a) Measured as CaCQ,.
(b) Combined NO3-N and NO2-N.
(c) The AX300 tank was regenerated on 5/16/99.
IN = inlet; OU = outlet.
80
-------
Table A-11. Analytical Results from Long-Term Sampling, Plant A (June 8, to Jun 17,1999)
Sampling Date,
Sampling Location
Parameter " ~ Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
Nitrate-Nitrite
As (total)
As (total soluble)
As (particulate)
As (ill)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/Lซ"
mg/L""
mg/L"1
mg/L""
pg/L
P9/L
Pg/L
pg/L
ug/L
P9/L
van.
ug/L
pg/L
pg/L
pg/L
J 06/08/99
*~H ~ ,
'- IN -
90
91
23
23
7.5
7.6
26.6
11.3
<30
0.6
OU
91
92
<5
<5
7.7
7.7
4.7
13.8
<30
0.8
. 06/13/99'ฐ' "
"IN
^"^
77
21
7.4
28.4
-.-
12.6
37.1
0.7
OU
89
<5
7.7
23.1
11.3
<30
0.5
06/14/99
- IN
92
25
7.6
31.7
<11
<30
0.8
- ou\
- ,ซ
40
16
7.2
45.5
12.5
<30
0.7
. 06/15/99
,JN~
86
24
7.6
43.3
105
<30
1.2
OU '
48
13
7.2
24.2
13.8
<30
0.8
06/17/99-
IN
86
23
7.7
43.9
<11
33.6
0.9
OU
69
<5
7.5
12.6
11.3
117
1.0
(a) Measured as CaCO3.
(b) Combined NO3-N and NO2-N.
(c) The AX300 tank was regenerated on 6/13/99 after samples were collected.
IN = inlet; OU = outlet.
81
-------
A.2 Technical Data on Puroiite A-300
82
-------
PUROLITE
Technical Data
A-300, A-300E
Strong Base Type II
Anion Exchange Resin
PRODUCT DESCRIPTION
Purolite A-300 is a Type II, strongly basic gel anion
exchange resin with outstanding operating capacity
and excellent regeneration efficiency. A-300 removes
all ions including silica and CO,, however, it operates
best on waters having a high percentage of strong
acids (FMA). A-300 can be used in all types of
demineralization equipment where regeneration effi-
ciency and high operating capacities are needed.
Purolite A-300 has excellent physical stability which
allows for long life and better efficiency within the
operating bed. Whole bead counts are a minimum of
92% clear beads with mechanical strengths ranging
over 300 grams. Purolite A-300 can be regenerated
with sodium chloride to remove alkalinity from different
water supplies. This dealkalization by ion exchange
prevents the formation of insoluble carbonate
precipitates and stops corrosion due to the formation
of carbonic acid. A-300 can also remove nitrates
wnซn regenerated with salt. In some dealkalization
cases, small amounts of caustic is used in combina-
tion with salt during the regeneration in order to
enhance the resin operation. This addition gives
higher operating capacity and lower silica leakage.
Purolite A-300E is a type 2 strong base anion devoid
of taste and odor. A-300E meets the requirements of
paragraph 121.1148 of the Food Additives Regulation
of the FDA.
Capacities and Leakages of A-300 or A-300E are based
on the regenerant reaching the bed at either 70ฐ or
95ฐ F. With some water supplies, it will be necessary
to preheat the beds prior to the introduction of the
regenerant.
In water supplies where the alkalinity is in excess of
50%, keep in mind that you may be unable to
achieve these leakages and capacities. This is
because CO, passing from the cation reacts with
anionic sites forming HCOป. During the regeneration
process of the anion, HCO, is displaced by NaOH.
Additional NaOH then reacts with the HCOป forming
NaปCOj. Since the above leakages and capacities are
based on having excess NaOH above theory, it may
be necessary to compensate for this problem.
Typical Chemical and Physical Characteristics
Polymer Structure , Polystyrene crosslinked with divinylbenzene
Functional Groups R (CHsfe (C^OHJN*
Physical Appearance Clear Spherical Beads
Ionic Form (as shipped) Chloride
Screen Size, U.S. Std. Mesh (Wet) 16-50
Particle Size Range +16 mesh<5%. -50 mesh<1%
Uniformity Coefficient 1.7 maximum
Water Retention , 40-45% (Clform)
Swelling Salt ^OH. 10%
pH Limitations None
Temperature limitations 120ฐF in OH form max.. 185ฐF in Cl form max.
Chemical Resistance Unaffected by dilute acids, alkalies, and most solvents
Whole Clear Beads 92% minimum
Shipping Weight 44 Ibs./ft.s (705 g/l)
Total Capacity , l .45-1.6 meq./ml. min. Volumetric
3.5-3.7 meq./gm. min. Weight
Standard Packaging 5 cu. ft. double polyethylene-lined fiber drums
Division of Bro-Uch Corporallon 150 Monument Road. Bala Cynwyd, PA 19004
83
-------
Operation
Service
Backwash
Regeneration
Rinse (Slow)
Rinse (Fast)
STANDARD OPERATING CONDITIONS
(TWO STAGE DEM1NERALIZER)
Rate
1-5 gpm/ft3
2-3 gpm/tt?
(50-7QฐF)
0.2-0.8 gpm/fP
0.2-0.8 gpm/tt3
1-5gpm/ft3(sameas
Service Flow Rate)
Solution
Effluent from
Cation exchanger
Influent Water
4% NaOH
Decationized Water
Decationized Water
Minutes Amount
5-20 10-25gals./fP
60 4-10 IDS.
60 15-30gals./tt3
25-45 gals./fP
Backwash Expansion 50-75%
Design Rising Space 100%
HYDRAULICS
Pressure drop of a fluid passing through an Ion ex-
change column is related to the flow rates, viscosi-
ty and temperature of the fluid. Typical values of
pressure drop are found in Figure 2.
Backwash removes all paniculate matter filtered
out by the exchanger and regrades the bed
eliminating any channels which may have formed.
Normally a backwash rate that expands the bed
50-75% for 5 to 10 minutes or till the effluent is
clear is recommended. Flow rate for the backwash
should be achieved gradually to prevent resin loss.
See Figure 1.
REGENERATION
Purollte A-300 is supplied in the chloride form and
must be regenerated with a good grade of sodium
hydroxide.
Both the slow and fast rinse remove the excess
regenerant from the exchanger bed. The slow
rinse displaces the regenerant while the fast rinse
rinses out all excess regenerant.
INFLUENT LIMITATION
Maximum FreeChlorine 0.05 ppm
Maximum Turbidity 5 A.P.H.A. Units
Maximum Iron and Heavy Metals 0.1 ppm
84
-------
15.0
12.5
?10.0
ฃ
>i
?
S.
o
OS
7.5
5.0
a
O
1.5
DEALKALIZATION CAPACITY
15.0
20% 40% 60% 80%
Percent Alkalinity of influent Water
Fig. 3
Capacity lor Dealkalization
S Ibs. NaCl/cubic toot
0.35 ibs. NaOH/cubic foot
Down Flow Regeneration
30 inch Bed Depth
Flowrate of 2 gpm/cubic loot
To 10% alkalinity End Point
100%
20% 40% 60% 80%
Percent Alkalinity of Influent Water
Fig. 4
Capacity for Dealkallzation
S Ibs. NaCl/cubic foot
Down Flow Regeneration
30 inch Bed Depth
Flowrale ot 2 gpm/cubic foot
To 10% Alkalinity End Point
100%
85
-------
NITRATE REMOVAL
CAPACITY FOB NITRATE (NOS)
PLUS SULFATE (SO,} REMOVAL
NO, plus SO? Capacity, Kgr. PerCu.Ft.
__!.-ซ._. -'CO
3i\j*.0ปooo.. io*-o> ooc
i
/
,
/
/
X
Re
_ Flo
En
/
X
X
X
X
X
janoration - 10 IDs. NaCI/cu. fl.
w Rate " 2 US. gpmfcu. ซ.
d Point ซ 2 ppm NOj (as CaCOJ
20%
Ptrctnl Exchangeable Anlons (NOJ + SO5)
Expressed at CiCOi
CAPACITY IN KILOGRAINS/Cu.fL
Lbt. NiOH/Cu. Ft.
@700F(21*C)
100% Concsntratlon
4
S
6
7
8
9
10
Lb*. NaOH/Cu. Ft.
@ 85BF{35ฐC)
100% Concentration
4
5
6
7
6
9
10
V, Silica of Total Anion Analysis
10%
20.0
22.7
24.0
25.2
25.8
26.3
26.6
20%
19.0
21.0
22.6
23.7
24.6
252
25.5
30%
17.9
19.9
21.8
23.1
24.0
24.7
25.0
40%
17.3
19.0
20.4
21.8
22.9
23.7
24.3
!
*
s
I
,. _ -R
S
It Silica of Total Anion Analysis
10%
22.9
24!
250
260
267
269
270
20%
220
23.1
24.0
24.9
254
26.0
262
30%
21.0
22.2
23.0
23.8
245
25.2
254
40%
20.1
21.3
222
23.1
23.8
244
24.6
._ O
|
.ซ
s.
J
86
-------
A.3 Water Usage Report
87
-------
Plant A Water Usage Report
Cumulative
Date of Usage
Regeneration (gal)
Water Treated per
Regeneration
(gal) (BVs)
02/01/1995
05/01/1995
08/01/1995
11/03/1995
02/01/1996
05/01/1996
08/09/1996-
11/01/1996
02/01/1997
05/10/1997
08/08/1997
11/05/1997
02/20/1998
05/06/1998
08/20/1998
11/10/1998
02/06/1999
03/21/1999
04/18/1999
05/16/1999
06/13/1999
07/16/1999
1,886,500
2,031,200
2,167,400
2,300,000
2,393,900
2,502,800
2,589,300
2,707,800
2,810,400
2,948,500
3,034,600
3,136,100
3,279,000
3,406,200
3,517,500
3,658,500
3,775,700
3,834,500
3,877,100
3,926,600
3,980,100
4,013,300
144,700
136,200
132,600
93,900
108,900
86,500
118,500
102,600
138,100
86,100
101,500
142,900
127,200
111,300
141,000
117,200
58,800
42,600
49,500
53,500
33,200
9,672
9,104
8,864
6,277
7,279
5,782
7,921
6,858
9,231
5,755
6,785
9,552
8,503
7,440
9,425
7,834
3,930
2,848
3,309
3,576
2,219
Bed volume = 2 cu ft = 14.96 gal.
* Regeneration performed on a quarterly basis prior to 2/6/99 and
on a monthly basis after March 21,1999.
88
-------
APPENDIX B
Plant B Data
89
-------
B.1 Complete Analytical Results from Long-Term Sampling at Plant B
90
-------
Table B-1. Analytical Results from Long-Term Sampling, Plant B (September 3 to 22,1998)
- Sampling Date"
Samplirig Location -
Parameter - Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
NO3-NO2 (N)
As (total) ,
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L!"
mg/L
NTU
mg/L<"
mg/L("
mg/L("
mg/L(b)
Mg/L
Mg/L
ug/L
Mg/L
P9/L
ug/L
pg/L
pg/L
ug/L
pg/L
pg/L
_ a/aHis'" -
!N
65
47
0.5
8.1
37
31.2
5.4
0.04
52.7
47.1
57.7
<0.1
0.9
56.8
24.0
20.7
142
134
3.0
2.7
<11
<30
2.0
" \oUi-:
6
<5
<0.1
6.7
4.0
3.2
0.8
0.03
1.7
1.7
2.8
3.0
<0.1
<0.1
0.3
0.3
2.5
2.7
20.0
14.3
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
^9/8/98"" ^--
3. - CM.
"""-- -IN-"
63
63
47
46
-
8.0
8.0
-
-
-
-
60.5
-
-
-
-
17.3
87.2
2.3
-
-
-
-OU -
12
16
<5
<5
-
7.5
1.5
-
-
-
-
0.8
-
-
-
-
17.1
<30
<0.5
-
-
-
sh&9&- ' -
'"M~
_na; * -
65
45
-
8.5
-
-
-
-
57.6
-
-
-
-
26.8
<30
<0.5
-
-
-
_ %*ป
^OU
5
<5
-
8.5
-
-
-
-
4.5
-
-
-
-
20.1
<30
<0.5
-
-
-
> .9/22/98
" IN
65
45
-
8.3
-
-
-
-
63.4
-
-
-
-
28.1
126
2.5
-
-
-
o"u-
6
<5
-
8.8
-
-
-
- u
2.6
-
-
-
-
27.5
<30
<0.5
-
-
-
(a) Measured as CaCO3.
(b) Combined NO3 and NO2 as N.
IN = inlet; OU = outlet,
91
-------
Table B-2. Analytical Results from Long-Term Sampling, Plant B (September 30 to October 20,1998)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
NOy-NOj (N)
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L(<)
mg/L
NTU
mg/L""
mg/L""
mg/L"1
mg/L0"
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
MO/L
Mg/L
Mg/L
Mg/L
Mg/L
9/30/98
IN
63
46
0.6
8.2
46.7
40.7
6.0
0.04
58.0
34.0"ป
57.1
56.2
0.9
<0.1
1.3
1.3
55.8
54.9
23.6
21.6
116
89.6
3.4
3.3
<11
<11
<30
<30
2.8
2.9
ou
6
<5
0.1
7.2
8.3
7.5
0.8
<0.02
2.4
3.8
2.0
. 1.9
0.4
1.9
0.2
0.3
1.8
1.6
19.0
16.8
<30
<30
<0.5
<0.5
15.2
<11
<30
<30
<0.5
<0.5
10/6/98
IN .
63
63
46
46
8.5
8.5
58.2
15.2
82.3
2.3
OU
17
17
<5
<5
8.5
8.4
1.1
<11
<30
<0.5
10/1^/98
IN
64
45
8.1
58.6
<11
49.6
2.2
- ou
10
<5
7.6
1.0
<11
<30
0.5
,10/20/98
5 ***" s &
" JN
64
43
8.2
53.7
12.0
56.2
2.2
"" ~OU'
6
<5
7.0
1.6
12.3
<30
<0.5
(a) Measured as CaCO,.
(b) Combined NO, and NO2 as N.
(c) Confirmed by sample reanalysis.
IN = inlet; OU = outlet.
92
-------
Table B-3. Analytical Results from Long-Term Sampling, Plant B (October 29 to November 17,1998)
Sampling Date
- Sampling Location
Parameter Unit"
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
N03-N0a (N)
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved AI
Dissolved Fe
Dissolved Mn
mg/L""
mg/L
NTU
mg/L<"
mg/Lw
mg/L""
mg/L""
MQ/L
ug/L
ug/L
M9/L
ug/L
M9/L
ug/L
ug/L
|jg/L
ug/L
M9/L
10/29/98
IN
63
43
0.5
8.4
40
34.5
5.8
0.03
57.7
57.7
56.7
55.9
1.0
1.8
0.8
0.7
55.9
55.2
<11
12.6
137
88.4
3.5
2.5
<11
<11
<30
<30
2.5
2.6
0U-
10
<5
<0.1
7.4
<2.0
<0.5
<0.8
<0.02
1.1
1.0
0.9
0.9
0.2
0.1
0.2
0.1
0.7
0.8
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
' 1*1/5/98 " _
'IN -
63
64
44
44
8.2
8.3
64.5
14.0
50.5
2.1
OU,i
6
6
<5
<5
8.0
8.0
1.3
16.9
<30
<0.5
11/10/98
IN-
64
44
8.6
61.7
11.0
91.4
3.0
QTJ -
16
<5
8.6
1.0
<11
<30
<0.5
11/17/98
IN-
65
44
8.2
55.8
19.7
>
<30
1.4
: ou -
9
<5
7.2
1.2
.15.0
<30
<0.5
(a) Measured as CaCO3.
(b) Combined NO3 and NO2 as
IN = inlet; OU = outlet.
N.
93
-------
Table B-4. Analytical Results from Long-Term Sampling, Plant B (November 24 to December 15,1998)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
NOa-NO2 (N)
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L""
mg/L
NTU
mg/L(a)
mg/L(1)
mg/L'"
mg/L(b)
Mg/L
Pg/L
pg/L
Pg/L
Pg/L
pg/L
Pg/L
Pg/L
Pg/L
pg/u
Pg/L
11/24/98*"
IN
OU
-
12/01/9X
IN
63
44
<0.1
8.1
37
31.5
5.8
0.02
54.4
54.3
43.7
44.0
10.7
10.3
0.8
0.6
42.9
43.4
22.0
23.3
104
85.4
2.2
2.1
<11
<11
<30
<30
1.7
1.7
OU
8.0
<5
<0.1
7.2
<2.0
<1.0
<1.0
<0.02
1.5
1.6
1.6
1.6
<0.1
<0.1
0.1
0.1
1.5
1.5
18.5
12.3
51.2
42.4
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
12/08/98 -' .-
IN:
63
64
46
45
8.2
8.2
57.0
<11
<30
1.8
. .OU _
5
5
<5
<5
7.1
7.1
1.7
13.5
<30
<0.5
12/15/98 '-,
" IN
64
47
8.4
58.5
<11
<30
1.0
- OU
12
<5
8.3
2.1
<11
<30
<0.5
(a) Measured as CaCO3.
(b) Combined NO, and NO2 as N.
(c) No sampling due to Thanksgiving holiday.
IN = inlet; OU = outlet.
94
-------
Table B-5. Analytical Results from Long-Term Sampling, Plant B (Dec 22, 1998 to Jan 12, 1999)
Sampling Date
Sampling Location
Parameter " Urfit
Alkalinity
Suifate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
N03-N02 (N)
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/L<"
mg/L<"
mg/L""
mg/Lw
ug/L
ug/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
M9/L
M9/L
M9/L
12/22/98(ฐ)
-IN ~
,-.-
^
'-"
--,
-
V
-
-
ป-
-
"~
" -QU' " -
S-^jArste >as N ~L
X '
: ' '~
* sM
'"
'
----- :
,- - -
-
-
"12/29/98^*- "_
' IN
"*-
"
r
/"-:
(.ซฃ 1-
_ - JT"
N.^ *^
- t.v ป
X
rf^^
- -"_"_
ป
'
'
OU -
"tHKt*. - _
'ff^,
*-ซ''* J
\~-~~- -
-
*
63
49
0.1
8.2
35
29.7
5.3
<0.02
51.9
52.7
60.5(d)
60.3(d)
<0.1
<0.1
0.2
0.6
60.3
59.7
26.0
26.3
124
118
2.2
2.1
<11
38.0
<30
212
3.0
1.4
- /OU
5
<5
<0.1
6.4
<2.0
<0.5
<0.8
<0.02
1.5
1.0
1.5
1.5
<0.1
<0.1
<0.1
<0.1
1.5
1.5
13.0
13.3
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
(a) Measured as-CaCO3.
(b) Combined NO, and NO2 as N.
(c) No sampling due to Christmas holiday.
(d) Confirmed by sample re-run.
IN = inlet; OU = outlet.
95
-------
Table B-6. Analytical Results from Long-Term Sampling, Plant B (Jan 19 to Feb 9,1999)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
NO,-N02 (N)
As (total)
As (soluble)
As (paniculate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/L("
mg/L<"
mg/L<"
mg/L1"
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
01/19/99
IN
63
64
46
45
8.4
8.4
51.3
21.4
139
3.0
OU
10
9
<5
<5
6.9
. 6.9
1.4
<11
<30
1.1
01/26/99*
IN
64
46
7.8
53.4
<11
51.3
0.6
IQU
8
<5
8.3
1.3
<11
<30
0.7
02/02/99
IN
64
44
8.3
57.9
68.3
123
1.6
,(*/- ,
8
<5
6.8
1.0
131
48.9
<0.5
02/Q
**
64
42
0.6
8.3
39
33.7
5.6
0.02
57.1
57.6
63.7
61.7
-------
Table B-7. Analytical Results from Long-Term Sampling, Plant B (Feb 16 to Mar 9,1999)
Sampling Date
Sampling Location
Parameter Unit .
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
NO3-NO2 (N)
As (total)
As (soluble)
As (partioulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L"ฐ
mg/L
NTU
mg/L!a)
mg/L""
mg/Lw
mg/Lw
ug/L
ug/L
ug/L
M9/L
M9/L
M9/L
ug/L
ug/L
ug/L
ug/L
pg/L
"02/16/99, "
IN
63
63
44
46
8.4
8.4
53.4
<11
132
3.5
OU "
7
7
<5
<5
8.6
8.5
1.0
<11
30.7
1.0
02/23/99 "*;
feป* ~ t
-IN-
63
36
8.3
55.6
11.2
79.2
1.6
ฐy. ,
4
<5
8.6
1.7
14.6
43.6
<0.5
-03/02/99
)N
62
46
8.3
58.8
12.9
74.6
1.9
' -lill -'
5
<5
6.3
1.8
<11
<30
0.6
-. 03/9/99
IN "-
P& - A*.? jr> >,
64
48
0.3
8.3
35
29.2
5.7
0.06
59.8
61.4
60.8
60.1
<0.1
1.3
0.6
0.6
60.2
59.5
<11
<11
40.1
51.8
1.5
1.6
<11
<11
<30
<30
2.1
1.4
~~OU
10
<5
0.2
8.6
<2.0
<1.0
<1.0
<0.02
1.1
1.8
1.0
1.0
0.1
0.8
0.3
0.2
0.7
0.8
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
(a) Measured as CaCO3.
(b) Combined NO3 and NO2 as N.
IN = inlet; OU = outlet.
97
-------
Table B-8. Analytical Results from Long-Term Sampling, Plant B (Mar 16 to Apr 6,1999)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
NOS-N02 (N)
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L1"
mg/L
NTU
mg/L<"
mg/L("
mg/L'"
mg/L""
ug/L
ug/L
ug/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
pg/t-
pg/L
03/16/99
IN
63
63
43
44
8.3
8.3
57.8
<11
48.7
3.6
OU
15
15
<5
<5
7.9
7.9
1.4
<11
30.2
5.5
03/23/99
IN
64
45
8.3
58.7
11.2
48.7
2.0
OU -
15
<5
8.0
1.7
<11
<30
<0.5
- ^03/30/99"' "
;IN/ -~
64
43
8.3
58.9
<11
52.4
1.7
OU
7
<5
6.5
1.8
<11
<30
<0.5
. , <,-04?0"6/99
XIN' - "
64
46
0.4
8.5
43
37.2
5.9
<0.02
63.0
62.0
60.6
61.2
2.4
0.8
0.7
0.4
59.9
60.8
<11
<11
53.0
65.8
2.2
2.1
<11
<11
36.0
35.6
2.3
2.3
-; OU
9
<5
0.2
6.9
<2.0
<1.0
<1.0
0.02
1.3
1.3
1.3
1.2
<0.1
0.1
0.3
0.2
1.0
1.0
<11
<11
72.2
73.2
<0.5
<0.5
<11
<11
30.7
31.7
<0.5
<0.5
(a) Measured as CaCO.,.
(b) Combined NO, and NO2 as N.
IN = inlet; OU = outlet.
98
-------
Table B-9. Analytical Results from Long-Term Sampling, Plant B (Apr 13 to May 4,1999)
Sampling Date
r
- Sampling Location,
Parameter _ Unit
Alkalinity
Sulfate
Turbidity
PH
Total Hardness
Ca Hardness
Mg Hardness
NO3-NO2 (N)
As (total)
As (soluble)
As (particulate)
As (111)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/Lw
mg/L
NTU
mg/L("
mg/Lw
mg/L!"
mg/L*'
M9/L
ug/L
ug/L
M9/L
M9/L
ug/L
ug/L
M9/L
ug/L
MO/L
M9/L
04/13/99
,IN
'X
65
64
38
37
8.3
8.3
55.7
<11
73.6
2.8
OU
3
4
<5
<5
6.4
6.3
1.5
<11
<30
<0.5
04/20/99
fN
64
44
8.3
59.5
20.3
37.3
2.0
.-."oil ,;
3
<5
6.1
1.6
<11
<30
<0.5
/ 04/27/99 - "
IN" -
64
44
8.3
56.8
<11
<30
2.2
OU""
6
<5
6.4
1.7
13.9
<30
<0.5
05/04/99^
IN
67
44
0.3
8.3
33
28.0
5.4
0.02
57.7
57.6
57.7
57.6
<0.1
<0.1
1.1
0.9
57.0
56.8
<11
11.6
<30
<30
1.7
1.6
<11
<11
<30
<30
1.5
1.5
OU -,
6
<5
<0.1
6.6
<2.0
<1.0
<1.0
<0.02
2.8
- 2.7
2.4
2.5
0.3
0.2
0.6
0.6
1.8
1.8
<11
<11
<30
<30
<0.5
<0.5
<11
<11
<30
<30
<0.5
<0.5
..(a) Measured as CaCO3.
(b) Combined NO3 and NO2 as N.
IN = inlet; OU = outlet.
99
-------
Table B-10. Analytical Results from Long-Term Sampling, Plant B (May 11 to May 25,1999)
Sampling Date
Sampling Location
Parameter Unit
Alkalinity
Sulfate
Turbidity
pH
Total Hardness
Ca Hardness
Mg Hardness
N03-N02 (N)
As (total)
As (soluble)
As (partioulate)
As (III)
As(V)
Total Al
Total Fe
Total Mn
Dissolved Al
Dissolved Fe
Dissolved Mn
mg/L("
mg/L
NTU
mg/Lซ"
mg/L("
mg/L("
mg/Lw
P9/L
pg/L
pg/L
pg/L
P9/L
Pg/L
Pg/L
Pg/L
pg/L
pg/L
pg/L
05/11/99
IN
65
. 65
44
44
8.3
8.3
60.1
12.6
39.3
2.4
OU
13
13
<5
<5
7.0
6.8
1.5
<11
<30
<0.5
05/18/99
IN -
64
46
8.3
58.4
<11
<30
1.6
'v ฐu
4
<5
6.4
1.8
<11
<30
<0.5
""/- ^5/|5/Qg^ -"
. IN
64
45
8.3
55.0
<11
76.1
2.5
OU
4
<5
6.2
1.9
11.6
30.1
1.1
(a) Measured as CaCO3.
(b) Combined NO, and NO., as N.
IN = inlet; OU = outlet.
100
-------
APPENDIX C
Plant C Data
C.1 Complete Analytical Results from Long-Term Sampling at Plant C
C.2 Technical Data on DD-2 AA
C.3 Water Usage Report
101
-------
C.1 Complete Analytical Results from Long-Term Sampling at Plant C
102
-------
oo
en
0)
03
ja
I
o
i
I
I
CD
CO,
o
^_J
CO
c
"o.
CO
cป
jj
o
i
tr
"cB
o
ca
6
0)
-
K
O
CO
co co
i^ r^
CD Ol
N r^
05 CO
K K
cn en
i^ i^-
CD
N
CO
^
CO
I~-
o>
I--
X
CO
in
ง
CM
m
fe
s
I Hardness
ฃ
1
c
0
5
CO f~
in in
l~- t>-
Tf CM
CO CD
^ Is*
co h-
ฃฃ
* -4
Kit
^
C
s
~3
01
Q
ffi
3
II
O
ji"
5
C
'ซ
a
ฃ
1
^
II
P
ฃ
S
. 0)
Z-E'
S i>
02
Z
O-oS
o s fe
leasured as Ce
ombined NO3 ฃ
nlet; TA1 = aft<
"
Jj'ca'S'z
103
-------
(O
2
ca
2
00
O)
CO
T-
S3
Si
CD CD
CM CM
88
ป
SS
en
CM
tn
co
CM
CO
CM
E
S
w
T-
o
,_
0
T-
O
V
r-
V
1-
=1
CO*
CD
00
0
CO
o
co'
CO CC
|s.' [x.'
o> en
en en
K K
o> o
t^ oc
CO
co
^
oo
00
a.
o
to
o
10
S
IO
1
al Hardness
jS
m
CM
CO
CM
8
^
CO
^
fe
L
E
)a Hardness
o
co
T
en
t
,_
co
.
en
1
Hg Hardness
,
o
T^
o
,_
o
CM
0
1
O
6
co
CM
to
d
CM
*'
in
CM
to
-
CM
CO
to
CM
to
q
oo to
1^- h-
O T-
Sict
en co
3$
CO -*
ss
s
I
3
-
CD CO
00 00
O CO
M 04
i- CO
o en
CD CO
tete
1
total soluble)
CO
__.
ฐฐ
T- T-
o o
V V
Y- T-
ฐฐ
V" 1
"v *v
s
particulate)
<
-
O O)
1- O
"* CO
O 0
co oo
"
in CM
CM CM
i
<
_'
w
-,
co rf
t^ ^
co in
8 Si
CO O
00 CO
v- *
88
1
CO
CM
en
o
S
'v
'_
-
""'
CD
CD
CM'
CM
V
CD CO
88
CO CO
I**- 't
CMct
en CM
00 CO
S
1
CM
ง
O
en
en
8
-
o
CO
V
1
1
1
o en
V V
O 0
CO 00
m co
O CM
5- co
1
ฃ
ฃ
CD
C5
CM
S
$
s
s
O)
CO
r-
CD O
i- CM
CD CO
r~ CM
RR
en en
CM T-
00 CO
oo en
S
c
1
' -
VV
i- co
CM CM
--
V 'v
a
i
s
'n
-
^ _,
--
V V
V V
$3
V V
i
ฃ
1
5
;>
-
tO CM
oo en
to to
CM O
00 t^.
o o
00 00
1
c
i
o
CO
n
CO
o
Q.
O>
C
f
g
o
1
i
CM
CO
ffl
J2
1
ca
o
5
CO
O
a.
D)
.2
1
0
1
CD
CD
S1
1
c
o
ฃ
CO
a
!
T5
co
c.
. -^
i'l
Z to CB
O a 2
cr""3 T3
j Z 0) C
73 TJ <0
c =
c
2
CD
104
-------
C35
<3>
CO
"I
co
O)
O)
CO
1
O
en
"5.
co
CO
a>
CO
CD
tr
"CO
o
is.
co
S
0)
ir -"
CD
=
1'
CO
1
Q
I
O
?
5^
is
o
t
i
z
0
T-
S
.*:
o
s"
;e
s
as
c
o
1-
ฃ2
-I'
s
R
co
S
co ง
S38
OJ O4
CO CO
O CO
en co
co
H
S
OJ
CO
s
CO
E5
CO
s
"c
1
CM
2
CD
in
q q
T T
ฐฐ
CO CO
CO CO
en
d
O5
d
in
in
CD
d
00
d
^
in
1
Fluoride
Si
8
8
Si
co in
CM CM
CO CD
OJ OJ
in in
OJ CM
co in
CM CM
s
Si
a
in
CM
a
s
Si
a
t
1
3
CO
3
d
i
CM
d
1
1
o
00
o
cd
CO
o
CO
T- 0
co cd
0 0
CO CO
en co
o o
CO CO
CM
oo
CO
o
CO
T
CO
OJ
CO
CO
cd
en
o
oo
a.
in
CM
in
in
u
|j
1?
Total Hardness
S
OJ
s
in
I
Ca Hardness
O
cd
"CM
CO
B
oq
1
Mg Hardness
ง
d
CO
d
d
1
1
d
d
CM
CM
in
q
n
CO
in
CO
d
in
CO
CM
CD
in in
CO CO
""
CO *
1-^ O5
CO CO
cri c\
m co
in
CO
d
CO
CM
CO
I
I
oo co
in -*
^^
r- i-
55
CM CO
CO CO
CO CD
4
total soluble)
3
,_ ^-
V V
1 T-
*v *v
_=
ฐฐ
T_ ^_
o o
V V
1
particulate)
CO
CD O)
CD CM
OJ T-
,_ _
o> en
co oo
00 CO
CM CM
1
CO
T- ,_
V V
T- t-
ฐฐ
CO CO
CO CO
"* 00
38
1
3
in
S3
co
CO
co
T^'
'v
CO
ct
8
en
S3
V
<- in
co en
CM CO
-t r-
CO CO
co in
o o
(^ CM
co in
CM in
งs
CM
in
d
CO
00
in
^
4
1
9
ซ
o
ซ
o
ซ
ซ
CO
ซซ
T-
88
o o
CO CO
V V
CO CO
CD m
00 C~
m
CM
o
o
CO
V
en
in
co
4
.ฃ-
CO
s
CD
cri
CD
CO
d
00
en
o
d
CO
co
cri
m
S
CD
te
en en
cri cri
sf <*
CO *
S?
00 OJ
en in
co co
00
05
i
00
CO
in
in
1
c
5
I
co co
CM' m
CM OJ
m o
Si Si
CO
V
^v V
1
Dissolved Al
w
V V
ซซ
88
V V
4
Dissolved Fe
CO CM.
d T^
in in
oo oo
d r-
in in
r-; o>
ง 00
* CO
in in
CO CO
1
Dissolved Mn
o
u
O
ishing tan
C03.
nd NO2 as N.
r the roughing tank; TA1 = after the pol
(a) Measured as Ca
(b) Combined NO3 a
IN = inlet; TB1 = afte
105
-------
CO
O
"c
OL
is.
CB
CO
I
O)
p
co
CD
DC
"m
.B
S
ca
04/28/99
04/14/99
03/31/99
r-
T
Sampling Date
0
Z
5
2
O
ฃ
p
2
O
ฃ
P
z
8
ฃ
m
z
Sampling Location
Parameter Unit
ง
in
CO
3
3
gg
to in
co co
I-- CO
co co
CO CO
CO CO
s
O5
r-.
s
ง
R
fc
S
ฃ
1
.-I
"(5
-^
<
*
*
*
i
*
CO CO
* *
* *
* rfr
CO
*
tn
in
in
T-
cq
Y-
t^;
tn
1
Fluoride
(O
CM
in
CM
%
&
co co
CM CM
CO N
CM CM
r- N
CM CM
CO CO
CM OJ
CO
CM
CO
CM
CO
CM
CO
CM
Si
8
8
%
1
i
1
CO
CO
o
V
o
V
71
o
V
*
d
I
.&
T3
In
I
O
co
co
h-:
en
i^
o
co
05 05
r^ r-^
o o
co co
o o
co co
co co
CO
t^
en
t^
en
r^
o
co
en
t^
en
r^
0
co
en
r>:
Q.
9
3
3
J?
1
Total Hardness
CM
8
CM
8
in
co
m
8
1
Ca Hardness
CO
r^
T-
t T
in *
o o
0 f-
E?S
l^. co
t- en
co in
o
CM
*
c\i
i
*
3
1
CO
<
O 0)
CM i-
<* *
0 0
co in
88
CO **
ง s
1
As (total soluble)
TT T~
%
f-
CO
co
C)
co
st
CM
O
CO
I-.
CM
CO
CD
CO
in
en
cri
T
* 1-
T- CO
CM T-
r- co
CO CO
O h-
cn co
CM i-
T T
V ^v
co
C3
CO
-------
O)
c.
i
O)
c\T
H
O
O)
"o.
co
CO
H
D5
3
O
CO
CD
DC
C3
If)
6
J2
ฃ1
-1-
"
&*
-*
" O5
- ง
ซ?
--.
0>
ง1 .
"ง
O>
->
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^
*C
, i^
OS
-
O
en
z
-O '
, <
1
5
<2
'Z.'"
"c
| "
D.
ฃS
O5 O
r-. co
T- O
CO CO
8S
s
8!
ง!
o
CD
CO
8
CM
CO
s
*
CO
1
.f
1
-+ ^
*~ T~
*-*
^~ T-.
rf*
Y T
Tf^t
"^ T~
CO
'-
co
T-
IO
"r~
CO
"*~
co
"^
CO
"
,J.
"
Tf
IT
I
Fluoride
88
co in
CM CM
in in
CM CM
in U3
CM CM
m
CM
Si
CO
CM
co
CM
8
CO
CM
8
8
1
1
t
o
V
__
0
__
ฐ
f
o
V
I)
z
;5
1
05 05
o o
co co
O5 O
r-~ co
o o
CO CO
o
oo
o
co
o
co
*-
CO
.,_
CO
o
CO
0
co
CO
Q.
r~
3
o
5ฐ
CO
O5
o
3
1
1
CM
s
in
T-
00
^
^
o
CM
CO
1
Ca Hardnes
in
CO
m
CO
co
CO
T
co
CO
1
CO
Mg Hardnes
CO
"-
m
o
o
,_
o
^
o
o
1
O
6"
co
^.
1
O
CO
*
CD
CO
CO CO
Tf Tt
1^. CD
T 1
CM T-
* *
in o
in to
05
CM
O5
d
co
3
m
O5
co
1
i
CO CO
** tt
in *
1 T
h- O
h- CO
CO CO
^ ^
1
~m
As (total soiubl
i- -r-
O O
CM CM
O O
T T-
"?
1
^
ca
CM
co
CM
r-~ co
CM CM
** co
f T-
m en
T- W
V V
T-:
CO
T~
V
^_
m
CO
co
1
I
O
Q
lvj
o
CO
V
m
8
0 O
CO CO
o o
^^
co r^
^~ T~
8
8
V
f
8
V
1
S.
I
O5
CO
O
r-
CM
0
^_
CO
CM
CM
in
O O5
CM i-
T T
,--*
1^ CD
* to
O O
co co
1^ lO
CO CO
m m
CM "
8
CO
CO
CM
oo
5
O5
CO
Tf
1
C
1
CM *
CM ฃ!
^ ^2
V V
O O5
CM i-
JI JI
V V
1
Dissolved Al
TJ-
O5 CO
V
o o
co co
V V
CO CO
V V
CO CO
1
Dissolved Fe
<* CM
o o
o o
CO CO
CO CM
88
co co
Kin1
i
Dissolved Mn
ts
3
o
II
O
-g
o>
_c
8.
CD
ฃ
J:
CO
II
ฃ
. O)
w ฃ.
* f
8 c -
CO CO CD
% f II
(a) Measured ;
(b) Combined
IN = inlet; TB1
107
-------
C.2 Technical Data on DD-2 AA
108
-------
Aluminum Company of America
Material Safety Data Sheet
aec. to 91/155/EEC
Printing date 02/28/97
Page 1/7
Reviewed on 12/19/96
CTBHICM. PRODUCT aim COMPANY
Product details!
Product Names Activated Aluminas
149
Other Designations:
Active bed supports, CG-20, CPA series, CPU, CSS series, DD-2, DD-410,
DD-420, DD-422, DD-431, DD-440, DD-450, DD-460, DD-471, DD-6, F-200,
HF-200, HPX, LD-5, LD-350, PSD-350, RC-400, RF-200, S-100,
S-400, S-431, and SRO.
Manufacturer/Supplier:
Aluminum Company of America
425 Sixth Avenue Alcoa Building
Pittsburgh, PA 15219-1850 USA
Health fi Safety: +1-412-553-4649
Alcoa Alumina & Chemicals, L.L.C.
HC-63 Box 4, Vidalia, LA 71373
Emergency +1-318-336-9601
3502 South Riverview Drive
Port Allen, LA 70767
Tel. +l-504r-389-9945
Emergency information:
USA: Chemtreci +1-703-527-3887 +1-800-424-9300 ALCOA: +1-412-553-4001
2 Composition/Data on components i
Chemical characterization
Components:
1333-84-2 Aluminum oxide (non fibrous)
EINECS: 215-691-6
14504-95-1 Aluminum silicate
EINECS: 233-5C9-7
Additional information:
Loss on ignition (water)
1333-84-2 (See Section 15)
<97
<0.2
4.0-7.0 *
3 Hazards identification
Chemical ingredient and possible processing hazards:
Alumina is a low health risk by inhalation and should be treated as a
nuisance dust as specified by the ACGIH.
This product contains total silicates at <1% by weight. Total silicates
content includes metal silicates, amorphous and crystalline silica. No
analytical method exists to detect and differentiate between amorphous
and crystalline silica and other silicates at <1% by weight. Based on
(Contd. on page 2)
USA-
109
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Material Safety Data Sheet
ace. to 91/155/EEC
Printing date 02/28/97
Page 2/7
Reviewed on 12/19/96
Product Name: Activated Aluminas
149
(Contd. of page 1)
tha chemistry of bauxite-derived products, crystalline silica is not
expected to be present in-this product.
Hazard description: :
Medical conditions aggravated by exposure to the productt
Asthma, chronic lung disease, and skin rashes.
Information pertaining to particular dangers for man and environment
not applicable
Classification system
The classification was made according to the latest editions of the EU-
lists, and expanded upon from company and literature data.
4 First aid measures
After inhalation
Remove to fresh air. ;
Check for clear airway, breathing, and pulse.
Provide cardiopulmonary resuscitation for persons without pulsa or
respirations.
Consult a physician.
* After skin contact
Wash with soap and water for at least 15 minutes.
Consult a physician.
After eye contact
Immediately flush eyes with plenty of water for at least 15 minutes.
Consult a physician.
After swallowing
Do not induce vomiting.
Never give anything by mouth to a convulsing or unconscious person.
If swallowed, dilute by drinking large amounts of water.
Consult a physician.
5 Fire fighting measures
Suitable extinguishing agents
Use fire fighting measures that suit the environment.
Protective equipment:
Wear self-contained respiratory protective device.
Wear fully protective suit.
6 Accidental release measures
Person-related safety precautions:
Wear protective clothing.
Measures for environmental protections No special measures required.
Measures for cleaning/collecting:
Clean up using dry procedures; avoid dusting.
Additional informationป No dangerous substances are released.
-USA'
110
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Material Safety Data Sheet
ace. to 91/155/EEC
Printing data 02/28/97
Page 3/7
Reviewed on 12/19/96
Product Name* Activated Aluminas
149
7 Handling and storage
Handling
Information for safe handling:
Ensure good ventilation/exhaust at the workplace.
Prevent formation of dust.
Provide suction extractors if dust is formed.
Information about protection against explosions and fires:
No special measures required.
Storage
Requirements to be met by storerooms and receptacles:
Keep material dry.
Information about storage in one common storage facility: Not required.
Further information about storage conditions: None.
8 Exposure controls and personal protection
Additional information about design of technical systems:
No further data; see item 7.
Components with limit values that require monitoring at the workplace;
1333-84-2 Aluminum oxide (non fibrous)
HAK (GERMANY): 6 R (respirable) mg/m3
OSHA: 15 total, 5 respirable mg/m3
TI,Vt 1O rag/m3
Personal protective equipment
General protective and hygienic measures
Do not inhale dust.
Avoid contact with the eyes.
Breathing equipment:
Use suitable respiratory protective device in case Of insufficient
ventilation.
Short term filter device:
Filter P2.
Protection of hands: Impervious gloves.
Eye protection: Safety glasses.
9 Physical .and chemical properties:
Form:
Crystalline powder
Gelatinous
Balls
Granules
Pellets
Color: Whitish
Odor: Characteristic
Value/Rancre Unit
Method
Change in condition
Melting point/Melting range:
Boiling point/Boiling range:
2038 C
undetermined
(Contd. on page 4)
111
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Material Safety Data Sheet
ace. to 91/155/EEC
Printing data 02/28/97
Page 4/7
Reviewed on 12/19/96
Product Name: Activated Aluminas
149
Flash points
Auto igniting:
Danger of explosion:
Product does not present an
explosion hazard.
Densityt
at 20
Solubility in / Miscibility with
Hater:
(Contd. of paga 3)
Hot applicable.
Product La not self igniting.
0.62-0.83 g/cm3
Insoluble
pH-valua:
at
20
9.4-10.1
10% in water
10 Stability and reactivity
Oheraal decomposition / condition* to be avoided:
Ho decomposition if used according to specifications.
Dangerous reactions Heating occurs when water is added.
Dangerous products of decomposition:
No dangerous decomposition products known
Additional information: Non-corrosive.
11 goxieolocrieal information
Primary irritant effect:
On the skin: Can cause mild irritation.
On the eye: Can cause mild irritation.
inhalation: Can cause mild upper respiratory tract irritation.
Zngestion: Can cause mild irritation.
Additional toxicological information:
The product is not subject to classification according to the
calculation method of the General EO Classification Guidelines for
Preparations as issued in the latest version:
12 Ecological information;
General notes:
Watar hazard class 0 (German Regulation) (Self-assessment): generally
not hazardous for water.
13 Disposal considerations
Product:
Recommendation
Collect in containers, bags, or covered dumpster boxes. If reuse or
recycling is not possible, material may be disposed of at an industrial
landfill.
Haste disposal key: 16 03 01 S13 05
Uncleaned packagings:
(Contd. on page 5)
: USA-
112
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Material Safety Data Sheet
ace. to 91/155/EEC
Printing date 02/23/97
Page 5/7
Reviewed on 12/19/96
Product Haass Activated Aluminas
149
fContd. of page 4)
Recommendation:
Disposal must be made according to official regulations.
14 Transport information
DOT regulationst
Remarks:
U.S.A. OOTs Not regulated - Enter the proper freight classification.
"USDS Number," and "Product Name" on the shipping paperwork.
Canadian TOG Hazard Class & PIN: Not regulated.
Maritime transport XKDGi
Marine pollutant: No
15 Regulations
U.S. Federal Regulations:
TSCA STATUS:
All components of this product ara listed on the TSCA inventory.
*For TSCA inventory reporting purposes, CAS No. 1344-28-1 was assigned
for all forms of aluminum oxide instead of the CAS No. 1333-84-2 as
indicated in Section 2.
CERCLA REPORTABLE QUANTITY: Nona.
SARA TITLE III:
Section 3O2 Extremely Hazardous Substances*
None.
Section 311/312 Hazardous Categories: Immediate (acute).
Section 313 Toxic Categories: None.
OTHER INFORMATION:
In reference to Title VI of the Clean Air Act of 1990, this material
does not contain nor was it manufactured using ozone-depleting
chemicals.
Markings according to EU guidelines:
Observe the general safety regulations when handling chemicals.
The product is not subject to identification regulations under EU
Directives and the Ordinance on Hazardous Materials (GefStoffV).
National regulations
Classification according to VbF: Void
Hater hazard class:
Hater hazard class 0 (German Regulation): generally not hazardous for
water.
International Regulations:
CANADIAN DOMESTIC SUBSTANCES LISTS
All components of this product are listed on the Canadian DSL.
AUSTRALIAN INVENTORY OF CHEMICAL SUBSTANCES:
All components of this product are listed on the AISC.
JAPAN Ministry of International Trade Industry (MITI):
All components of this product are listed on MITI.
_^ . USA-
113
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Material Safety Data Sheet
ace. to 91/155/EEC
Printing data 02/28/97
Page 6/7
Reviewed on 12/19/96
Product Kanex Activated Aluminas
149
16 Other information:
This information is based on our present knowledge. However, this shall
not constitute a guarantee for any specific product features and shall
not establish a legally valid contractual relationship.
Department issuing MSDS:
Hazardous Materials Control Committee, Alcoa, Pittsburgh, PA 15219 USA
19.12.96
Alcoa HAZHIN jfl 000445
Appendix:
Guide to Occupational Exposure Values 1995, Compiled by the American
Conference of Governmental Industrial Hygienists (ACGIH).
Documentation of the Threshold Limit Values and Biological Exposure
Indices, Sixth Edition, 1991, Compiled by the American Conference of
Governmental Industrial Hygienists, Inc. (ACGIH).
- NIOSH Pocket Guide to Chemical Hazards, U.S. Department of Health and
Human Services, June 1994.
- Dangerous Properties of Industrial Materials, Sax, N. Irving,
Van Nostrand Reinhold Co., Inc., 1984.
- Patty's Industrial Hygiene and Toxicology: Volume II: Toxicology,
4th ed., 1994, Patty, F. A.; edited by Clayton, G. D. and Clayton,
F. E.s New York: John Wiley & Sons, Inc.
LEGEND:
ACGIH American Conference of Governmental Industrial Hygienists
CAS Chemical Abstract Services
CERCLA Comprehensive Environmental Response, Compensation, and
Liability Act
CFR Code of Federal Regulations
DOT Department of Transportation
DSL Domestic Substances List (Canada)
ECOIN European Core Inventory
EINECS European Inventory of Existing Commercial Chemical Substances
EWC European Waste Catalogue
EPA Environmental Protective Agency
IARC International Agency for Research on Cancer
LC Lethal Concentration
LD Lethal Dose ,
MAK Maximum Workplace Concentration (Germany)
"maximale Arbeitsplatz-Konzentration"
NDSL Non-Domestic Substances List (Canada)
NIOSH National Institute for Occupational Safety and Health
NTP National Toxicology Program
OSHA Occupational Safety and Health Administration
PEL Permissible Exposure Limit
PIN Product Identification Number
RCRA Resource Conservation and Recovery Act
SARA Superfund Amendments and Reauthorization Act
STEL Short Term Exposure Limit
TCLP Toxic Chemicals Leachats Program
TDG Transportation of Dangerous Goods
TLV Threshold Limit Value
TSCA Toxic Substances Control Act
(Contd. on page 7)
114
-------
Material Safety Data Sliest
ace. to 91/155/EBC
Printing data 02/28/97
Paga 7/7
Reviewed on 12/19/96
Product Kamai Activated Aluainac
149
TWA Time Weighted Average
m mater, cm centimeter, mm millimeter, in inch,
g gram, kg kilogram, Ib pound, j/g microgram,
ppra parts per million
(Contd. of page 6}
-USA'
115
-------
C.3 Water Usage Report
116
-------
Plant C Water Usage Report
Date
08/28/1997
06/11/1998
07/13/1998
08/19/1998
09/03/1998
09/08/1998
09/11/1998
09/14/1998
09/15/1998
09/16/1998
09/17/1998
09/18/1998
09/21/1998
09/22/1998
09/23/1998
09/24/1998
09/25/1998
09/28/1998
09/29/1998
09/30/1998
10/01/1998
10/02/1998
10/05/1998
10/06/1998
10/07/1998
10/08/1998
10/12/1998
10/13/1998
10/14/1998 '
10/15/1998
10/16/1998
10/19/1998
10/20/1998
10/21/1998
10/22/1998
10/23/1998
10/26/1998
10/27/1998
10/28/1998
10/30/1998
11/02/1998
11/03/1998
11/06/1998
11/09/1998
11/10/1998
11/12/1998
11/16/1998
11/17/1998
11/18/1998
11/19/1998
11/20/1998
11/23/1998
11/24/1998
11/25/1998
11/30/1998
12/01/1998
12/02/1998
12/03/1998
12/04/1998
12/07/1998
12/08/1998
12/09/1998
12/10/1998
12/11/1998
12/14/1998
Cumulative
Water Usage
(gal)
1,357,900
1,753,200
1,796,200
1,801,900
1,806,200
1,830,300
1,840,700
1,843,600
1,847,300
1,851,700
1,854,800
1,860,100
1 ,863,300
1,865,100
1,866,800
1,868,700
1,870,800
1,872,700
1,874,700
1,876,900
1,880,100
1,884,800
1,888,000
1,890,300
1,892,800
1,895,100
1 ,899,600
1,902,800
i;965,80CT
1,909,100
1,912,400
1,919,700
1 ,922,200
1,924,100
1,926,500
1,929,400
1,932,300
1,935,300
1,938,600
1,942,800
1,944,700
1,947,300
1,955,100
1,957,300
1,959,300 >">
1,959,700
1 ,963,000
1,964,900
1,966,700
1,968,800
1,970,900
1,973,400
1,976,400
1,979,100
1,981,000
1,985,200
1,987,000
1,988,300
1 ,990,200
1,992,200
1,994,500
1,996,600
1,998,500
2,000,600
2,002,700
Water Treated Since AA
Installed
(gal) (BVs) Remarks
0
395,300
438,300
444,000
448,300
472,400
482,800
485,700
489,400
493,800
496,900
502,200
505,400
507,200
508,900
510,800
512,900
514,800
516,800
519,000
522,200
526,900
530,100
532,400
534,900
537,200
541,700
544,900
547&00 '
551,200
554,500
561,800
564,300
566,200
568,600
571,500
574,400
577,400
580,700
584,900
586,800
589,400
597,200
599,400
601,400 "
601,800
605,100
607,000
608,800
610,900
613,000
615,500
618,500
621,200
623,100
627,300
629,100
630,400
632,300
634,300
636,600
638,700
640,600
642,700
644,800
0 AA System Installed
6,606
7,325
7,420
7,492
7,894
8,068
8,117
8,178
8,252
8,304
8,392
8,446
8,476
8,504
8,536
8,571
8,603
8,636
8,673
8,727
8,805
8,859
8,897
8,939
8,977
9,052
9,106
9,156,' ' Arsenic breakthrough in TA2 (50-ng/L)
9,211
9,266
9,388
9,430
9,462
9,502
9,550
9,599
9,649
9,704
9,774
9,806
9,850
9,980
10,017
' 10,050 Arsenic breakthrough in TA1 (50-jjg/L)
10,057
10,112
10,144
10,174
10,209
10,244
10,286
10,336
10,381
10,413
10,483
10,513
10,535
10,567
10,600
10,638
10,673
10,705
10,740
10,775
117
-------
Plant C Water Usage Report (continued)
Date
12/16/1998
12/17/1998
12/18/1998
12/21/1998
12/22/1998
12/23/1998
12/28/1998
01/04/1999
01/05/1999
01/06/1999
01/07/1999
01/08/1999
01/11/1999
01/12/1999
01/13/1999
01/14/1999
01/19/1999
01/20/1999
01/21/1999
01/22/1999
01/25/1999
01/26/1999
01/27/1999
01/28/1999
02/02/1999
02/03/1999
02/04/1999
02/05/1999
02/08/1999
02/09/1999
02/10/1999
02/11/1999
02/12/1999
02/15/1999
02/16/1999
02/17/1999
02/18/1999
02/19/1999
02/23/1999
03/01/1999
03/02/1999
03/03/1999
03/04/1999
03/05/1999
03/08/1999
03/10/1999
03/11/1999
03/16/1999
03/17/1999
03/18/1999
03/19/1999
03/22/1999
03/23/1999
03/24/1999
03/25/1999
03/26/1999
03/29/1999
03/30/1999
03/31/1999
04/02/1999
04/05/1999
04/06/1999
04/08/1999
04/14/1999
Cumulative .
Water Usage
(gal)
2,007,000
2,009,200
2,011,300
2,013,700
2,015,900
2,019,100
2,020,400 - :
2,020,800
2,024,100
2,026,500
2,028,000
2,031,300
2,033,900
2,035,900
2,039,000
2,041,300
2,043,400
2,043,600
2,045,800
2,048,000
2,055,200
2,057,600
2,059,700 '
2,062,200
2,067,800
2,071,700
2,073,300
2,077,200
2,084,100
2,087,700
2,090,700
2,092,500
2,094,500
2,096,600
2,098,500
2,101,000
2,102,700
2,104,800
2,107,100
2,108,300
2,110,000
2,112,100
2,116,000
2,119,700
2,122,300
2,130,700
2,133,200 ,
2,137,200
2,138,800
2,140,900
2,143,800
2,149,800
2,152,100
2,154,200
2,156,300'
2,158,200
2,160,800
2,162,800
2,166,100'
2,175,000
2,177,100
2,179,500
2,186,800
2,191,100
Water Treated Since AA
Installed
(gal) (BVs) Remarks
649,100
651,300
653,400
655,800
658,000
661,200
sr 661,500 .ป.>
662,900
666,200
668,600
670,100
673,400
676,000
678,000
681,100
683,400
685,500
685,700
687,900
690,100
697,300
699,700
701 ,800
704,300
709,900
713,800
715,400
719,300
726,200
729,800
732,800
734,600
736,600
738,700
740,600
743,100
744,800
746,900
749,200
750,400
752,100
754,200
758,100
761,800
764,400
772,800
775,300
779,300
780,900
783,000
785,900
791,900
794,200
796,300
798,400
800,300
802,900
804,900
808,200
817,100
819,200
821,600
828,900
833,200
10,847
10,884
10,919
10,959
10,996
11,049
1 1 ,071 AA changeout in TA1 and TA2
11,078
11,133
11,173
11,198
11,253
11,297
11,330
11,382
11,420
11,456
11,459
11,496
11,532
11,653
11,693
11,728
11,770
11,863
11,928
11,955
12,020
12,136
12,196
12,246
12,276
12,309
12,345
12,376
12,418
12,447
12,482
12,520
12,540
12,569
12,604
12,669
12,731
12,774
12,914
12,956
13,023
13,050
13,085
13,133
13,234
13,272
13,307
13,342
13,374
13,417
13,451
13,506
13,655
13,690
13,730
13,852
13,924
118
-------
Plant C Water Usage Report (continued)
Date
04/15/1999
04/16/1999
04/19/1999
04/20/1999
04/21/1999
04/22/1999
04/23/1999
04/29/1999
05/03/1999
05/04/1999
05/05/1999
05/06/1999
05/07/1999
05/10/1999
05/11/1999
05/12/1999
05/15/1999
05/17/1999
05/18/1999
05/19/1999
05/20/1999
05/21/1999
05/25/1999
05/26/1999
05/27/1999
06/01/1999
06/02/1999
06/04/1999
06/09/1999
06/10/1999
06/11/1999
06/14/1999
06/15/1999
06/17/1999
06/18/1999
07/16/1999
Cumulative
Water Usage
(gal)
2,199,200
2,201,400
2,200,000
2,208,300
2,210,400
2,213,800
2,216,000
2,219,800
2,220,100
2,223,000
2,225,600
2,230,900
2,233,500
2,236,600
2,239,200
2,241,200
2,246,500
2,253,100
2,258,400
2,261,500
2,263,600
2,267,800
2,273,200
2,275,700
2,279,800
2,288,900
2,291 ,700
2,290,600
2,303,500
2,308,100
2,310,100
2,327,700
2,334,200
2,337,600
2,339,800
2,358,200
Water Treated Since AA
Installed
(gal) (BVs) Remarks
841,300
843,500
842,100
850,400
852,500
855,900
858,100
861,900
862,200
865,100
867,700
873,000
875,600
878,700
881,300
883,300
888,600
895,200
900,500
903,600
905,700
909,900
915,300
917,800
921,900
931,000
933,800
932,700
945,600
950,200
952,200
969,800
976,300
979,700
981,900
1,000,300
14,059
14,096
14,073
14,211
14,246
14,303
14,340
14,403
14,408
14,457
14,500
14,589
14,632
14,684
14,728
14,761
14,850
14,960
15,048
15,100
15,135
15,206
15,296 .
15,338
15,406
15,558
15,605
15,587
15,802
15,879
15,912
16,207
16,315
16,372
16,409
16,716
Bed volume = 4 cu ft per tank = 29.92 gal.
119
-------
-------
APPENDIX D
Plant D Data
D.1 Complete Analytical Results from Long-Term Sampling at Plant D
D.2 Technical Data on CPN AA
D.3 System Plumbing Diagram
D.4 Water Usage Report
121
-------
D.1 Complete Analytical Results from Long-Term Sampling at Plant D
122
-------
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IN = inlet; TB1 = al
123
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JO
CL
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15
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12/23/98'"
CO
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04/28/99
04/14/99
03/31/99
03/17/99
Sampling Date
3
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m
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88
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10 m
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(b) Combined NO3 and NO2 as
IN = inlet; TB1 = after the roug
126
-------
O5
CO
CM
(D
ZJ
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co
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co
CO
f^
1
Q.
I"
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1
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ฃ
Mg Hardness
^
o"
6"
^
o
CO
o
CO
T
CO
o
CO
4
I
4
1 As (total soluble)
4
As (particulate)
4
=-
4
>
<0
CO
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1^.
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cn
T
4
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lv
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m
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m
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m
o
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to
<$
4
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4
Dissolved Al
4
Dissolved Fe
4
Dissolved Mn
I
I
m
ปง>-*
n
1^5
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o
CO
S
0)
129
-------
D.2 System Plumbing Diagram
130
-------
131
-------
D.3 Water Usage Report
132
-------
Plant D Water Usage Report
Water Meter Readings (gal)
Cumulative Water Treated (BV)
Date
04/16/96
05/08/96
06/19/96
07/22/96
08/20/96
09/06/96
10/15/96
11/13/96
12/20/96
01/09/97
02/21/97
03/21/97
04/17/97
05/15/97
06/12/97
07/14/97
08/15/97
09/12/97
10/15/97
11/18/97
12/23/97
01/19/98
02/24/98
03/25/98
04/15/98
05/19/98
06/15/98
07/23/98
08/27/98
09/16/98
10/15/98
11/12/98
12/21/98
01/19/99
02/16/99
03/18/99
04/28/99
05/25/99
06/22/99
07/14/99
08/25/99
09/17/99
10/29/99
11/22/99
12/29/99
Entrance
2,295,800
2,333,260
2,409,900
2,466,374
2,523,670
2,553,380
2,631,240
2,703,750
2,770,410
2,800,240
2,888,940
2,948,004
3,000,610
3,059,700
3,108,910
3,157,310
3,208,400
3,250,280
3,295,576
3,357,040
3,411,900
3,447,000
3,509,210
3,560,110
3,594,940
3,661,900
3,720,820
3,778,580
3,830,990
3,856,690
3,897,300
3,936,270
3,982,560
4,015,700
4,055,600
4,095,300
4,147,400
4,181,200
4,218,500
4,269,800
4,346,800
4,376,700
4,438,700
4,470,300
4,517,500
A1B1
400
18,800
56,200
83,800
111,900
126,400
164,700
200,300
233,000
247,700
291,900
321,000
346,900
376,000
400,300
424,500
449,300
469,900
492,200
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
504,800
522,800
548,000
585,200
599,600
629,600
644,800
667,500
A2B2
42,900
61,600
100,200
128,600
157,300
172,300
211,400
247,800
281,200
296,100
339,900
369,400
395,700
425,200
449,800
473,900
499,400
520,300
543,000
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
557,100
575,800
601,700
641,300
656,700
688,600
704,800
729,100
B1A1
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
17,200
43,200
60,500
91,200
116,400
133,600
167,100
196,200
224,800
250,800
263,600
283,800
303,000
326,000
342,500
362,300
382,000
407,900
424,600
424,600
424,600
424,600
424,600
424,600
424,600
424,600
B2A2
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
17,600
45,100
62,200
93,100
118,400
135,700
168,600
197,600
226,200
252,100
264,900
285,000
304,300
327,200
343,600
363,400
383,100
408,900
425,600
425,600
425,600
425,600
425,600
425,600
425,600
425,600
A1B1
0
246
746
1,115
1,491
1,684
2,197
2,672
3,110
3,306
3,897
4,286
4,632
5,021
5,346
5,670
6,001
6,277
6,575
6,743
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
241
578
1,075
1,267
1,668
1,872
2,175
A2B2
0
250
766
1,146
1,529
1,730
2,253
2,739
3,186
3,385
3,971
4,365
4,717
5,111
5,440
5,762
6,103
6,382
6,686
6,874
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
250
596
1,126
1,332
1,758
1,975
2,299
B1A1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
0
231
642
979
1,209
1,656
2,045
2,428
2,775
2,947
3,217
3,473
3,781
4,001
4,266
4,529
4,876
5,099
0
0
0
0
0
0
0
B2A2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
0
254
667
1,005
1,237
1,676
2,064
2,447
2,793
2,964
3,233
3,491
3,797
4,016
4,281
4,544
4,889
5,112
0
0
0
0
0
0
0
Remarks
AA system installed in 2/96
Arsenic breakthrough
TA2 (50-tig/L)
Arsenic breakthrough
TA1 (50-ng/L)
TA1,TA2rebeddedin
11/97
TB1 , TB2 rebedded in
12/97
*
in
in
Rebedded TB1 , TB2 on
5/25/99
Rebedded TA1 on 7/23/99
Bed volume = 10 cu ft per tank = 74.8 gal.
* Arsenic breakthrough was detected in TB1 based on Battelle's sampling results of 3/3/99.
6 U.S. QOVEtOMENT PRINTING OFFICE: 2000-650-101/40003
133
-------
-------
-------
United States
Environmental Protection Agency
National Risk Management
Research Laboratory, G-72
Cincinnati, OH 45268
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detach or copy, and return to the address in the upper
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