EPA/600/R-11/040
April 2011
Arsenic and Nitrate Removal from Drinking Water by Ion Exchange
U.S. EPA Demonstration Project at Vale, OR
Final Performance Evaluation Report
by
Lili Wang§
Abraham S.C. Chen§
Anbo Wang*
Wendy E. Condh4
^attelle, Columbus, OH 43201-2693
§ALSA Tech, LLC, Columbus, OH 43219-6093
Contract No. 68-C-00-185
Task Order No. 0029
for
Thomas J. Sorg
Task Order Manager
Water Supply and Water Resources Division
National Risk Management Research Laboratory
Cincinnati, Ohio 45268
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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DISCLAIMER
The work reported in this document is funded by the United States Environmental Protection Agency
(EPA) under Task Order 0029 of Contract 68-C-00-185 to Battelle. It has been subjected to the Agency's
peer and administrative reviews and has been approved for publication as an EPA document. Any
opinions expressed in this paper are those of the author(s) and do not, necessarily, reflect the official
positions and policies of the EPA. Any mention of products or trade names does not constitute
recommendation for use by the EPA.
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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 actions 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 environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's center for investigation
of technological and management approaches for preventing and reducing risks from pollution that
threaten human health and the environment. The focus of the Laboratory's research program is on
methods and their cost-effectiveness 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, sediments and groundwater; prevention and control of indoor air pollution; and restoration of
ecosystems. NRMRL collaborates with both public and private sector partners to foster technologies that
reduce the cost of compliance and anticipate emerging problems. NRMRL's research provides solutions
to environmental problems by developing and promoting technologies that protect and improve the
environment; advancing scientific and engineering information to support regulatory and policy
decisions; and providing the technical support and information transfer to ensure implementation of
environmental regulations and strategies at the national, state, and community levels.
This publication has been produced as part of the Laboratory's strategic long-term research plan. It is
published and made available by EPA's Office of Research and Development to assist the user
community and to link researchers with their clients.
Sally Gutierrez, Director
National Risk Management Research Laboratory
in
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ABSTRACT
As part of the EPA Arsenic Removal Technology Demonstration Program, a 540-gal/min (gpm) ion
exchange (IX) system proposed by Kinetico was selected for demonstration at Vale, OR to remove
arsenic and nitrate from a groundwater supply to meet their respective maximum contaminant level
(MCL) of 10-|o,g/L and 10-mg/L (as N). This report documents the activities performed and results
obtained from a 3.5-year long demonstration study that evaluated the performance of IX technology for
arsenic and nitrate removal, determined the required system operation and maintenance (O&M) and
operator skills, characterized the residuals produced by the technology, and determined the capital and
O&M cost of the technology.
This demonstration study was divided into three periods: Study Periods I and II and an interim period
between the two. Study Period I (extending from September 19, 2006, through January 14, 2008)
evaluated the originally proposed Purolite Arsenex II anion exchange (AIX) resin. Because of its
deteriorating performance due to organic fouling and difficulties in restoring its exchange capacity after
resin cleaning, a dual resin approach was identified and implemented in the interim period to address the
relevant issues. In February 2009, Arsenex II resin was replaced with Purolite PFA300E resin, which was
overlain with an organic scavenger, Purolite A850END. The performance of PFA300E/A850END was
evaluated in Study Period II from February 10, 2009, through March 22, 2010.
Summary of System Design
The IX treatment system consisted of two banks of sediment filters, two 63-in x 86-in pressure vessels
configured in parallel, two 11-ton salt saturators, two 1,050-gal day tanks, two brine transfer pumps, one
automatic system control panel, and associated valves, pressure gauges, flow totalizers, and sample ports.
By design, each vessel was to be loaded with 110 ft3 of AIX resin, treating 270 gpm of flow at a hydraulic
loading rate of 12.5 gpm/ft2 and an empty bed contact time (EBCT) of 3 min.
The amount of Arsenex II resin in each vessel was found to be less than the design value of 110 ft3.
During resin replacement in February 2009, it was discovered that the maximum amount of dual resin that
could be loaded into each vessel was 98.5 ft3, which was 90% of the design value. The volume of
Arsenex II resin in each vessel, based on the freeboard measurement, was estimated to be 93 ft3, which
was 85% of the design value. The smaller resin bed resulted in a shorter EBCT, i.e., 2.6 min for Arsenex
II and 2.8 min for dual resin (on average).
Summary of System Operation
Routine operational data and sample collections were conducted in Study Periods I and II. The IX system
operated for atotal of 4,440 and 3,215 hr, treating approximately 128 and 93.6 million gal of water in
Study Periods I and II, respectively. The average daily operating time was 9.5 hr in both periods.
Average flowrates were 534 and 536 gpm in Study Periods I and II, respectively, very close to the design
value of 540 gpm. Pressure losses across each IX vessel averaged 11 pounds per square inch (psi), as
expected for a 5-ft deep resin bed. However, two 270-gpm flow restrictors installed at vessel outlets to
prevent overrun during regeneration created additional headlosses (up to 30 psi) across the IX system.
The IX system was regenerated in a downflow, co-current mode using brine. Triggered automatically by
a volume throughput setpoint in a programmable logic controller (PLC), the two IX vessels were
regenerated sequentially, each cycling through the steps of spent brine draw, fresh brine draw, slow rinse,
and fast rinse before returning to service. The spent brine draw step was designed to minimize
wastewater production, but was discontinued in December 2007 due to concerns over possible resin
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fouling caused by dissolved organic matter (DOM) accumulating in the spent brine solution. The
regeneration waste stream was discharged to an evaporation pond outside of the treatment plant.
A total of 278 and 144 regeneration cycles took place in Study Periods I and II, respectively.
Regeneration parameters, such as brine draw rate, brine volume, and specific gravity of diluted brine were
monitored and adjusted, if needed. During the first six months of Study Period I, salt usage per
regeneration cycle was much higher than the target level of 12 lb/ft3 (up to 25.1 lb/ft3). After a brine
injection pump had been installed to replace the Venturi eductor, the control of salt usage was greatly
improved. In Study Period II, the average salt usage was 8.4 lb/ft3, 16% lower than the target value of
10 lb/ft3.
Summary of System Performance
Based on analytical data from a total of 63 sampling events in both study periods, raw water contained
16.0 to 31.8 ug/L of total arsenic (averaged 21.1 ug/L, primarily as soluble As[V]) and 1.4 to 7.6 mg/L
(as N) of nitrate (averaged 5.5 mg/L [as N]). Although arsenic and nitrate concentrations showed some
variations (presumably due to fluctuations in individual wells), the water quality, in general, remained
rather constant in both study periods. On average, raw water had a pH of 7.4, 319 mg/L of total alkalinity
(as CaCO3), 78 mg/L of sulfate, 277 ug/L of total phosphorus, 58 mg/L of silica (as SiO2), 506 mg/L of
total dissolved solids (TDS), 1.9 mg/L of total organic carbon (TOC), 53 ug/L of total vanadium, and
165 mg/L of total hardness (as CaCO3). Total iron was below its reporting limit of 25 ug/L and total
manganese was less than 1 ug/L.
Weekly samples were collected from the treatment process during both study periods. Five run length
studies also were conducted on Arsenex II and PFA300E/A850END to obtain breakthrough curves of
arsenic, nitrate, and other competing anions. At system startup in September 2006, Arsenex II achieved a
run length of 562,000 gal (or 404 bed volume [BV]) to 10-ug/L arsenic breakthrough, which was 59% of
the vendor-projected run length of 680 BV. Since then, the system performance continued to deteriorate,
as evidenced by more frequent exceedance of the arsenic MCL in system effluent and increasingly
shortened useful run lengths (e.g., to 450,000 gal and then to 376,900 gal after four and seven months of
operation, respectively). Analysis of a resin core sample revealed that the resin was severely fouled by
organic matter. A cleaning procedure using a mixture of caustic/brine was developed in the laboratory by
Purolite and implemented in the field in October 2007. Although the cleaning was able to restore the
resin's capacities, such as volumetric capacity and strong base capacity, to 93% and 79% of the virgin
resin level, respectively, the total organic content of the resin was reduced only by 24% and the useful run
length improved only by 20% to 445,700 gal (320 BV). While organic matter continued to build up on
the resin, the useful run length was shortened again to 323,500 gal (233 BV) about 10 months after the
cleaning.
Shorter run lengths (i.e., only 34 to 47% of the vendor projection) would require more frequent resin
regeneration and produce more wastewater, which potentially could overflow the evaporation pond. In
seeking an alternative approach to address DOM in source water, the City of Vale expressed its desire to
continue with the IX technology in case nitrate became an issue in the future, and to achieve a volume
throughput of 600,000 gal to prevent the pond from overflowing. Thus, the option of replacing Arsenex
II resin with other resin types was explored. Purolite proposed a dual resin approach, i.e., PFA300 top-
dressed with A800END, which had been successfully implemented at the McCook Water Treatment Plant
in McCook, NE for the removal of arsenic, nitrate, and uranium from water containing >3 mg/L of TOC.
Following a site visit to McCook and a run length and elution study, it was confirmed that the dual resin
approach could be an effective remedy to treat waters containing high levels of TOC.
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After the IX system was rebedded with PFA300E/A850END in February 2009, weekly sampling data and
run length study results revealed that the system could achieve a useful run length of approximately
454,400 gal (or 372 BV). This run length was calculated based on the actual PFA300E resin volume of
163.3 ft3. For a system containing 220 ft3 of resin, it would treat 612,174 gal of water. Therefore, the
smaller resin bed was the key reason for not meeting the treatment target of 600,000 gal desired by the
City. TOC concentrations in treated water were consistently removed below the reporting limit of 1
mg/L, confirming the usefulness of the dual resin approach to address DOM issues throughout the desired
service cycle.
Because the IX system was set to regenerate at 600,000 gal during most of the study, it was not surprising
to detect high arsenic concentrations in system effluent when samples were collected past the resin's
useful run lengths. Periodically, effluent concentrations exceeded raw water concentrations, a
phenomenon referred to as chromatographic peaking or arsenic dumping. Arsenic dumping is caused by
displacement of arsenic by more preferred anions such as sulfate, which often has a concentration three
orders of magnitude higher than that of arsenic. Arsenic dumping is a major drawback of the IX
technology and can be mitigated by properly controlling system run lengths and regeneration frequencies.
Nitrate chromatographic peaking also was observed in system effluent, but effluent nitrate concentrations
never exceeded its MCL. Total phosphorus concentrations in system effluent were reduced to <10 ug/L
most of the time but rose rapidly to exceed influent levels after reaching a throughput of approximately
415,000 gal in Study Period I and 488,000 gal in Study Period II. Sulfate was removed to less than
1 mg/L most of the time in both study periods and began to break after reaching a throughput of
376,940 gal in Study Period I and 487,940 gal in Study Period II. It reached 1/3 to 1/2 of its influent
concentration at the end of the 600,000-gal service cycle. Because of its higher selectivity than arsenate
and nitrate, sulfate continued to be removed even when arsenate and nitrate had reached their respective
MCL in the effluent. Vanadium was removed to <5 ug/L in system effluent most of the time.
Chromatographic peaking was not observed for vanadium in either period, suggesting that vanadium
might have an equivalent or even higher selectivity than sulfate.
Slight reductions in treated water pH values were observed for a short period immediately after the
system had just been regenerated. Although pH changes were small, i.e., no more than 0.3 pH unit,
corresponding reductions in total alkalinity across the system were significant (up to 50%). The reduction
in pH and alkalinity was attributed to removal of bicarbonate ions by the AIX resin. pH values of treated
water returned to raw water levels afterwards due to complete breakthrough of bicarbonate ions, which
had a lowest selectivity by the strong base AIX resin.
Distribution system water samples were collected only in Study Period I. Because treated water from the
IX system was stored in a 200,000-gal reservoir before supplying the distribution system, the water
quality of the distribution system water samples reflected the general quality of the plant effluent after
being blended in the reservoir. After system startup, arsenic concentrations at all three sampling locations
ranged from 7.1 to 24.0 (ig/L and averaged 12.6 ug/L, which were significantly lower than the baseline
levels, but not to the low level (i.e., <5 (ig/L) that would be expected from an IX treatment plant because
the IX system had been operated beyond 10 ug/L. Although occasionally, some low pH and low
alkalinity were measured in treated water samples collected from the freshly regenerated vessels, the
blending effect in the reservoir had mitigated any pH or alkalinity swing. Therefore, low pH and low
alkalinity were never measured in the distribution samples.
Residual Characterization
Residuals produced by the IX system, including spent brine and rinse water, were discharged to the
evaporation pond adjacent to the treatment building. Ferric chloride was added to the spent brine stream
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in an attempt to precipitate arsenic and allow the iron sludge to settle in the evaporation pond. The
design and construction of the evaporation pond and the ferric chloride treatment system were performed
by the City's contractors.
The volume of wastewater produced was determined by regeneration frequency and the volume of
wastewater produced per regeneration cycle. On average, each regeneration cycle produced 8,681 gal of
wastewater per vessel in Study Period I and 7,244 gal per vessel in Study Period II, which is 17% less
than that in Study Period I.
To characterize the quality of residuals, samples were collected from the waste stream from each
regeneration step as well as the pond water. Total arsenic concentrations in spent brine, fresh brine, slow
rinse, and fast rinse samples averaged 2,678, 2,221, 527, and 11.3 (ig/L, respectively, for Arsenex II, and
averaged 2,203, 150, and 3.4 (ig/L, respectively for PFA300E/A850END (note that spent brine draw was
not used). Similarly, nitrate concentrations averaged 122, 517, 194, and 3.6 mg/L (as N) for Arsenex II
and 450, 68, and 2.6 mg/L (as N) for dual resins.
With a pH of 9.3 to 9.8 and a total alkalinity of 4,560 mg/L, the evaporation pond water contained 16 to
25.6 g/L of chloride, 13 to 30.2 g/L of sodium, and 38.2 to 60.1 g/L of TDS, indicating a highly alkaline
and saline water. The pond water also contained up to 1.3 mg/L of total arsenic, 7.3 g/L of sulfate, 9.2
mg/L (as N) of nitrate, 13.3 mg/L of total phosphorus (as P), and 4.1 mg/L of vanadium. High arsenic
concentrations in the pond water suggested ineffective ferric chloride treatment, presumably due to high
TDS content and the presence of competing ions in the pond water.
A regeneration elution study performed on dual resins indicated that the percent recoveries were 112% for
arsenic, 131% for nitrate, 113% for vanadium, and 98.5% for TOC.
Cost of Technology
The capital cost of the IX system was $395,434, which included $260,194 for equipment, $49,840 for site
engineering, and $85,400 for installation, accounting for 66%, 12%, and 22% of the total capital
investment, respectively. This capital cost was normalized to the system's rated capacity of 540 gpm (or
777,600 gal/day [gpd]), which resulted in $732 per gpm (or $0.51 per gpd). The cost associated with
design and construction of a new building, an evaporation pond, and a ferric chloride addition system (to
treat the brine waste) was funded separately by the City of Vale, and not included in the cost of the
system.
The O&M cost for the IX system included the incremental cost associated with the salt supply, electricity
consumption, and labor, which was estimated to be $0.35/1,000 gal of water treated. The cost of salt and
caustic soda was the most significant add-on, approximately $32,826 per year, or $0.29/1,000 gal.
Because the current salt saturators can only hold half truckload of salt, if more salt storage capacity is
added to allow delivery of a full truckload, then the overall salt cost could be further reduced.
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CONTENTS
DISCLAIMER ii
FOREWORD iii
ABSTRACT iv
APPENDICES ix
FIGURES ix
TABLES x
ABBREVIATIONS AND ACRONYMS xii
ACKNOWLEDGMENTS xiv
1.0: INTRODUCTION 1
1.1 Background 1
1.2 Treatment Technologies for Arsenic Removal 2
1.3 Project Objectives 2
2.0 SUMMARY AND CONCLUSIONS 5
3.0: MATERIALS AND METHODS 7
3.1 General Project Approach 7
3.2 System O&M and Cost Data Collection 8
3.3 Sample Collection Procedures and Schedules 9
3.3.1 Source Water 9
3.3.2 Treatment Plant Water 9
3.3.3 Regeneration Wastewater 12
3.3.4 Distribution System Water 12
3.4 Real-Time Arsenic Monitoring with ArsenicGuard™ 12
3.5 Run Length and Regeneration Elution Studies 13
3.5.1 Run Length Studies 13
3.5.2 Regeneration Elution Study 15
3.6 IX Resin Cleaning 16
3.7 Sampling Logistics 16
3.7.1 Preparation of Arsenic Speciation Kits 16
3.7.2 Preparation of Sampling Coolers 17
3.7.3 Sample Shipping and Handling 17
3.8 Analytical Procedures 17
4.0: RESULTS AND DISCUSSION 18
4.1 Facility Description 18
4.1.1 Source Water Quality 18
4.1.2 Distribution System Water Quality 23
4.2 Treatment Process Description 23
4.2.1 Ion Exchange Process 23
4.2.2 Treatment Process 27
4.3 System Installation 36
4.3.1 Permitting 36
4.3.2 Construction of Treatment Building and Evaporation Pond 36
4.3.3 System Installation, Shakedown, and Startup 38
4.4 System Operation 40
4.4.1 Operational Parameters 41
4.4.2 Regeneration 42
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4.4.2.1 Regeneration Set Points 42
4.4.2.2 Regeneration Monitoring 44
4.4.2.3 Salt Usage 46
4.4.3 IX Resin Fouling 48
4.4.4 Dual IX Resin Approach 49
4.4.4.1 Dual Resin Options 50
4.4.4.2 Concerns over Solids in IX Resin Beds 50
4.4.4.3 Special Study at McCook, NE 51
4.4.4.4 Dual Resin Installation 54
4.4.5 Residual Management 54
4.4.6 System Operation Requirement 55
4.4.6.1 Required System Operation and Operator Skills 55
4.4.6.2 Preventive Maintenance Activities 56
4.4.6.3 Chemical/Media Handling and Inventory Requirements 56
4.5 System Performance 56
4.5.1 Treatment Plant Sampling 56
4.5.1.1 Arsenic Speciation 60
4.5.1.2 Arsenic Removal 62
4.5.1.3 Nitrate Removal 65
4.5.1.4 TOC, Sulfate, Phosphate, and Vanadium Removal 67
4.5.1.5 Other Water Quality Parameters 67
4.5.2 Real-Time Arsenic Monitoring by ArsenicGuard™ 73
4.5.3 Run Length Studies 74
4.5.4 Regeneration Elution Study 79
4.5.5 Regeneration Residual Sampling 82
4.5.6 Analysis of Evaporation Pond Water 85
4.5.7 Distribution System Water Sampling 86
4.6 System Cost 88
4.6.1 Capital Cost 89
4.6.2 Operation and Maintenance Cost 90
5.0 REFERENCES 92
APPENDICES
APPENDIX A: Vale Arsenic System IX Resin Cleaning Procedure
APPENDIX B: Vale, OR Project Chronology
APPENDIX C: Operational Data
APPENDIX D: Analytical Data
FIGURES
Figure 3-1. Process Flow Diagram and Sampling Locations/Analyses for Vale IX System 11
Figure 3-2. Real-Time Arsenic Analyzer- ArsenicGuard™ 13
Figure 3-3. Regeneration Monitoring Setup 15
Figure 4-1. Existing Well House in Vale, OR 19
Figure 4-2. Existing Chlorination System in Vale, OR 19
Figure 4-3. Historic Nitrate Data from Wells No. 1 Through No. 7 22
Figure 4-4. Simulation of Arsenex II Resin Run Length 26
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Figure 4-5. Simulation of A850END/PFA300E Resin Run Length (June 2008) 26
Figure 4-6 Schematic of Kinetico's IX-263 As/N Removal System for Vale, OR 27
Figure 4-7. System Inlet Piping and Booster Pump 29
Figure 4-8. Photograph of Two Banks of Cartridge Filters 30
Figure 4-9. Photographs of Arsenic/Nitrate Removal IX System at Vale, OR 31
Figure 4-10. Skid-Mounted Piping/Varying Rack 31
Figure 4-11. Photographs of IX Regeneration System at Vale, OR 33
Figure 4-12. Salt Delivery to Fill Salt Saturators 34
Figure 4-13. Wastewater Evaporation Pond 35
Figure 4-17. Vale Treatment System Delivering and Offloading 38
Figure 4-18. PLC Regeneration Setpoints Shown on OIP 43
Figure 4-19. The McCook, NE Water Treatment Plant 51
Figure 4-20. Sample Collection and pH/TDS Monitoring during Regeneration of AIX Vessel 5
at McCook, NE 52
Figure 4-21. Results of McCook AIX Vessel 5 53
Figure 4-22. Concentrations of Arsenic Species across Treatment System 61
Figure 4-23. Total Arsenic Concentrations Measured During Study Period 1 63
Figure 4-24. Total Arsenic Concentrations Measured During Study Period II 64
Figure 4-25. Reconstructed Breakthrough Curves for Nitrate 66
Figure 4-26. Reconstructed Breakthrough Curves for Sulfate 68
Figure 4-27. Reconstructed Breakthrough Curves for Total Phosphorus 69
Figure 4-28. Reconstructed Breakthrough Curves for Total Vanadium 70
Figure 4-29. pH Measured During Study Period 1 71
Figure 4-30. Reconstructed Breakthrough Curves for Total Alkalinity 72
Figure 4-31. Examples of Real-Time Arsenic Monitoring by ArsenicGuard™ 73
Figure 4-32. Vessel A Breakthrough Curves from Run Length Study 1 75
Figure 4-33. Vessel A Breakthrough Curves from Run Length Study 2 75
Figure 4-34. Vessel A Breakthrough Curves from Run Length Study 3 76
Figure 4-35. Combined Effluent Breakthrough Curves from Run Length Study 4 77
Figure 4-36. Breakthrough Curves from Run Length Study 5 78
Figure 4-37. pH and Alkalinity Breakthrough Curves from Run Length Study 5 79
Figure 4-38. Vessels A and B Elution Curves 80
Figure 4-39. Vessels A and B Elution Curves for TDS andpH 81
Figure 4-40. Results of Vale Pond Water Jar Tests 86
TABLES
Table 1-1. Summary of Round 1 and Round 2 Arsenic Removal Demonstration Locations,
Technologies, and Source Water Quality 3
Table 3-1. Pre-Demonstration Study Activities and Completion Dates 7
Table 3-2. Evaluation Objectives and Supporting Data Collection Activities 8
Table 3-3. Sampling and Analysis Schedule at Vale, OR 10
Table 3-4. Sampling and Analysis Schedules for Run Length Studies 14
Table 3-5. Sampling and Analysis Schedules for Resin Elution Study 16
Table 4-1. Construction Details of Wells No. 1 to No. 7 18
Table 4-2. Vale, OR Source Water Data for Combined Wells No. 1 to No. 7 20
Table 4-3. Wells No. 1 to No. 7 Water Quality Data from June 2000 to August 2000 21
Table 4-4. Wells No. 1 to No. 7 Water Quality Data from EPA (December 2004) 21
Table 4-5. Wells No. 1 to No. 7 Nitrate Concentrations (mg/L [as N]) from Source (February
2001 to October 2004) 21
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Table 4-6. Physical and Chemical Properties of IX Resins 25
Table 4-7. Design Specifications of IX System 28
Table 4-8. System Punch List during Startup 39
Table 4-9. Key Demonstration Study Activities/Events 40
Table 4-10. Summary of System Operational Data 41
Table 4-11. IX System Regeneration Setpoints at Vale, OR 44
Table 4-12. IX System Regeneration Monitoring at Vale, OR 45
Table 4-13. Vale, IX System Salt Loading Calculations 47
Table 4-14. Resin Analyses After Laboratory or Field Cleaning 48
Table 4-15. Freeboard Measurements During Rebedding at Vale, OR 54
Table 4-16. Summary of Arsenic and Nitrate Analyses in Study Periods I and II 57
Table 4-17. Summary of Other Water Quality Parameters in Study Period 1 58
Table 4-18. Summary of Other Water Quality Parameters in Study Period II 60
Table 4-19. Mass Balance Calculations for Total Arsenic, Nitrate, Vanadium, and TOC 83
Table 4-20. Regeneration Residual Sampling Results 84
Table 4-21. Analytical Data for Pond Water at Vale, OR 85
Table 4-22. Distribution System Sampling Results in Study Period I at Vale, OR 87
Table 4-23. Cost Breakdowns of Capital Investment for Vale IX System 89
Table 4-24. O&M Cost for Vale, OR Treatment System 90
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ABBREVIATIONS AND ACRONYMS
AAL American Analytical Laboratories
AIX anion exchange
Al aluminum
AM adsorptive media
As arsenic
ASV anodic stripping voltammetry
ATS Aquatic Treatment Systems
bgs below ground surface
BV bed volume
C/F coagulation/filtration
Ca calcium
Cl chlorine
Cu copper
DHS DWP (Oregon) Department of Human Service, Drinking Water Program
DO dissolved oxygen
DOM dissolved organic matter
DVB divinylbenzene
EBCT empty bed contact time
EPA U.S. Environmental Protection Agency
F fluoride
Fe iron
FRP fiberglass reinforced plastic
gpd gallons per day
gph gallons per hour
gpm gallons per minute
FŁAA5 haloacetic acids
HOPE high-density polyethylene
HIX hybrid ion exchanger
hp horsepower
ICP-MS inductively coupled plasma-mass spectrometry
ID identification
IX ion exchange
LCR Lead and Copper Rule
MCL maximum contaminant level
MDL method detection limit
MEI Magnesium Elektron, Inc.
Mg magnesium
MOD million gallon per day
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Mn manganese
mV millivolts
Na sodium
NRMRL National Risk Management Research Laboratory
NSF NSF International
NTU nephelometric turbidity units
O&M operation and maintenance
OIP operator interface panel
OIT Oregon Institute of Technology
ORD Office of Research and Development
ORP oxidation-reduction potential
P&ID piping and instrumentation diagram
PLC programmable logic controller
POU point of use
ppb parts per billion
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
RO reverse osmosis
SBA strong-base anion
SDWA Safe Drinking Water Act
STS Severn Trent Services
TCLP Toxicity Characteristic Leaching Procedure
TDH total dynamic head
TDS total dissolved solids
TOC total organic carbon
TTHMs trihalomethanes
V vanadium
VFD variable frequency drive
WTP Water Treatment Plant
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ACKNOWLEDGMENTS
The authors wish to extend their sincere appreciation to the staff of the Department of Public Works at the
City of Vale, OR. The primary operators, Mr. Les Bertalotto and Mr. Terry Harris, monitored the
treatment system daily and collected water samples from the treatment and distribution systems on a
regular schedule throughout the study period. This performance evaluation would not have been possible
without their efforts.
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1.0 INTRODUCTION
1.1 Background
The Safe Drinking Water Act (SDWA) mandates that the United States Environmental Protection Agency
(EPA) identify and regulate drinking water contaminants that may have adverse human health effects and
are known or anticipated to occur in public water supply systems. In 1975 under the SDWA, EPA
established a maximum contaminant level (MCL) for arsenic (As) at 0.05 mg/L. Amended in 1996, the
SDWA required that EPA develop an arsenic research strategy and publish a proposal to revise the
arsenic MCL by January 2000. On January 18, 2001, EPA finalized the arsenic MCL at 0.01 mg/L (EPA,
2001). To clarify the implementation of the original rule, EPA revised the rule text on March 25, 2003, to
express the MCL as 0.010 mg/L (or 10 (ig/L) (EPA, 2003). The final rule required all community and
non-transient, non-community water systems to comply with the new standard by January 23, 2006.
In October 2001, EPA announced an initiative for additional research and development of cost-effective
technologies to help small community water systems (< 10,000 customers) meet the new arsenic standard,
and to provide technical assistance to operators of small systems in order to reduce compliance cost. As
part of this Arsenic Rule Implementation Research Program, EPA's Office of Research and Development
(ORD) proposed a project to conduct a series of full-scale, onsite demonstrations of arsenic removal
technologies, process modifications, and engineering approaches applicable to small systems. Shortly
thereafter, an announcement was published in the Federal Register requesting water utilities interested in
participating in Round 1 of this EPA-sponsored demonstration program to provide information on their
water systems. In June 2002, EPA selected 17 out of 115 sites to host the demonstration studies
In September 2002, EPA solicited proposals from engineering firms and vendors for cost-effective arsenic
removal treatment technologies for the 17 host sites. EPA received 70 technical proposals for the 17 host
sites, with each site receiving from one to six proposals. In April 2003, an independent technical panel
reviewed the proposals and provided its recommendations to EPA on the technologies that it determined
were acceptable for the demonstration at each site. Because of funding limitations and other technical
reasons, only 12 of the 17 sites were selected for the demonstration program. Using the information
provided by the review panel, EPA in cooperation with the host sites and the drinking water programs of
the respective states selected one technical proposal for each site.
In 2003, EPA initiated Round 2 arsenic technology demonstration projects that were partially funded with
Congressional add-on funding to the EPA budget. In June 2003, EPA selected 32 potential demonstration
sites. The City of Vale, OR was one of those selected.
In September 2003, EPA again solicited proposals from engineering firms and vendors for arsenic
removal technologies. EPA received 148 technical proposals for the 32 host sites, with each site
receiving from two to eight proposals. In April 2004, another technical panel was convened by EPA to
review the proposals and provide recommendations to EPA with the number of proposals per site ranging
from none (for two sites) to a maximum of four. The final selection of the treatment technology at the
sites that received at least one proposal was made, again, through a joint effort by EPA, the state
regulators, and the host site. Since then, five sites have withdrawn from the demonstration program,
reducing the number of sites to 27. An ion exchange (IX) system proposed by Kinetico was selected for
demonstration at the Vale, OR, site for the removal of arsenic and nitrate from drinking water supplies.
As of February 2011, the performance evaluations of all 39 systems have been completed.
-------
1.2 Treatment Technologies for Arsenic Removal
The technologies selected for the Round 1 and Round 2 demonstration host sites include 25 adsorptive
media (AM) systems (the Oregon Institute of Technology [OIT] site has three AM systems), 13
coagulation/filtration (C/F) systems, two IX systems, 17 point-of-use (POU) units (including nine under-
the-sink reverse osmosis [RO] units at the Sunset Ranch Development site and eight AM units at the OIT
site), and one process modification. Table 1-1 summarizes the locations, technologies, vendors, system
flowrates, and key source water quality parameters (including arsenic, iron, and pH) at the 40 demon-
stration sites. An overview of the technology selection and system design for the 12 Round 1
demonstration sites and the associated capital cost is provided in two EPA reports (Wang et al, 2004;
Chen et al., 2004), which are posted on the EPA Web site at
http: //www. epa. gov/ORD/NRMRL/wswrd/dw/arsenic/index.html.
1.3 Project Objectives
The objective of the Round 1 and Round 2 arsenic demonstration program was to conduct full-scale
arsenic treatment technology demonstration studies on the removal of arsenic from drinking water
supplies. The specific objectives were to:
• Evaluate the performance of the arsenic removal technologies for use on small systems.
• Determine the required system operation and maintenance (O&M) and operator skill levels.
• Characterize process residuals produced by the technologies.
• Determine the capital and O&M cost of the technologies.
This report documents the performance of the Kinetico IX system at the City of Vale, OR, from
September 19, 2006, through March 22, 2010. The types of data collected included system operation,
water quality (both across the treatment train and in the distribution system), residuals, and capital and
preliminary O&M cost. Short-term special studies also were conducted to troubleshoot operational and
performance issues and improve the overall effectiveness and efficiency of the treatment system.
-------
Table 1-1. Summary of Round 1 and Round 2 Arsenic Removal Demonstration
Locations, Technologies, and Source Water Quality
Demonstration
Location
Site Name
Technology (Media)
Vendor
Design
Flow rate
(gpm)
Source Water Quality
As
(ug/L)
Fe
(Mg/L)
PH
(S.U.)
Northeast/Ohio
Wales, ME
Bow,NH
Goffstown, NH
Rollinsford, NH
Dummerston, VT
Felton, DE
Stevensville, MD
Houghton, NY(d)
Buckeye Lake, OH
Springfield, OH
Springbrook Mobile Home Park
White Rock Water Company
Orchard Highlands Subdivision
Rollinsford Water and Sewer District
Charette Mobile Home Park
Town of Felton
Queen Anne's County
Town of Caneadea
Buckeye Lake Head Start Building
Chateau Estates Mobile Home Park
AM (A/I Complex)
AM(G2)
AM(E33)
AM(E33)
AM (A/I Complex)
C/F (Macrolite)
AM(E33)
C/F (Macrolite)
AM (ARM 200)
AM(E33)
ATS
ADI
AdEdge
AdEdge
ATS
Kinetico
STS
Kinetico
Kinetico
AdEdge
14
70w
10
100
22
375
300
550
10
250(e)
38W
39
33
36W
30
30W
19w
27W
15W
25w
<25
<25
<25
46
<25
48
270(c)
l,806(c)
1,312W
1,615W
8.6
7.7
6.9
8.2
7.9
8.2
7.3
7.6
7.6
7.3
Great Lakes/Interior Plains
Brown City, MI
Pentwater, MI
Sandusky, MI
Delavan, WI
Greenville, WI
Climax, MN
Sabin, MN
Sauk Centre, MN
Stewart, MN
Lidgerwood, ND
City of Brown City
Village of Pentwater
City of Sandusky
Vintage on the Ponds
Town of Greenville
City of Climax
City of Sabin
Big Sauk Lake Mobile Home Park
City of Stewart
City of Lidgerwood
AM(E33)
C/F (Macrolite)
C/F (Aeralater)
C/F (Macrolite)
C/F (Macrolite)
C/F (Macrolite)
C/F (Macrolite)
C/F (Macrolite)
C/F&AM(E33)
Process Modification
STS
Kinetico
Siemens
Kinetico
Kinetico
Kinetico
Kinetico
Kinetico
AdEdge
Kinetico
640
400
340(e)
40
375
140
250
20
250
250
14W
13W
16W
20W
17
39W
34
25W
42W
146W
127w
466W
1,387W
l,499(c)
7827(c)
546W
l,470(c)
3,078(c)
1,344W
l,325(c)
7.3
6.9
6.9
7.5
7.3
7.4
7.3
7.1
7.7
7.2
Midwest/Southwest
Arnaudville, LA
Alvin, TX
Bruni, TX
Wellman, TX
Anthony, NM
Nambe Pueblo, NM
Taos, NM
Rimrock, AZ
Tohono O'odham
Nation, AZ
Valley Vista, AZ
United Water Systems
Oak Manor Municipal Utility District
Webb Consolidated Independent School
District
City of Wellman
Desert Sands Mutual Domestic Water
Consumers Association
Nambe Pueblo Tribe
Town of Taos
Arizona Water Company
Tohono O'odham Utility Authority
Arizona Water Company
C/F (Macrolite)
AM(E33)
AM(E33)
AM(E33)
AM(E33)
AM(E33)
AM (E33)
AM(E33)
AM(E33)
AM (AAFS50/ARM 200)
Kinetico
STS
AdEdge
AdEdge
STS
AdEdge
STS
AdEdge
AdEdge
Kinetico
770(e)
150
40
100
320
145
450
90(b)
50
37
35(a)
19w
56W
45
23W
33
14
50
32
41
2,068(c)
95
<25
<25
39
<25
59
170
<25
<25
7.0
7.8
8.0
7.7
7.7
8.5
9.5
7.2
8.2
7.8
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Table 1-1. Summary of Round 1 and Round 2 Arsenic Removal Demonstration
Locations, Technologies, and Source Water Quality (Continued)
Demonstration
Location
Site Name
Technology (Media)
Vendor
Design
Flow rate
fepm)
Source Water Quality
As
(ug/L)
Fe
(ug/L)
PH
(S.U.)
Far West
Three Forks, MT
Fruitland, ID
Homedale, ID
Okanogan, WA
Klamath Falls, OR
Vale, OR
Reno, NV
Susanville, CA
Lake Isabella, CA
Tehachapi, CA
City of Three Forks
City of Fruitland
Sunset Ranch Development
City of Okanogan
Oregon Institute of Technology
City of Vale
South Truckee Meadows General
Improvement District
Richmond School District
Upper Bodfish Well Cffi-A
Golden Hills Community Service District
C/F (Macrolite)
IX (A300E)
POU RO(1)
C/F (Electromedia-I)
POE AM (Adsorbsia/ARM 200/ArsenXnp)
and POU AM (ARM 200)(g)
IX(ArsenexII)
AM (GFH/Kemiron)
AM (A/I Complex)
AM(HIX)
AM (Isolux)
Kinetico
Kinetico
Kinetico
Filtronics
Kinetico
Kinetico
Siemens
ATS
VEETech
MEI
250
250
75gpd
750
60/60/30
525
350
12
50
150
64
44
52
18
33
17
39
37W
35
15
<25
<25
134
69(0
<25
<25
<25
125
125
<25
7.5
7.4
7.5
8.0
7.9
7.5
7.4
7.5
7.5
6.9
AM = adsorptive media; C/F = coagulation/filtration; EHX = hybrid ion exchange; IX = ion exchange process; RO = reverse osmosis
ATS = Aquatic Treatment Systems; MEI = Magnesium Elektron, Inc.; STS = Severn Trent Services
(a) Arsenic existing mostly as As(III).
(b) Design flowrate reduced by 50% due to system reconfiguration from parallel to series operation.
(c) Iron existing mostly as Fe(II).
(d) Withdrew from program in 2007. Selected originally to replace Village of Lyman, NE site, which withdrew from program in June 2006.
(e) Facilities upgraded systems in Springfield, OH from 150 to 250 gpm, Sandusky, MI from 210 to 340 gpm, and Amaudville, LA from 385 to 770 gpm.
(f) Including nine residential units.
(g) Including eight under-the-sink units.
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2.0 SUMMARY AND CONCLUSIONS
Based on the data collected from this 3.5-year long demonstration study at Vale, OR, the following
summary and conclusions were made relating to the overall objectives of the treatment technology
demonstration study.
Performance of the IX arsenic/nitrate removal technology for use on small systems:
• Arsenex II resin can remove arsenic and nitrate from water supplies to below their respective
MCLs of 10-|o,g/L and 10-mg/L (as N), provided that the system is regenerated timely. The
Vale, OR IX plant achieved an initial run length of 562,000 gal (or 404 bed volumes [BV]) at
10-|o,g/L arsenic breakthrough. However, due to organic fouling, the useful run length was
reduced to up to 80% of the initial level after seven months of system operations.
• PFA300E top-dressed with A850END is effective at removing arsenic and nitrate and is less
susceptible to organic fouling. The system can treat 454,400 gal (or 372 BV) of water before
regeneration is required. Regenerating dual resins with an alkaline brine periodically (i.e.,
once every four months) can prevent PFA300E fouling.
• The smaller resin bed was the key reason for not meeting the treatment target of 600,000 gal
desired by the City of Vale. To meet this treatment target, an additional 55 to 60 ft3of
PFA300E resin would be required.
• Both Arsenex II and A850END/PFA300E consistently removed vanadium from an average
of 52 |o,g/L in raw water to <5 |o,g/L in treated water for at least 600,000 gal (i.e., 431 BV).
• Arsenic and nitrate peaking can occur if the system was operated beyond exhaustion. To
avoid peaking, the IX system must be regenerated timely.
• The presence of 1.4 to 2.2 mg/L of total organic carbon (TOC) in raw water can result in
severe resin fouling. Cleaning the fouled IX resin with a mixture of caustic/brine can be
effective in restoring resin's volumetric and strong base capacities and moisture content, but
may not improve resin run length to the same extent.
• Simulation of the IX resin run length by computer software was found to over-estimate the
resin performance by as high as 50%.
Required system O&M and operator skill levels:
• Under normal operating conditions, the skill requirements to operate the system were
minimal, with a typical daily demand on the operator of 40 min. Other skills needed
for performing O&M activities include replacing filter bags periodically, using a
hydrometer to check brine concentrations, monitoring salt inventory levels,
scheduling salt delivery, and working with the vendor to troubleshoot and perform
minor onsite repairs.
• Monitoring salt usage during a regeneration cycle can ensure that the IX resin is properly
regenerated.
-------
• Salt unloading can generate excessive salt dust that is corrosive to the electrical and
mechanical components of the treatment system. Placing the salt saturators in a separate
room can minimize the salt dust and corrosion issues.
Process residuals produced by the technology:
• Residuals produced by the IX system included spent brine and rinse water. The
volume of wastewater produced was dependent upon regeneration frequency and
settings.
• Design of residual (brine) disposal should consider that projections of wastewater
production may be low because of lower than projected run lengths.
• Ferric chloride treatment was ineffective at removing arsenic in spent brine
discharged to the evaporation pond, probably caused by high total dissolved solids
(TDS).
Cost of the technology:
• Using the system's rated capacity of 540 gal/min (gpm) (or 777,600 gal/day [gpd]), the
capital cost was $732/gpm (or $0.51/gpd) of the design capacity.
• Cost of salt supply was the significant add-on to the previous plant operation. The cost for
salt and caustic soda was $0.29/1,000 gal of water treated.
• Design of the salt saturator should consider the storage capacity required for entire truckload
delivery of salt to achieve maximum cost savings.
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3.0 MATERIALS AND METHODS
3.1
General Project Approach
Table 3-1 summarizes all predemonstration activities and respective completion dates. The performance
evaluation study of the IX system at Vale, OR began on September 19, 2006, and ended on March 22,
2010. Table 3-2 summarizes types of data collected and/or considered as part of the technology
evaluation process. The overall system performance was evaluated based on its ability to consistently
remove arsenic and nitrate to below their respective MCLs of 10 |o,g/L and 10 mg/L (as N) through the
collection of water samples across the treatment train, as described in a Performance Evaluation Study
Plan (Battelle, 2006). The reliability of the system was evaluated by tracking the unscheduled system
downtime and frequency and extent of equipment repairs and replacement. The plant operator recorded
unscheduled downtime and repair information on a Repair and Maintenance Log Sheet.
Table 3-1. Pre-Demonstration Study Activities and Completion Dates
Activity
Introductory Meeting Held
Letter of Understanding Issued
Request for Quotation Issued to Vendor
Vendor Quotation Received by Battelle
Purchase Order Completed and Signed
Engineering Package Submitted to Oregon DHS DWP
Treatment System Permit Issued
Building Construction Begun
Building Construction Completed
Letter Report Issued
Treatment System Shipped
Treatment System Arrived
System Installation Completed
System Shakedown Completed
Study Plan Issued
Performance Evaluation Begun
Date
December 2, 2004
March 2, 2005
March 10, 2005
March 30, 2005
April 5, 2005
July 22, 2005
August 11, 2005
December 5, 2005
February 28, 2006
March 30, 2006
May 8, 2006
May 12, 2006
June 5, 2006
July 23, 2006
September 14, 2006
September 19, 2006
DHS DWP = Department of Human Service Drinking Water Program
The required system O&M and operator skill levels were evaluated based on a combination of
quantitative data and qualitative considerations, including the need for pre- and/or post-treatment, level of
system automation, extent of preventive maintenance activities, frequency of chemical and/or media
handling and inventory, and general knowledge needed for relevant chemical processes and health and
safety practices. The staffing requirements for the system operation were recorded on an Operator Labor
Hour Log Sheet.
The quantity of residuals generated was estimated by tracking the flowrate and duration of each regenera-
tion step (i.e., brine draw, slow rinse, and fast rinse) and the number of regeneration cycles during the
study period. Spent regenerant samples were collected and analyzed for chemical characteristics.
The system cost was evaluated based on the capital cost per gpm (or gpd) of design capacity and the
O&M cost per 1,000 gal of water treated. This required tracking the capital cost for equipment, site
engineering, and installation, as well as the O&M cost for salt supply, electrical power use, and labor.
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Table 3-2. Evaluation Objectives and Supporting Data Collection Activities
Evaluation
Objective
Performance
Reliability
System O&M and
Operator Skill
Requirements
Residual
Management
System Cost
Data Collection
-Ability to consistently meet 10 \ig/L of arsenic MCL and 10 mg/L of
nitrate (as N) MCL in treated water
-Unscheduled system downtime
-Frequency and extent of repairs, including a description of problems,
materials and supplies needed, and associated labor and cost
-Pre- and post-treatment requirements
-Level of automation for system operation and data collection
-Staffing requirements, including number of operators and laborers
-Task analysis of preventive maintenance, including number, frequency,
and complexity of tasks
-Chemical handling and inventory requirements
-General knowledge needed for relevant chemical processes and health and
safety practices
-Quantity and characteristics of aqueous and solid residuals generated by
system operation
-Capital cost for equipment, site engineering, and installation
-O&M cost for chemical usage, electricity consumption, and labor
3.2
System O&M and Cost Data Collection
The plant operator performed daily, weekly, and monthly system O&M and data collection according to
instructions provided by Kinetico and Battelle. The plant operator recorded system operational data, such
as pressure, flowrate, system throughput, hour meter, and regeneration counter readings on a Daily
System Operation Log Sheet; checked brine day tank and salt saturator levels; and conducted visual
inspections for leaks or faults. If any problems occurred, the plant operator contacted the Battelle Study
Lead, who would then determine if Kinetico should be contacted for troubleshooting. The plant operator
recorded all relevant information, including problem encountered, course of action taken, materials and
supplies used, and associated cost and labor incurred, on the Repair and Maintenance Log Sheet. On a
weekly basis, the plant operator measured water quality parameters, including pH, temperature, dissolved
oxygen (DO), and oxidation-reduction potential (ORP), and recorded the data on a Weekly Water Quality
Parameters Log Sheet. During the study period, the system was regenerated automatically when triggered
by a pre-determined throughput setpoint. Occasionally, system regeneration was initiated by the operator
for sampling purposes.
The capital cost for the arsenic-removal system consisted of the cost for equipment, site engineering, and
system installation. The O&M cost consisted primarily of the cost for salt usage, electricity consumption,
and labor. Salt was delivered to the treatment plant in bulk quantities by Handy Wholesale Products, Inc.
in Burley, ID, on a monthly or as-needed basis. Salt usage was tracked through monthly invoices.
Electricity consumption was obtained from utility bills for the study period. The labor for routine system
O&M, system troubleshooting and repairs, and demonstration-related work, was recorded on an Operator
Labor Hour Sheet. Routine O&M included activities such as completing field logs, ordering supplies,
performing system inspections, and others as recommended by the vendor. The labor for demonstration-
related work, including activities such as performing field measurements, collecting and shipping
samples, and communicating with the Battelle Study Lead, was recorded but not used for cost analysis.
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3.3 Sample Collection Procedures and Schedules
System operation underwent three separate yet inter-related periods:
• Study Period I (from September 19, 2006 through January 14, 2008)
• Interim Period (from January 15, 2008 through February 9, 2009)
• Study Period II (from February 10,2009 through March 22, 2010)
Sampling was performed only in Study Periods I and II with schedules noted in Section 3.3.2. The plant
operator collected water samples from the treatment plant/distribution system and during regeneration
either on a regular basis as summarized in Table 3-3, or through special run length/regeneration studies as
described in Section 3.5. Table 3-3 provides sampling schedules and analytes measured during each
regular sampling event. Figure 3-1 presents a process flow chart, along with applicable sampling/analysis
schedules, for the IX system. Specific sampling requirements for analytical methods, sample volumes,
containers, preservation, and holding times are presented in Table 4-1 of the EPA-endorsed Quality
Assurance Project Plan (QAPP) (Battelle, 2004).
3.3.1 Source Water. During the initial visit to the site on December 2, 2004, one set of source
water samples was collected for detailed water quality analyses (Table 3-3). The source water also was
speciated onsite for total and soluble As (including soluble As[III) and soluble As[V]), iron (Fe),
manganese (Mn), uranium (U), and vanadium (V). Special care was taken to avoid agitation, which
might cause unwanted oxidation.
3.3.2 Treatment Plant Water. Routine treatment plant water samples were collected from
September 20, 2006, through January 14, 2008 during Study Period I; and from March 25, 2009, through
February 8, 2010 during Study Period II.
Study Period I: The plant operator collected water samples across the treatment train weekly on a four-
week cycle. For the first week of each four-week cycle, water samples were collected and speciated at
four locations (i.e., at the wellhead [IN], after Vessel A [TA], after Vessel B [TB], and at the combined
effluent from Vessels A and B [TT]) and analyzed for the analytes listed under the monthly treatment
plant analyte list in Table 3-3. For the other three weeks, treatment plant samples were collected at three
locations (i.e., IN, TA, and TB) and analyzed for the analytes listed under the weekly treatment plant
analyte list in Table 3-3.
During Study Period I, several changes were made to the routine sampling schedule:
• Weekly sampling was not performed during the Thankgiving and Christmas holidays in 2006.
• One additional set of weekly samples was collected on February 6, 2007.
• The four-week-cycle treatment plant water sampling was discontinued on April 16, 2007, due
to performance issue related to short run lengths (Section 4.4.3).
• From July 16, 2007 through January 14, 2008, limited weekly water sampling was conducted
with samples collected at the TT location and analyzed for total As only.
Study Period II: Weekly sampling resumed on March 25, 2009, after dual resins had been installed.
Water samples were collected at IN, TA, TB, and TT locations and analyzed for the same set of analytes
done before plus TOC and V. Onsite water quality measurements and arsenic speciation were not
performed during this study period. Treatment plant water sampling ended on February 8, 2010.
-------
Table 3-3. Sampling and Analysis Schedule at Vale, OR
Sample
Type
Source
Water
Treatment
Plant Water
(Study
Period I)
Treatment
Plant Water
(Study
Period II)
Distribution
System
Water
(Study
Period I)
Residuals
Sampling
Locations'3'
IN
IN, TA, and
TB
IN, TA, TB,
andTT
IN, TA, TB,
andTT
Two LCR
and one
Non-
Residence
Locations
Drain pipe
off T A and
TB
No. of
Sampling
Locations
1
3
4
4
3
j(b)
Frequency
Once
Weekly
Monthly
Weekly
Monthly
4 times
Analytes
Onsite: pH, temperature,
DO, and ORP
Off site:
As (total and soluble),
As(III), As(V),
Fe (total and soluble),
Mn (total and soluble),
U (total and soluble),
V (total and soluble),
Na, Ca, Mg, Cl, F, NO2,
NO3, NH3, SO4, SiO2, P,
turbidity, alkalinity,
TDS, and TOC
Onsite: pH, temperature,
DO, and ORP
Off site: As (total),
Fe (total), Mn(total),
NO3, SO4, SiO2, P,
turbidity, alkalinity, and
TDS
Same as those for
weekly samples plus
following:
Off site: As (soluble)
As(III), As(V), Fe
(soluble), Mn (soluble),
V (total and soluble),
F, Ca, and Mg
Offsite: As (total),
Fe (total), Mn (total),
V (total), NO3, SO4,
SiO2, P, turbidity,
alkalinity, TDS, and
TOC
pH, alkalinity,
As (total), Fe (total),
Mn (total), Pb (total),
and Cu (total)
As (total), NO3, SO4,
TDS, and pH
Sampling
Date
12/02/04
See Appendix D
(09/20/06-
01/14/08)
See Appendix D
(09/20/06-
01/14/08)
See Appendix D
(03/25/09-
02/08/10)
Baseline:
(06/15/05-
09/21/05)
Monthly:
(10/10/06-
04/10/07)
12/20/06,
01/31/07,
03/20/07, and
06/29/09
(a) Abbreviations in parentheses corresponding to sample locations in Figure 3-1: IN = at wellhead,
TA = after Vessel A, TB = after Vessel B, and TT = conbined effluent.
(b) One composite sample from each regeneration step (i.e., reused brine draw, fresh brine draw,
slow rinse, and fast rinse).
DO = dissolved oxygen; ORP = oxidation-reduction potential; TDS = total dissolved solids; TOC = total
organic carbon
10
-------
INFLUENT
(COMBINED WELLS NO. 1-7)
Monthly^
BOOSTER PUMP WITH VFD
), temperature*), DO*), ORP*),
As (total and soluble), As(III), As(V),
Fe (totaland soluble), Mn (total and soluble),
V (total and soluble), Ca,Mg, F, NO3, SO4,
SiO2, P, turbidity, alkalinity, and IDS
BRINE WASTE LAGOON
4
pH,TDS,
As (total),
NO3, SO4
pH*), temperature*), DO*), ORP*),
As (total and soluble), As(III), As(V),
Fe (totaland soluble), Mn (total and soluble),
V (total and soluble), Ca,Mg, F, NO3, SO4,
SiO2, P, turbidity, alkalinity, and TDS
CARTPJDGE
FILTRATION
Vale, OR
Ion Exchange
Design Flow: 540 gpm
Weekly^)
pH*), temperature*), DO*),
• As (total), Fe (total), Mn (total), NOs, SO4,
SiO2, P, turbidity, alkalinity, and TDS
-pH*), temperature*), DO*),
As (total), Fe (total), Mn (total), NO3, SO4f
" SiO2, P, turbidity, alkalinity, and TDS
ATMOSPHERIC RESERVOIR
(200,000 gal)
BOOSTER PUMPS
Footnotes
(a) Applicable only to Study Period I
(b) Onsite analyses
DISTRIBUTION
SYSTEM
^0
o
1-1
fl
1
1
LEGEND
e At Wellhead
After Vessel A
rTBj After Vess el B
©After Vessels A and B
Combined
/D/--N Regeneration Sampling
\^^/ Location
f SS j Sludge SamplingLocation
CARTRIDGE TT -^
FILTRATION UnitProcess
DA: C12 Chlorine Disinfection
Figure 3-1. Process Flow Diagram and Sampling Locations/Analyses for Vale IX System
11
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3.3.3 Regeneration Wastewater. Regeneration wastewater samples were collected three times in
Study Period I and once in Study Period II. For each sampling event, one composite sample was
collected from each of the four regeneration steps, i.e., spent brine draw, fresh brine draw, slow rinse, and
fast rinse, during regeneration of one IX vessel. A portion of regeneration effluent was diverted to a 32-
gal plastic container via a garden hose over the duration of each regeneration step. After the content in
the container was thoroughly mixed, a portion of the liquid was transferred to a sample bottle and
analyzed for the analytes listed under "Residuals" in Table 3-3. A total of four samples were collected
during each sampling event. Arsenic speciation was not performed on these residual samples.
3.3.4 Distribution System Water. Water in the distribution system was sampled to assess the
impact of the IX system on the water chemistry in the distribution system, specifically, the arsenic,
nitrate, lead, and copper levels. Prior to the installation/operation of the treatment system, four sets of
baseline distribution system water samples were collected on a monthly basis starting in June 2005.
Three sampling locations were selected, including two residences within the city's sampling network
under the Lead and Copper Rule (LCR) and one non-residential location. Following system startup,
distribution system sampling continued on a monthly basis for seven months at the same three locations.
For the two LCR sampling locations, the plant operator delivered sample bottles to the residences and
picked up sample bottles after sampling was complete. For the non-residential location, the plant operator
collected samples directly from a spigot. Sampling followed an instruction sheet developed according to
the Lead and Copper Rule Monitoring and Reporting Guidance for Public Water Systems (EPA, 2002).
First-draw samples were collected from a cold-water faucet that had not been used for at least 6 hr to
ensure that stagnant water was sampled. The samplers recorded the date and time of last water use before
sampling and the date and time of sample collection for calculation of stagnation time. Arsenic speciation
was not performed on these samples. Analytes for the baseline and monthly distribution system water
samples are listed in Table 3-3. Distribution system sampling discontinued after April 10, 2007.
3.4 Real-Time Arsenic Monitoring with ArsenicGuard™
On November 19, 2008, an automated online arsenic analyzer, ArsenicGuard™ (Figure 3-2), was
installed at the site to monitor total arsenic concentrations in the IX system influent (IN) and effluent
(TT).
ArsenicGuard™ was developed by TraceDetect (Seattle, WA) to measure total inorganic arsenic in
drinking and groundwater using anodic stripping voltammetry (ASV), a voltammetric method for
quantitative determination of a specific ionic species. According to the vendor, the normal measurement
range is 1 to 25 (ig/L. Because the analyzer also supports dilution up to 50:1, the measurement range can
be extended upwards to 50 to 1,250 (ig/L. The accuracy in the normal range is 1 (ig/L or ±20%
(whichever is larger), and 50 (ig/L or ±20% for the extended range. Because the sensor is only sensitive
to arsenite, sample treatment is required prior to measurements. Each measurement begins with
acidification of a sample to pH -0.7 with 2M HC1, followed by reduction of arsenate to arsenite with
0.05N sodium thiosulfate. The analyzer then makes calibrated measurements by first scanning for arsenic
in the treated sample, followed by adding a metered quantity of arsenite (the spike) and re-scanning.
Upon completion of the measurements, the differences between the original peak and the spikes are used
to calculate the concentration of the original sample. This method of standard additions is a way of
calibrating the sensor for each sample matrix.
ArsenicGuard™ utilizes an electrochemical plating and stripping technique to measure part-per-billion
(ppb) quantities of arsenic. The treated sample as mentioned above is drawn into a measurement cell,
which houses a sensor along with a reference and an auxiliary electrode. The voltage of this
electrochemical cell is manipulated so that arsenic is first plated onto the tip of the sensor during an
12
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Figure 3-2. Real-Time Arsenic Analyzer - ArsenicGuard™
accumulation phase, and then stripped off the sensor during a stripping phase. The duration of the
accumulation phase is adjusted to ensure a good stripping signal, i.e., high concentrations are measured
using a short accumulation time and low concentrations using a longer accumulation time. The sensing
action occurs during the stripping phase of the measurement, during which the voltage of the
electrochemical cell is ramped from the accumulation potential, due to the release of the stripping
potential of arsenic. When arsenic is stripped off the sensor, it dissolves back into the test solution. This
stripping process releases three electrons per arsenic atom and, therefore, the amount of arsenic
accumulated on the tip of the sensor is proportional to the current measured during the stripping
operation. This current is recorded for the treated sample as well as for the spiked sample in order to
calculate the arsenic concentration in the original sample stream.
3.5
Run Length and Regeneration Elution Studies
3.5.1 Run Length Studies. Because routine weekly samples collected from the treatment plant
represented only discrete data points on breakthrough of arsenic and nitrate from multiple service cycles,
it was desirable to collect samples from complete service cycles to delineate breakthrough of arsenic,
nitrate, and other competing anions and determine the appropriate run length of the IX system. The
results of the studies were used to assess the system performance and to adjust the regeneration setpoint.
Table 3-4 summarizes sampling and analytical schedules of five run length studies (three in Study Period
I and two in Study Period II), during which effluent samples were collected from either one or both IX
vessels throughout five complete service cycles. The totalizer on the combined effluent ("TT") was used
to track the volume of water treated since last regeneration. The totalizer was automatically reset to
"zero" when Vessel A regeneration was completed, which signaled the beginning of a service cycle even
13
-------
Table 3-4. Sampling and Analysis Schedule for Run Length Studies
No.
1
2
3
4
5
Sampling
Date
09/19/06-
09/22/06
10/24/07-
10/26/07
12/08/08-
12/10/08
04/21/09-
04/22/09
06/29/09-
07/01/09
Study
Period
I
II
Sampling
Location
TA
TA
IN(a)/TA
TT
INW/TA/
TB/TT(a)
Regene-
ration
Setpoint
(gal)
905,300
600,000
600,000
600,000
600,000
No. of
Samples
10
7
13
6
26
Analytes
As (total), NO3, SO4, V (total), P
(total), and alkalinity
As (total), NO3, SO4, and alkalinity
As (total), V (total), and silica
As (total), NO3, V (total), P (total), and
TOC
As (total), NO3, SO4,V (total), P (total),
silica, alkalinity, pH, and TOC
(a) Sample collected once during run length study.
though Vessel B regeneration was just started. The service cycle ended when the totalizer reached a set
throughput value, which triggered the next regeneration cycle beginning with the Vessel A regeneration.
Additional information for each of the studies is provided below.
Run Length Study 1. At system startup, a run length study was conducted by Battelle staff during
September 19 through 22, 2006, to establish baseline performance of the IX system. Ten samples were
collected from Vessel A effluent ("TA") during a service cycle. Sampling began shortly after the service
cycle had started, and continued periodically, except during the night. Flow rates and throughput values
were recorded at the time of sampling for run length calculations. Samples were analyzed for total As, V,
and P, nitrate, sulfate, and total alkalinity.
Run Length Study 2: Following a caustic/brine cleaning on October 22, 2007, the operator performed a
run length study from October 24 through 26, 2007, to determine the effectiveness of the cleaning. Seven
samples were collected from Vessel A effluent ("TA") during a service cycle. Flow rates and throughput
were recorded at the time of sampling. Samples were analyzed for total arsenic, nitrate, sulfate, and total
alkalinity.
Run Length Study 3. Towards the end of Study Period I, the operator performed another run length
study from December 8 through 10, 2008, to determine the extent of resin fouling. One raw water sample
and 12 effluent samples from Vessel A ("TA") were collected during a service cycle. Flow rates and
throughput values were recorded at the time of sampling. Samples were analyzed for total As, total V,
and silica.
Run Length Study 4. At the startup of Study Period II, a run length study was conducted by the operator
on April 21 through 22, 2009, to assess the performance of the dual resin IX system. Six samples were
collected from the combined effluent from both vessels ("TT") during a service cycle. Flow rates and
throughput values were recorded at the time of sampling. Samples were analyzed for total As, V, and P,
nitrate, and TOC.
Run Length Study 5: To further confirm the performance of the dual resin system, Battelle staff
conducted a run length study onsite from June 29 through July 1, 2009. Twelve effluent samples were
collected from each vessel effluent during a service cycle. One influent (IN) and one combined effluent
(TT) sample also were collected. Flow rates and throughput values were recorded at the time of
14
-------
sampling. pH was monitored periodically onsite using a handheld pH probe. Samples were analyzed for
total As, V, and P, nitrate, sulfate, total alkalinity, and TOC.
3.5.2 Regeneration Elution Study. In Study Period II, an elution study was conducted by Battelle
staff members to evaluate the effectiveness of the regeneration process in removing arsenic, nitrate, and,
especially, TOC from the dual IX resin beds and to explore the possibility of optimizing the regeneration
process. Both the elution and follow-on run length studies were originally scheduled for March 2
through 4, 2009. However, all study activities had to be suspended due to an incident involving salt spills
in the treatment plant building during a salt delivery/loading. The studies were rescheduled for June 29,
2009.
The IX resin vessels were set to regenerate for a volume throughput of 600,000 gal in a service cycle.
Regeneration consisted of brine draw, slow rinse, and fast rinse with one vessel being taken offline for
regeneration while the other remained in service. An 8% brine solution (specific gravity of 1.06) was
used for brine draw. Raw water was used for slow and fast rinse. Figure 3-3 shows the experimental
setup, including the use of a flow-through cell, for the elution study. A side stream of spent brine/rinse
water was directed from the regeneration waste discharge line via a piece of 3/s-in Tygon tubing to an 800-
mL plastic beaker, or a flow-through cell, in which a Hanna HI 9635 conductivity/TDS probe (Hanna
Instruments, Inc., Woonsockett, RI) and a VWR pH probe were placed (after calibration) for continuous
measurements of TDS and pH. Because the flow-through cell was secured using a 3-in spring clamp just
inside the rim of a 32-gal plastic container, the solution that overflowed the flow-through cell was
collected into the plastic container. Upon completion of one regeneration step, the flow-through cell was
immediately transferred to another 32-gal plastic container for continuing measurements. This process
continued until all three regeneration steps were complete. A stopwatch was used to measure elapsed
time. Table 3-5 lists the number of samples collected and analyzed during each regeneration step.
Figure 3-3. Regeneration Monitoring Setup
15
-------
Table 3-5. Sampling and Analysis Schedule for Resin Elution Study
Regeneration
Steps
Brine Draw
Slow Rinse
Fast Rinse
Sampling
Time
(min)
0-21
22-66
67-81
Number of
Grab
Samples
Vessel A: 6
Vessel B: 6
Vessel A: 7
Vessel B: 7
Vessel A: 3
Vessel B: 3
Number of
Composite
Samples
Vessel A: 1
Vessel B: 1
Vessel A: 1
Vessel B: 1
Vessel A: 1
Vessel B: 1
Analytes
Total As, V, and
P, NO3, SO4,
TDS, pH,
temperature,
silica, TOC, and
alkalinity
Note that a caustic/brine cleaning was performed one week prior to the elution study. The cleaning was
conducted to remove accumulated TOC, if any, from the dual IX resin beds. The caustic/brine cleaning
followed the procedures presented in Appendix A.
3.6
IX Resin Cleaning
Due to deteriorating resin performance, resin core samples were collected from both IX vessels by
Kinetico in March 2007 and shipped to Purolite for analyses. The resin samples were cleaned in
Purolite's laboratory with either 10% brine or a mixture of 2% caustic and 10% brine and analyzed for
moisture content, volumetric capacity, strong base capacity, and total organic fouling. The results are
discussed in Section 4.4.3.
In light of positive laboratory results with the use of 2% caustic/10% brine in Purolite's laboratory and
positive field results with 5% caustic/10% brine at another EPA arsenic removal demonstration site in
Fruitland, ID (where similar fouling issues were experienced with its Purolite A300E resin and the Vale
operators were invited to observe field cleaning in June 2007), a decision was made to perform resin
cleaning at Vale, OR using similar procedures presented in Appendix A. Field cleaning was performed
by Kinetico in late October 2007. The caustic/brine mixture was prepared by dispensing two 55-gal
drums of 50% NaOH into the brine day tank using a drum pump, followed by filling the day tank with
saturated brine up to 1,050 gal. The specific gravity of the mixture was about 1.042, corresponding to a
6% brine.
The caustic/brine mixture was drawn from the day tank downward through Vessel A or B for about 20
min. By the end of brine draw, a hand valve was closed manually to allow the resin to soak into the
caustic/brine mixture for 30 min. Slow and then fast rinse were then followed for about 45 and 15 min,
respectively. Upon completion of the field cleaning in October 2007, a resin core sample was taken from
Vessel A using a piece of 2-in diameter and 4 ft long polyvinyl chloride (PVC) pipe and sent to Purolite
for analyses. The top, middle, and bottom sections of the core sample were analyzed individually for the
same set of analytes mentioned above.
3.7
Sampling Logistics
All sampling logistics including arsenic speciation kit preparation, sample cooler preparation, and sample
shipping and handling are discussed as follows.
3.7.1 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(III) (Edwards et al., 1998).
Arsenic speciation kits were prepared in batches at Battelle laboratories according to the procedures
detailed in Appendix A of the EPA-endorsed QAPP (Battelle, 2004).
16
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3.7.2 Preparation of Sampling Coolers. For each sampling event, a sample cooler was prepared
with the appropriate number and type of sample bottles, disc filters, and/or speciation kits. All sample
bottles were new and contained appropriate preservatives. Each sample bottle was taped with a pre-
printed, colored-coded, and waterproof label. The sample label consisted of sample identification (ID),
date and time of sample collection, collector's name, site location, sample destination, analysis required,
and preservative. The sample ID consisted of a two-letter code for a specific water facility, sampling
date, a two-letter code for a specific sampling location, and a one-letter code for the specific analysis to be
performed. The sampling locations were color-coded for easy identification. For example, red, yellow,
green, and blue were used for IN, TA, TB, and TT sampling locations. Pre-labeled bottles for each
sampling location were placed in separate zip-lock bags (each corresponding to a specific sampling
location), which were then packed in a sample cooler. When arsenic speciation samples were to be
collected, arsenic speciation kits also were included in the cooler.
When appropriate, the sample cooler was packed with bottles for the three distribution system sampling
locations. In addition, a packet containing all sampling and shipping-related supplies such as latex
gloves, sampling instructions, chain-of-custody forms, prepaid FedEx air bills, and bubble wrap also was
placed in the cooler. Except for the operator's signature, the chain-of-custody forms and prepaid FedEx
air bills had already been completed with the required information. The sample coolers were shipped via
FedEx to the facility approximately 1 week prior to the scheduled sampling date.
3.7.3 Sample Shipping and Handling. After sample collection, samples for offsite analyses were
packed carefully in the original coolers with wet ice and shipped to Battelle. Upon receipt, sample
custodians verified that all samples indicated on the chain-of-custody forms were included and intact.
Sample IDs were checked against the chain-of-custody forms and the samples were logged into the
laboratory sample receipt log. Any discrepancies were addressed with the field sample custodian, and the
Battelle Study Lead was notified.
Samples for metal analyses were stored at Battelle's inductively coupled plasma-mass spectrometry (ICP-
MS) laboratory. Samples for other water quality analyses were packed in coolers and picked up by
couriers from American Analytical Laboratories (AAL) in Columbus, OH, or TCCI Laboratories in New
Lexington, OH, both of which were under contract with Battelle for this demonstration study. The chain-
of-custody forms remained with the samples from the time of preparation through analysis and final
disposal. All samples were archived by the appropriate laboratories for the respective duration of the
required hold time and disposed of properly thereafter.
3.8 Analytical Procedures
The analytical procedures described in detail in Section 4.0 of the EPA-endorsed QAPP (Battelle, 2004)
were followed by Battelle ICP-MS, AAL, and TCCI Laboratories. Laboratory quality assurance/quality
control (QA/QC) of all methods followed the prescribed guidelines. Data quality in terms of precision,
accuracy, method detection limit (MDL), and completeness met the criteria established in the QAPP, i.e.,
relative percent difference (RPD) of 20%, percent recovery of 80% to 120%, and completeness of 80%.
The QA data associated with each analyte will be presented and evaluated in a QA/QC summary report to
be prepared under separate cover.
Field measurements of pH, temperature, DO, and ORP were conducted by the plant operator using a
WTW Multi 340i handheld meter, which was calibrated for pH and DO prior to use following the
procedures provided in the user's manual. The ORP probe also was checked for accuracy by measuring
the ORP of a standard solution and comparing it to the expected value. The plant operator collected a
water sample in a clean, plastic beaker and placed the Multi 340i probe in the beaker until a stable value
was obtained.
17
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4.0 RESULTS AND DISCUSSION
4.1
Facility Description
The City of Vale, located in eastern Oregon, has a population of 1,976. In 2004, the average daily
demand for water was 263,000 gpd, with the peak daily demand of 388,000 gpd occurring in July 2004.
As shown in Table 4-1, the water demand was met by seven groundwater wells (Wells No. 1 through No.
7), operating on a rotating basis to achieve a combined flowrate of 525 gpm. This flowrate represents a
hydraulic utilization of 35% based on the average daily demand and a corresponding run time of 8.3
hr/day. Water from the individual wells was blended and then chlorinated in a centralized treatment
building. In 2004, Wells No. 1 through No. 5 each operated for approximately 3 to 8.5 hr/day, while
Wells No. 6 and No. 7 were used only as backup wells. The City blended raw water from the various
wells in order to minimize nitrate concentrations in water entering the distribution system. In addition to
the seven wells, a 500-gpm groundwater well on Washington Street in downtown also serves as a backup
well.
Table 4-1. Construction Details of Wells No. 1 to No. 7
Well
Diameter (in)
Depth of Well (ft)
Screened Interval (ft bgs)
Static Water Level (ft bgs)
Pump Capacity (gpm)
No. 1
8
33
18-28
8 to 9
200
No. 2
8
33
18-28
8 to 9
100
No. 3
8
33
18-28
8 to 9
180
No. 4
8
33
18-28
8 to 9
100
No. 5
8
28.5
13.5-23.5
NA
NA
No. 6
8
33
18-28
NA
NA
No. 7
8
28.5
13.5-23.5
NA
NA
bgs = below ground surface; NA = not available
Wells No. 1 though No. 7 and the treatment building are located in the airfield of the county airport. The
treatment building was 10 ft tall and built to the Federal Aviation Administration height limit (Figure 4-
1). The Kinetico system was designed to incorporate lower-profile tanks so that the new building could
be constructed near the airfield runway. Due to lack of sewer tie-ins at the airfield, a 1.8-acre evaporation
basin along with a 0.2-acre drying bed both lined with a high-density polyethylene (HOPE) liner was
constructed onsite to hold the regeneration waste.
A MIOX sytem was used to generate sodium hypochlorite onsite. As shown in Figure 4-2, the MIOX
system consisted of a 78-gal salt drum, an electrolytic cell, an 8-gal/hr (gph) metering pump, and a
500-gal storage tank for the sodium hypochlorite solution. The target chlorine dosage was 0.2 mg/L (as
C12) and the target residual level in treated water was 0.025 mg/L (as C12). Once chlorinated, the water
flowed under pressure to a 200,000-gal atmospheric reservoir installed at the airport in 2001 and then was
boosted by two booster pumps before entering the city's distribution system and two older reservoirs
located on the hillside east of town. These reservoirs were built in 1917 and 1977 and had a capacity of
105,000 and 750,000 gal, respectively. Due to the additional pressure loss across the new arsenic and
nitrate treatment system, a booster pump with a capacity of 600 gpm at 130 ft H2O (56 psi) total dynamic
head (TDH) was installed to raise the influent pressure and to supply water during system regeneration.
4.1.1 Source Water Quality. Analytical results from the raw source water sampling event held on
December 2, 2004, are presented in Table 4-2 and compared to the data collected by the vendor and the
city for the site selection of this demonstration study. When onsite, a Battelle staff member measured pH,
temperature, DO, and ORP using a WTW 340i handheld meter. In addition, source water was filtered for
18
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Figure 4-1. Existing Well House in Vale, OR
Figure 4-2. Existing Chlorination System in Vale, OR
19
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Table 4-2. Vale, OR Source Water Data for Combined Wells No. 1 to No. 7
Parameter
Date
pH
Temperature
DO
ORP
Conductivity
Total Alkalinity (as CaCO3)
Hardness (as CaCO3)
Turbidity
TDS
TOC (as C)
Nitrate (as N)
Nitrite (as N)
Ammonia (as N)
Chloride
Fluoride
Sulfate
Silica (as SiO2)
Phosphorus (as P)
As(total)
As (total soluble)
As (paniculate)
As(III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
U (total)
U (soluble)
V (total)
V (soluble)
Na (total)
Ca (total)
Mg (total)
Units
S.U.
°c
mg/L
mV
umhos
mg/L
mg/L
NTU
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
^g/L
^g/L
^g/L
^g/L
Mfi/L
Mfi/L
Mfi/L
^g/L
^g/L
^g/L
^g/L
Mfi/L
Mfi/L
mg/L
mg/L
mg/L
Facility
Data
Various
7.5
NA
NA
NA
NA
NA
NA
NA
NA
NA
8 to 12
NA
NA
NA
NA
83
NA
NA
20
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
164
NA
NA
Kinetico
Data
Not
Specified
7.4
NA
NA
NA
775
284
173
NA
NA
NA
NA
NA
NA
25.3
0.6
84
53.5
0.5
18
NA
NA
NA
NA
<30
NA
<10
NA
NA
NA
NA
NA
114
46.5
14
Battelle
Data
12/02/04
7.5
13.1
4.8
236
NA
158
181
0.1
446
2.1
4.1
0.01
0.05
15.0
0.5
75.0
56.7
0.3
16.7
16.5
0.2
1.9
14.6
<25
<25
1.1
0.8
6.1
6.3
46.8
50.4
110
51.1
13.0
07/23/08
NA
NA
NA
NA
NA
278
120
0.2
458
NA
3.5
NA
NA
NA
NA
63.9
57.7
0.3
20.5
NA
NA
NA
NA
<25
NA
0.3
NA
NA
NA
51.2
NA
NA
30.0
10.8
DO = dissolved oxygen; NA
TDS = total dissolved solids;
= not available; ORP
TOC = total organic
= oxidation-reduction potential;
carbon
soluble arsenic, iron, manganese, uranium, and vanadium, and speciated for As(III) and As(V).
Historical data from individual wells collected by EPA and the city are given in Tables 4-3, 4-4, and 4-5.
Overall, Batte lie's data are comparable to those provided by the other parties with the exception of the
nitrate results that depend on the combination of wells as discussed previously. The analytical results of
the source water sampling and implications for water treatment are briefly discussed below.
20
-------
Table 4-3. Wells No. 1 to No. 7 Water Quality Data from June 2000 to August 2000°
Parameter
pH
Conductivity
Alkalinity
Hardness
TDS
Nitrate (as N)
Nitrite (as N)
Fluoride
Sulfate
As (total)
Fe (total)
Mn (total)
Na (total)
Unit
S.U.
umhos
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
^g/L
^g/L
^g/L
mg/L
Welll
8.2
626
241
142
343
4.7
<0.01
0.6
77
23
820(b)
50
160
Well 2
8.2
492
207
144
390
2.4
<0.01
0.6
51
22
480(b)
70
76
Well 3
8.4
722
275
136
833
6.9
0.01
0.5
91
16
5,760(b)
280
200
Well 4
-
-
-
-
-
-
-
-
-
-
-
-
-
Well 5
-
-
-
-
-
12.7
<0.01
-
-
10
-
-
-
Well 6
-
-
-
-
-
16.7
<0.01
-
-
20
-
-
-
Well 7
-
-
-
-
-
14.4
<0.01
-
-
25
-
-
-
(a) Samples analyzed by Analytical Laboratories, Inc. in Boise, ID.
(b) Iron levels elevated in these wells compared to other historical source water data.
Table 4-4. Wells No. 1 to No. 7 Water Quality Data from EPA (December 2004)
Parameter
As (total)
Fe (total)
Mn (total)
P (total)
unit
Hg/L
^g/L
Hg/L
mg/L
Welll
16.0
43.8
ND
0.27
Well 2
12.0
5.2
ND
0.29
Well 3
10.0
10.5
0.9
0.28
Well 4
14.0
11.8
0.7
0.21
Well 5
13.0
14.5
ND
0.28
Well 6
28.0
23.7
ND
0.36
Well 7
28.0
66.5
1.8
0.40
ND = not detected
Table 4-5. Wells No. 1 to No. 7 Nitrate Concentrations (mg/L [as N]) from Source
(February 2001 to October 2004)(a)
Sampling Date
02/28/01
07/03/01
08/14/01
08/21/01
02/12/02
02/19/02
05/08/02
08/14/02
11/13/02
05/13/03
09/09/03
11/04/03
02/10/04
05/11/04
10/12/04
Welll
5.46
5.78
5.38
5.54
6.24
-
7.12
6.40
4.99
5.54
3.21
2.86
4.10
2.70
2.37
Well 2
5.06
2.14
4.15
4.84
5.39
-
5.60
5.36
4.09
4.24
2.14
2.81
3.03
1.88
1.75
Well 3
7.10
6.03
6.08
6.02
6.26
-
10.70
10.70
7.83
8.47
3.00
3.12
5.34
3.12
3.42
Well 4
11.50
11.70
12.00
-
13.70
-
14.30
13.50
8.86
10.50
9.57
6.82
5.17
5.24
5.82
Well 5
14.70
13.70
13.60
-
-
13.60
13.80
12.10
8.36
9.85
7.48
6.63
7.43
4.80
4.81
Well 6
12.50
12.20
11.70
11.00
-
11.30
14.50
12.20
9.21
14.50
10.50
10.30
12.70
12.60
7.38
Well 7
13.30
10.60
5.52
5.42
-
16.90
18.00
9.14
10.70
18.90
10.80
10.50
13.70
14.30
8.14
(a) Samples analyzed by Magic Valley Labs in Twin Falls, ID.
21
-------
Arsenic. Total arsenic concentrations in the blended source water ranged from 16.7 to 20 |o,g/L
(Table 4-2). Total arsenic concentrations in raw water from the individual wells ranged from 10 to 28
|o,g/L (Tables 4-3 and 4-4). Based on the source water sampling results obtained by Battelle, out of
16.7 |o,g/L of total arsenic, 14.6 |o,g/L existed as soluble As(V). Therefore, As(V) was the predominating
arsenic species. At raw water pH values of 7.4 to 7.5, As(V) is present primarily as HAsO42", which can
be removed electrostatically by anion exchange resin.
Nitrate. The City blended source water from various wells to minimize nitrate concentrations in the
blended water to below the 10 mg/L MCL. As shown in Table 4-5 and Figure 4-3, nitrate concentrations
in Wells No. 1 and No. 2 were less than 7.1 mg/L (as N) and exhibited a decreasing trend starting from
2002. Nitrate concentrations in Well No. 3 peaked at 10.7 mg/L (as N) and then decreased to just over
3.0 mg/L (as N) by 2004. Wells No. 4 to No. 7 had historical nitrate levels mostly over 10 mg/L and as
high as 18.9 mg/L (as N). Concentrations in wells No. 4 and No. 5 also showed a significant decreasing
trend with concentrations measured at 4.8 to 5.8 mg/L (as N) by October 2004. Concentrations in Wells
No. 6 and No. 7 remained elevated from 2000 through 2004; the measurements made in October 2004
were less than 10 mg/L (as N) for both wells. Combined source water values were 8 to 12 mg/L (as N)
from the facility and 4.1 mg/L (as N) from Battelle (Table 4-2). Similar to arsenic, the water treatment
process relied upon the exchange of nitrate in source water with chloride on the resin.
Figure 4-3. Historic Nitrate Data from Wells No. 1 Through No. 7
Sulfate. Sulfate concentrations ranged from 51 to 91 mg/L in Wells No. 1 through No. 3 (Table 4-3) and
from 75 to 84 mg/L in combined wells (Table 4-2). Because sulfate is preferred over arsenate and nitrate
and because of its higher concentrations, sulfate competes strongly with arsenic and nitrate for exchange
sites.
22
-------
Iron, Manganese, Silica, and TOC. Iron and manganese concentrations in source water were less than
30 and 10 |og/L, respectively, and, therefore, should not cause iron or manganese fouling to the IX resin.
Silica concentrations averaged 56 mg/L (as SiO2); polymerization of silica on the resin surface could
adversely impact the IX process. TOC measured at 2.1 mg/L; it is well known that AIX resins are
susceptible to fouling by dissolved organic matter (DOM) (Boodoo, 2004).
Other Water Quality Parameters. Total dissolved solids (TDS) measured at 446 mg/L, a level which
may impact the performance of the IX resin. Total phosphorus concentrations in the individual wells
ranged from 0.2 to 0.4 mg/L (as P) (Table 4-4), which could affect the exchange of arsenic and nitrate
anions. Concentrations of uranium and vanadium were measured at 6.1 and 46.8 |o,g/L, respectively,
which could compete with arsenic and nitrate for exchange sites.
Total alkalinity in source water ranged from 158 to 284 mg/L (as CaCO3); bicarbonate anions also
compete for exchange sites, especially immediately after resin regeneration. Removal of bicarbonate
causes the treated water pH to decrease, making the treated water corrosive as it enters the distribution
system. The pH value of raw water was 7.4 or 7.5. Unlike adsorptive media, IX resins are not sensitive
to water pH.
4.1.2 Distribution System Water Quality. The distribution system sampling for the EPA
demonstration study included three residences (i.e., 629 15th Street North, 780 15th Street North, and 252
B Street West) supplied by the combination of Wells No. 1 through No. 7. These locations are a good
representation of the distribution system and the first two also are part of the City's sampling network for
the LCR. The distribution system consisted of PVC mains with HOPE or copper service lines to
individual homes.
Water in the distribution system was sampled once a year for haloacetic acids (HAA5) and
trihalomethanes (TTHMs) under EPA's Disinfection Byproducts Rule. In 2004, the HAA5 level was
0.009 mg/L, compared to the MCL of 0.06 mg/L. The TTHMs level was 0.03 mg/L, compared to the
MCL of 0.08 mg/L. The treated water also was sampled once every three years at 10 residences under
EPA's LCR. During the latest sampling round in 2002, the lead concentration was 0.004 mg/L, compared
to the action level of 0.015 mg/L, and the copper concentration was 0.865 mg/L, compared to the action
level of 1.3 mg/L.
4.2 Treatment Process Description
4.2.1 Ion Exchange Process. Ion exchange is a proven technology for removing arsenic and
nitrate from drinking water supplies (Clifford, 1999; Ghurye et al., 1999; and Wang et al., 2002). It is a
physical/chemical process that removes dissolved arsenate and nitrate ions from water by exchanging
them with chloride ions on an AIX resin. Once its capacity is exhausted, the resin is regenerated with a
brine solution containing high concentrations of chloride to displace the arsenate and nitrate on the resin.
Strong-base anionic (SBA) IX resins are commonly used for arsenate and nitrate removal. Resin capacity
typically is not sensitive to water pH (in the range of 6.5 to 9.0). An SBA IX resin tends to have a higher
affinity for more highly charged anions, resulting in a general hierarchy of selectivity as follows:
SO 2 >HAsO 2 >NO >NO >C1 >H AsO , HCO » Si(OH) ; H AsO
4 4 3 2 243 v/434
Because sulfate is preferred over arsenate and nitrate and because its concentration is at least three orders
of magnitude higher than those of arsenic, it is a major competing anion to arsenate and nitrate removal
by the IX process. High TDS levels also can significantly reduce arsenic and nitrate removal efficiencies.
In general, the IX process is not economically attractive if source water contains >500 mg/L of TDS and
23
-------
>150 mg/L of sulfate. Also, participates in feed water can potentially foul the SBA IX resin, and,
therefore, must be removed prior to IX process.
Most nitrate removal plants use either a nitrate selective resin or an SBA Type II or Type I resin. Nitrate
selective resins typically have triethylamine functional groups, which show higher selectivity for
hydrophobic anions (such as nitrate and perchlorate) over hydrophilic divalent anions (such as sulfate and
arsenate). Therefore, sulfate and arsenate will break before nitrate. Since arsenate is less selective than
sulfate, it will break before sulfate. Operating to arsenic breakthrough using a nitrate selective resin has
two major issues: (1) the operating cost is higher because of a shorter run length to arsenic breakthrough
than to nitrate breakthrough and (2) it is more expensive to monitor arsenic breakthrough than nitrate
breakthrough in real time. Therefore, a nitrate selective resin would not be a good choice for removing
both arsenic and nitrate (Boodoo, 2004). When sulfate is relatively low, Type II and Type I SBA resins
are preferred due to their lower prices. For drinking water applications, Type II is preferred over Type I
because of a fishy odor associated with Type I resins.
Two types of SBA IX resins were evaluated during the demonstration study at Vale. Purolite Arsenex II
was used in Study Period I. However, due to organic fouling, the resin had to be replaced with PFA300E
top-dressed with A850END, in Study Period II. These resins are NSF International (NSF) Standard 61
approved for use in drinking water treatment. Their physical and chemical properties are presented in
Table 4-6 and highlighted as follows:
Arsenex II was claimed by the vendor as a proprietary, arsenic selective IX resin, specifically designed
for arsenic removal in the presence of high sulfate. However, it was not clear whether the term "arsenic
selective" actually meant higher affinity for arsenic than sulfate (like the term "nitrate selective" for
higher affinity for nitrate than sulfate). No literature was available for this resin, which was posted on
Purolite's Web site.
PFA300 is a gel-Type II SBA resin, which has a high operating capacity at a low regeneration level
because of its uniform particle size distribution (i.e., uniformity coefficient is 1.2). It is less susceptible to
organic fouling than standard gel-type SBA resins. Except for its narrower size distribution, PFA300 is
very similar to A300E, which was evaluated for arsenic and nitrate removal at another EPA
demonstration site in Fruitland, ID (Wang et al., 2010). The physical and chemical properties of A300E
also are listed in Table 4-6 for reference.
A850END is specially produced from A850 with a narrower size grading of 300- to 600-|o,m diameter.
A850 is a gel-Type I SBA resin with an acrylic matrix. This gel or highly macroporous acrylic-based
SBA Type I resin can remove most naturally occurring DOM, such as humic and fulvic acids, to at least
50 to 80%. A850END can be regenerated with lower levels of sodium hydroxide than those required for
a polystyrene-based Type I resin.
Resin run lengths for arsenic and nitrate removal at Vale were estimated by Purolite using its
computerized simulator. Figure 4-4 shows the simulation for ArseneX II based on a modeling run with
20 |og/L of arsenic, 53 mg/L of nitrate (as N), and 83 mg/L of sulfate in water. The results indicate that
bicarbonate breaks first, followed by nitrate, arsenic, and sulfate. Nonetheless, breakthrough of arsenic at
10 |o,g/L would occur first at 680 BV followed by nitrate breakthrough at 9 mg/L (as N) at 740 BV (1 BV
= 220 ft3). These run lengths, however, were significantly over-predicted than the actual run lengths
(generally less than 431 BV or 600,000 gal) as discussed in Section 4.4.3.
24
-------
Table 4-6. Physical and Chemical Properties of IX Resins
Parameters
Polymer Structure
Functional Group
Physical Form/ Appearance
Whole Bead Count
Resin Type
Ionic Form, as Shipped
Shipping Weight (lbs/ft3 or g/L)
Specific Gravity (g/mL)
Mesh Size (U.S. Standard) (Wet)
Bead Size Range (mm)
Uniformity Coefficient
Moisture Retention (%)
Reversible Swelling
Total Exchange Capacity, Cl"
Form (eq/L) (wet, volumetric)
pH Range
Maximum Temperature Limit
(°C/°F)
Study Period I
Arsenex II
Gel polystyrene
crosslinked with
DVB
Dimethyl ethanol
amine
Opaque spherical
beads
95% minimum
SBA Type II
cr
43
-
16x50
0.3-1.2
-
42-54
cr to so427NO3-
Negligible
1.0
0-14
100/212
Study Period II
A850ta)
Gel polyacrylic
crosslinked with
DVB
Trimethylamine
Clear spherical
beads
-
SBA Type I
cr
42.5-45.6 or
680-730
1.09
-
0.60-0.85
1.70
57-62
cr to OH-
15% (max)
1.25
1-10
85/185
PFA300
Gel polystyrene
crosslinked with
DVB
Dimethyl ethanol
amine
Amber spherical
beads
95% minimum
SBA Type II
cr
43 or 690
1.10
25 x40
+0.710mm
-------
IX-SIM -Arsenex II Removal of As
and N at Vale OR (Kinetico)
ATt ~"*
A nn -
*HJU
O
O 350 -
O
T ^nn -
O9^n -
onn -
o
W 150 -
n 1 nn -
a
t;n -
0 -
u
/ l'\
/
i i \
1 ' \
s-J
^Sj\_
s f — — — — — j««™«
-60
-50 E
Q.
-40*
O
-30 <«
-20-g.
Q.
-10
'SSlalsSsaslgli
SO4
HCO3
--•As
BvS N peaks at 9 ppm as N at 740 BVs
As breaks at 1 0 ppb at 680 Bvs
Figure 4-4. Simulation of Arsenex II Resin Run Length
90
80
70
a 60
a
o DU
w 40
o
t 30
W 20
I 10
Q.
0 ^
Vale OR, Simulating As & NO3 removal with PFA300E -virgin
resin -capacity for regenerate resin will be lower
Cycle time dependent on NO3 break -expect 523 Bvs to NO3-N break at
10ppm - regenerated w/10 Ibs NaCI/ft3 resin -Coflow
or 485 Bvs Counter-flow
Regenerate at 523 Bvs
with 10lbs/ft3 NaCI
to 10ppm NO3-N break
OLOoinomoino
cococn^roin-^tcirM
CMCoco^mintocDr--
SO4
N03-N
-AsV
in o in o in
r-~ co co rr o>
I"- CO CO OJ O5
IX-SIM _Purolite
-I
BVs
Figure 4-5. Simulation of A850END/PFA300E Resin Run Length (June 2008)
26
-------
4.2.2 Treatment Process. The Vale IX system utilized the packed-bed anionic IX technology to
remove arsenic and nitrate from source water. Figure 4-6 is a process schematic of the treatment system.
The process equipment included two banks of five skid-mounted bag filters, two skid-mounted resin
vessels, two salt saturators, two brine day tanks, three pre-wired brine transfer/injection pumps, one air
compressor, one post-chlorination system, as well as associated valves, sample ports, pressure gauges,
and flow elements/controls. The IX system was fully automated and controlled by a central control panel
consisting of a programmable logic control (PLC), a touch screen operator interface panel (OIP), and a
data communication modem. The OIP allowed the operator to monitor system flowrate and volume
throughput since last regeneration, change system setpoints, and check the status of alarms. The modem
allowed the vendor to remotely dial in for monitoring and troubleshooting. All pneumatic valves were
constructed of PVC and all plumbing was Schedule 80 PVC solvent bonded. Table 4-7 summarizes the
design specifications of the IX system.
Booster
Pumps (2)
Sediment
Filters (2)
Regeneration Waste
to Pond or Reused
Brine Day Tank
Raw Water from Well
/-K/-H
Brine Drawn by
Eductor on Ion
Exchange Skid
11 -Ton
Salt
Saturator
11 -Ton
Salt
Saturator
Brine
Day
Tank
Treated Water to
Storage/Distribution
Jl
Brine Transfer
Pump
Reused
Brine
Day Tank
Reused Brine to 2" Inlet
on Ion Exchange Skid
I
Existing I
NOT TO SCALE
Reused
Brine Pump
Baiteiie
VALE PROCESS01 CDR
Figure 4-6. Schematic of Kinetico's IX-263 As/N Removal System for Vale, OR
27
-------
Table 4-7. Design Specifications of IX System
System Component/Parameter
Study Period I
Study Period II
Pre-treatment
Bag Filter Assembly
Two banks of five 20-|am
bag filters in parallel
5-|am filter bags
IX Vessels and Media Beds
Vessel Size (in)
Cross-Sectional Area (ft2/vessel)
Number of Resin Vessels
Configuration
Resin Type(s)
IX Resin Quantity (ft3/vessel)(a)
Flint Gravel Support Media (ft3/vessel)
63 D x 86 H
21.6
2
Parallel
Purolite Arsenex II
110
4
Same
Same
Same
Same
Purolite A850END/PFA300E
15 and 95 ft3, respectively
Same
Service
Design Flowrate (gpm)
Hydraulic Loading Rate (gpm/ft2)
Specific Flowrate (gpm/ft3)
EBCT (min)
Estimated Working Capacity (BV)
Volume Throughput (gal)
540
12.5
2.45
3.0
550-680
905,300-1,119,280
Same
Same
Same
Same
523-604
860,650-993,940
Regeneration
Regeneration Mode
Regeneration Level (Ib salt/ft3 resin)
Brine Concentration (%)
Reused Brine Draw Duration, Flowrate,
and Volume03'
Fresh Brine Draw Duration, Flowrate,
and Volume*'
Slow Rinse Duration, Flowrate, and
Volume(b)
Fast Rinse Duration, Flowrate, and
Volume(b)
Wastewater Volume per Regeneration
Event (gal)(b)
Salt Consumption per Regeneration
Event (Ib)
Co-current downflow
12
10
15 min, 50 gpm, 750 gal
17 min, 50 gpm, 850 gal
40 min, 50 gpm, 2,000 gal
20 min, 220 gpm, 4,400
gal
7,250 (per vessel),
14,500 (total)
760 (per vessel),
1,520 (total)
Same
10
8
Discontinued
21 min, 64 gpm, 1,344 gal
45 min, 44 gpm, 1,980 gal
15 min, 260 gpm, 3,900 gal
7,224 (per vessel),
14,448 (total)
760 (per vessel),
1,520 (total)
Brine System
Brine Day Tank Size (in)
Brine Day Tank Material
Fresh Brine Transfer Pump
Fresh Brine Venturi Eductor
Reused Brine Injection Pump
Salt Saturator Size (ton)
Salt Saturator Material
61 D x97H(two)
HOPE
1.5 hp, max. 90 gpm@
25 ft H2O TDH
2 in (draw factor 0.75 to
1.0)
5 hp, max. 200 gpm @ 45
ft H2O TDH
11 (two)
Fiberglass
Use one tank only
Same
Same
Discontinued
Discontinued
Same
Same
Post-treatment
Target Chlorine Residual (mg/L [as C12])
0.025
Same
(a) Actual amounts were 93 ft for Arsenex II and 16.7 and 81.7 ft for
respectively.
(b) Source: Kinetico "Brine Waste Minimization Memo for Vale, OR"
A850END and of PFA300E,
dated April 4, 2006.
28
-------
Major process steps and system components are presented as follows:
• Intake. Raw water from Wells No. 1 through 7 was pumped to the treatment building and
then combined at a common header. To overcome the anticipated headless from the
treatment system, the incoming water was boosted by a 25-horsepower (hp) booster pump to
meet the minimum influent pressure requirement of the IX system. Two booster pumps (one
on standby), each rated for 600 gpm at 130 ft H2O head (or 56 psi), and a three-phase
Danfoss VLT8000 series variable frequency drive (VFD) were installed at the common
header. System inlet piping and a booster pump is shown in Figure 4-7.
Figure 4-7. System Inlet Piping and Booster Pump
• Sediment Filtration. Prior to entering the FX resin vessels, raw water was filtered through
two parallel, skid-mounted bag filter assemblies to remove sediment. Each assembly
consisted of five parallel FSIXI00 polypropylene housing units, each lined with a 20-um (in
Study Period I) or 5-um filter bag (in Study Period II). Each filter was rated at 65 gpm,
giving a total capacity of 325 gpm per assembly or 650 gpm for both. Filter bags in the two
assemblies were cleaned or replaced when headlosses across each assembly had reached 10-
to 15-lb/in2 (psi) levels. Figure 4-8 presents a photograph of the bag filter assemblies. This
filtration step was used to prevent the resin beds from being clogged and/or fouled by
particulates.
29
-------
Figure 4-8. Photograph of Two Banks of Cartridge Filters
• Ion Exchange. After passing through the bag filters, water flowed downward through two
63 in x 86 in pressure vessels configured in parallel (Figures 4-9 and 4-10). Mounted on a
polyurethane-coated, welded steel frame, the pressure vessels were of fiber reinforced plastic
(FRP) construction and rated for 150 psi working pressure. Each vessel had a 6-in top and
bottom flanges, and was equipped with a difftiser-style upper distributor and a hub and
laterals-style underdrain. All pneumatic valves were PVC, and all plumbing was Schedule 80
PVC solvent bond. By design, each vessel was to be loaded with 4 ft3 of flint gravel support
on the bottom, 110 ft3 of resin in the middle (about 61 in deep), and 4 ft3 of polyethylene
filler beads on the top. The filler material was intended to prevent resin from being washed
away in an upflow, counter-current regeneration. Filler beads were not added because they
were not needed for co-current regeneration.
The IX system was designed for 540 gpm, yielding a hydraulic loading rate of 12.5 gpm/ft2
and an empty bed contact time (EBCT) of 3 min. Each vessel was equipped with a 270-gpm
flow restrictor on the effluent piping to help balance the flow between the two vessels and
prevent overrun during regeneration. An insertion-type paddle wheel flow element was
installed on the combined effluent line to register flowrate and throughput of the product
water since last regeneration. When a pre-determined throughput setpoint was reached,
Vessel A was automatically taken out of service for regeneration, whereas Vessel B remained
online for treatment. Once Vessel A regeneration was complete, the totalizer was
automatically reset to zero and began to register the water treated by Vessel A. Meanwhile,
Vessel B was taken out of service for regeneration. After Vessel B regeneration was
complete, the totalizer registered the amount of water treated by both vessels.
30
-------
Figure 4-9. Photographs of Arsenic/Nitrate Removal IX System at Vale, OR
Figure 4-10. Skid-Mounted Piping/Valving Rack
31
-------
For the study purposes, two additional insertion-type paddle wheel flow elements were
installed on the individual vessel outlet to accurately trackthe throughput from each vessel.
These flow elements were not wired to the PLC and did not reset to zero after each
regeneration.
• Resin Regeneration. The purpose of resin regeneration is to restore exhausted resin back to
its chloride form for service. The regeneration process can either be co-current (i.e., in the
same direction of the process flow) or counter-current (i.e., in the opposite direction of the
process flow). A counter-current regeneration maximizes the chemical's ability to regenerate
the resin and minimize the volume of waste. The vendor decided to use downflow, co-
current regeneration, which was thought to be superior to upflow, counter-current
regeneration for arsenic and nitrate because the counter-current regeneration would force the
contaminants concentrated at the bottom of the resin bed back through the entire bed, thus
leaving more contaminants in the bed (Clifford et al., 1987, 2003). In addition, co-current
regeneration was easier to implement. One drawback of co-current regeneration is
arsenic/nitrate leakage, which may occur in the early stage of a service cycle, as observed at
Fruitland (Wang et al., 2010).
The Vale system was retrofitted in July 2006 by Kinetico to be capable of counter-current
regeneration, if desired. However, due to a series of mechanical problems that occurred to
the Fruitland system after similar retrofitting (from co-current to counter-current to curb
arsenic/nitrate leakage), the Vale system remained co-current throughout the entire study
period.
Regeneration could be initiated either automatically based on a throughput setpoint or
manually by pressing a push-button on the PLC. Once regeneration was initiated, it followed
a sequence of four pre-set steps, including spent brine draw, fresh brine draw, slow rinse, and
fast rinse. There was no backwash step in the original design and it could not be added later
due to lack of freeboard in the vessels. During the demonstration study, the regeneration
scheme was adjusted several times to optimize the regeneration efficiency and reduce waste
production (Section 4.4.2.1). In doing so, the duration of each regeneration step was reset on
the PLC and the brine concentration was adjusted by changing the brine draw rate using a
hand valve located upstream of an eductor or a brine injection pump. The brine concentration
was confirmed by measuring the specific gravity of the adjusted solution using a hydrometer.
Unlike most of the IX systems, including the Fruitland system where treated water is used for
preparing the brine solution and rinsing the beds, raw water was used at Vale due to
insufficient head in the 200,000-gal atmospheric reservoir at the airfield. Figure 4-11 shows
photographs of major regeneration system components. Table 4-7 presents relevant
regeneration settings. The four regeneration steps are discussed below.
Step 1. Spent Brine Draw - The treatment system was originally designed with a brine
reclaim feature to minimize salt usage and brine waste. During the first half of brine draw, a
spent brine solution with a concentration of 9 to 10% was pumped from a 1,050-gal day tank
at approximately 50 gpm for 15 min using a 5-hp centrifugal pump. The entire volume of
waste produced during spent brine draw was discharged to an evaporation pond. The volume
of spent brine was tracked by a 2-in mechanical totalizer installed on a brine feed line. The
use of spent brine could reduce the brine waste volume by 137 gal/vessel and the
corresponding salt consumption by 885 to 758 Ib/vessel, or 14%. The brine reclaim,
however, was discontinued on December 10, 2007, due to concerns that DOM might
accumulate in spent brine and would increase the resin fouling (Section 4.4.3).
32
-------
Figure 4-11. Photographs of IX Regeneration System at Vale, OR
Step 2. Fresh Brine Draw - Fresh brine was used for the second half of brine draw.
Saturated brine was drawn from a second 1,050-gal day tank and mixed with make-up water
(i.e., raw water) via a Venturi educator (later changed to a chemical injection pump) before
entering a resin vessel. The day tank was equipped with a high- and a low-level sensor
interlocked with a 1.5-hp brine transfer pump to fill the tank with saturated brine (about 23 to
26%) from two salt saturators. Each salt saturator was 8-ft in diameter, 10-ft tall with an 11-
ton salt storage capacity. This was modified from the initial design of one 22-ton saturator
due to the height restriction on the building near the airport runway. The salt saturators were
sized to hold 30 days of salt supply for daily regeneration and were re-filled by a salt delivery
truck (Figure 4-12) on a monthly or as-needed basis. A 2-in mechanical totalizer was
installed on the brine line to track the volume of saturated brine used.
By design, 336 gal of saturated brine would be drawn from the fresh brine day tank and
mixed with approximately 530 gal of make-up water to produce 866 gal of a 10% brine
solution. As the fresh brine was drawn into a resin vessel, approximately 750 gal of spent
brine was first directed to the spent brine day tank until reaching a high-level setpoint. The
remainder of spent brine (-100 gal) was discharged directly to the evaporation pond.
Step 3. Slow Rinse - At the end of brine draw, a valve on the saturated brine feed line was
shut, and only the make-up water (i.e., raw water) was introduced to the resin vessel at 50
gpm for 40 min to rinse off the brine from the resin bed. This step produced approximately
2,000 gal of wastewater to be discharged directly to the evaporation pond. The resin
manufacturer recommended 2.5 BV (1 BV = 110 ft3 = 823 gal), or 2,057 gal, of water for
slow rinse.
33
-------
Figure 4-12. Salt Delivery to Fill Salt Saturators
Step 4. Fast Rinse - Fast rinse was performed at the service flowrate of approximately 220
gpm to further remove/flush out residual brine from resin beads and blind spots in the IX
vessels. This step was set to last for 20 min and would produce 4,400 gal of wastewater to be
discharged directly to the evaporation pond. The resin manufacturer recommended 5 BV (or
4,114 gal) for fast rinse.
Post Chlorination. The target chlorine dosage was 0.2 mg/L (as C12) and the target residual
level for disinfection of treated water was 0.025 mg/L (as C12). Once chlorinated, the water
flowed to the 200,000-gal atmospheric reservoir near the airport, from which it was sent by
two booster pumps to the city's distribution system and two older reservoirs located on the
other side of the town.
Residual Disposal. Due to lack of connection to the City sewer, an evaporation pond was
constructed adjacent to the treatment building for disposal of spent brine and rinse water from
the regeneration process (Figure 4-13). The evaporation pond consisted of a 368 ft (length) x
214 ft (width) x 13 ft (depth) evaporation basin and a 200 ft (length) x 55 ft (width) x 16 ft
(depth) drying bed. The evaporation basin had a surface area of 1.8 acre and a storage
capacity of 7,657,844 gal (or 23.5 acre-ft).
As part of the pond design, ferric chloride (FeCl3) was added to spent brine prior to being
discharged to the pond (see Figure 4-14). Specifically, 0.25 gal of a commercial grade FeCl3
solution (40% with specific gravity of 1.4) was fed to the waste brine stream at a rate of 1.0
gph for 15 min. Based on the design brine draw rate of 50 gpm, the iron dosage would be
approximately 63 mg/L (as Fe). Because FeCl3 was fed in a batch mode into a total waste
volume of 7,250 gal (per vessel), the average iron dosage was only 6.65
34
-------
Figure 4-13. Wastewater Evaporation Pond
Figure 4-14. Ferric Chloride Addition to Treat Spent Brine
35
-------
mg/L. The wastewater traveled via a 4-in underground PVC pipe to a wet well, then was
pumped to the evaporation basin via a 6-in PVC pipe. By design, the FeCl3-treated water was
expected to precipitate and settle to the bottom of the evaporation basin. Over a period of
time, the sludge would accumulate in a 1-ft wide, 16-ft deep depressed area (with an 8:1
sloped bottom) at one end of the basin, and then be pumped to the adjacent drying basin
periodically. However, due to the presence of high TDS in the wastewater, the FeCl3
treatment was not effective at removing arsenic from the brine waste (see Section 4.5.6).
4.3 System Installation
4.3.1 Permitting. Engineering plans for the system permit application were prepared by Holladay
Engineering (Payette, ID), a subcontractor to Kinetico (the firm also provided engineering services to the
City). The plans included general arrangement diagrams, specifications of the IX system, and drawings
detailing connections between the treatment system and the building. After incorporating comments from
the vendor and Battelle, the City submitted the plans on July 22, 2005, to the Oregon DHS DWP for
review. On August 11, 2005, the permit packages were approved by Oregon DHS DWP.
4.3.2 Construction of Treatment Building and Evaporation Pond. The City issued an
Advertisement for Bid on August 10, 2005, for the earthwork necessary to construct and complete a 1.8-
acre evaporation basin and a 0.2-acre drying bed, a HOPE liner, fencing, a wet well lift station, a new
building, a walkway, a ferric chloride shed, and chemical equipment, etc. Only one bidder submitted a
bid for a total amount of $498,844.00 on September 1, 2005, which was significantly higher than the
city's budget of $325,000.00. The high bid might have been affected by rebuilding efforts following the
aftermath of hurricane Katrina in the Gulf of Mexico region, which created a high demand for materials,
equipment, and contractors in that area. Therefore, the city council voted to re-advertise for bid on
October 13 through November 13, 2005, with a new construction schedule and a final completion date of
May 16, 2006. Four bids ranging from $388,960.00 to $436,070.00 were received and opened on
November 14, 2005, with all exceeding the city's budget again. The city negotiated a contract with the
low bidder - Holcomb Construction, and signed the Notice of Award and Notice to Proceed in early
December 2005.
The building construction began on December 5, 2005, and was completed ahead of schedule on February
28, 2006. The 20 ft-tall addition covered 1,025 ft2 of floor space (41-ft long and 25-ft wide) and had a
wood frame, steel siding and roofing, and a 12-ft wide roll-up door. Figure 4-15 shows photographs of
the new structure, adjacent to the existing pump house.
Construction of the evaporation pond didn't begin until the ground dried out for earthwork, was
interrupted by the weather in April, and was completed in late May 2005, just before system startup. The
pond consisted of an evaporation basin and a drying bed. A 40-mil textured HOPE liner was installed in
the evaporation basin and drying bed to prevent any leakage to groundwater. An 8-ft tall exterior fence
consisting of steel posts, wire mesh, and an access gate was installed surrounding the pond. Figure 4-16
is a photograph of the evaporation pond under construction; photographs of the completed pond are
presented in Figure 4-13.
Based on the cost breakdowns from the construction contractor, the cost for mobilization/demobilization
and clearing/grubbing the entire construction site was $36,140.00. The cost for earthwork, HOPE liner,
and fencing was $81,809.00. The cost for the new building, walkway, and ferric chloride shed was
$111,018.00. The cost for the chemical equipment for ferric chloride addition was $11,353.00, including
a hand truck for hauling chemical barrels, a wall-mounted chemical metering pump, and a wall-mounted
first aid kit, and a combination shower/eyewash station.
36
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Figure 4-15. Vale Treatment Plant Building Construction
05.25,2008 08:22
Figure 4-16. Installation of HOPE Liner in Evaporation Pond
37
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4.3.3 System Installation, Shakedown, and Startup. The IX system was delivered to Vale, OR
on two flatbeds on May 12, 2006. Upon arrival, system components were offloaded (Figure 4-17) and
installation activities began immediately thereafter. A Kinetico technician was onsite from May 22
through May 26, 2006, to perform resin loading and system startup and then returned on June 1, 2006, to
complete system startup and shakedown. The technician provided operator's training on June 6, 2006.
The system was placed online in a fully automatic mode on June 21, 2006, after relevant control issues
had been addressed by the city to synchronize the operation of the wells and booster pumps with the PLC
of the treatment system. However, automatic regeneration of the system was found to cut short and did
not complete the full cycle as designed. This problem was resolved by programming changes made by
Kinetico on June 30, 2006.
Figure 4-17. Vale Treatment System Delivering and Offloading
38
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During the first week of July 2006, when the system was first brought online, an unusually low system
flowrate (i.e., 300 gpm at 60 psi inlet pressure) and an unusually high pressure drop across the IX beds
(i.e., 35 to 40 psi) were experienced, which prompted a recommendation by the vendor to backwash the
IX beds. Because the system was not designed/equipped for resin backwashing, the vendor proposed to
retrofit the piping in the field to allow for backwashing as well as counter-current regeneration, if desired.
Revised piping drawings were provided to Battelle on July 17, 2006.
A Kinetico technician returned to the site on July 20, 2006, to complete the retrofit and system
shakedown. Four, 4-in PVC butterfly valves were added to the system piping to re-direct the flow for IX
vessel backwashing, which, however, could be performed only manually by physically operating the
valves. After backwashing, the system flowrate and headless across each IX vessel became normal at 577
gpm and 13 psi, respectively. Although the vender attributed the low system flowrate and excessive
pressure drop to sediment buildup in bag filters, it was apparent that the IX resin beds had to be
backwashed to remove fines upon loading. Factory settings in the PLC also were adjusted in the field as
needed. One of the changes made was to shorten the spent brine draw time from 15 to 10 min to avoid
draining of the spent brine tank. The system was placed online in a co-current mode on July 23, 2006.
Battelle performed system inspections and operator training from September 19 through 21, 2006.
Training included calibration and use of the water quality meter, collection and recording of operational
data, proper sample collection techniques, arsenic speciation, and sample handling and shipping
procedures. The first set of samples was collected from the IX system on September 20, 2006, signifying
the official start of the performance evaluation study at Vale, OR. Table 4-8 summarizes punch list items
identified during the system start-up and inspection as well as corrective actions taken.
Table 4-8. System Punch List during Startup
1
2
3
4
5
6
Punch List/Operational Issues
Fresh brine draw rate about twice
the design value
Flow totalizers after Vessels A
and B appeared to be out of
calibration; meter for Vessel B
appeared to be off by 36%,
yielding higher readings than
those for Vessel A over same
time period
Flow element displayed only
throughput since last regeneration
Pressure gauge PI-5 had a wide
span, causing inaccurate readings
Excessive salt dust generated
from salt delivery
Reused brine pump failed
Corrective Action(s) Taken
Actions taken from October 2006
through March 2007 to reduce salt
usage to target level of 12 lb/ft3
Kinetico verified meters; flow through
Vessel B continued to be higher than
that through Vessel A in Study Period
I
Cumulative volume of water
processed added to PLC display
Old gauge replaced; new gauge
worked well
Kinetico installed a water line to
alleviate salt dust
Pump functional after being taken
apart and cleaned
Resolution
Date
03/05/07
10/19/06
10/25/06
10/20/06
10/20/06
10/19/06
39
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4.4
System Operation
Table 4-9 presents key demonstration study activities and events taking place during the three study
periods. Study Period I, extending from September 19, 2006, through January 14, 2008, focused on
evaluation of Purolite Arsenex II resin that was originally selected for the demonstration. At the end of
this period, the system was taken offline for 4.5 months for well rehabilitation. Due to deteriorating
performance of Arsenex II resin and unsuccessful attempts to clean the resin, the focus of the Interim
Period was to identify an alternative approach to address the resin fouling issue. Study Period II,
extending from February 10, 2009, through March 22, 2010, focused on evaluation of dual resins -
Purolite® A850END/PFA300E. Table 4-9 highlights key demonstration activities under each study
period, which will be discussed in this section. A more complete site chronology is presented in
Appendix B for reference.
Table 4-9. Key Demonstration Study Activities/Events
Demonstration Study Activities/Events
Study Period I. Evaluating Arsenex II Resin
• Run Length Study 1 performed
• Site visit by Kinetico to address punch-list items
• Meeting with Kinetico and EPA at Battelle to discuss performance issues
• Site visit by Kinetico to install brine injection pump in place of educator
and to collect resin samples
• Regular weekly sampling discontinued
• Limited weekly sampling at TT location
• Site visit by Kinetico to conduct resin cleaning; reused brine draw
discontinued; resin samples collected
• Run Length Study 2 performed
Interim Period. Identifying Alternative Approaches
• IX system shutdown due to well rehabilitation
• System operation resumed
• Meeting with Vale, EPA, and consultants at Battelle to discuss available
options
• Site visit by Battelle to inspect resin and vessels
• Special study on dual resin system at McCook, NE
• ArsenicGuard installed to provide online arsenic monitoring
• Run Length Study 3 performed
• New resins procured and arrived at site
Study Period II. Evaluating A 850END/PFA300E Dual Resins
• Dual resins installed
• Arsenic in system effluent monitored with ArsenicGuard
• Special study aborted due to salt loading incident
• Weekly sampling resumed
• Run Length Study 4 performed
• Resin cleaning performed
• Run Length Study 5 performed
• Elution study performed
• Resin cleaning performed
• System bypassed due to faulty flow sensor
• Weekly sampling resumed
Date
09/19/06-01/14/08
09/19/06-09/22/06
10/20/06-10/23/06
02/21/07
02/28/07-03/07/07
04/16/07
07/16/07-01/14/08
10/22/07
10/24/07-10/26/07
01/14/08-02/09/09
01/14/08-05/01/08
05/02/08
07/15/08
08/15/08
08/25/08
11/19/08
12/08/08-12/10/08
12/26/08
02/10/09 to 03/22/10
02/10/09-02/13/09
02/13/09-03/02/09
03/02/09-03/04/09
03/25/09-12/16/09
04/21/09-04/22/09
06/24/09
06/29/09-07/01/09
06/29/09-07/01/09
10/16/09
12/22/09-01/15/10
02/02/10-02/08/10
40
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4.4.1 Operational Parameters. Operational data were collected for a total of 70 weeks in Study
Period I and 52 weeks in Study Period II. Table 4-10 summarizes key operational parameters collected
from each study period. The complete set of operational data is presented in Appendix C after tabulation.
In Study Period I, the IX system operated for a total of 4,440 hr based on readings of an hour meter
installed at the wellhead. Excluding October 19, 2006, and a week in November 2007, the system
operated for 466 days, resulting in an average daily run time of 9.5 hr. The system processed
approximately 128,000,000 gal of water based on readings of a wellhead Mag meter (excluding the
amount of water used for regeneration). Due to the lack of Mag meter readings between September 27
through October 25, 2006, the throughput for that period was estimated based on the average daily
demand of 274,473 gpd. The peak daily demand was 497,751 gpd, which occurred on May 31. 2007.
In Study Period II, the IX system operated for a total of 3,215 hr in 337 days (excluding 24 days from
December 22, 2009, through January 15, 2010, when the system was not in operation). The average daily
run time also was 9.5 hr. The system processed approximately 93,600,000 gal of water with an average
daily demand of 277,653 gpd. The 524,463-gpd peak daily demand occurred on July 31, 2009.
Table 4-10. Summary of System Operational Data
Parameter
Data Collection Period
Total Operating Time (hr)
Total Operating Days (day)
Average Daily Run Time (hr/day)
Throughput to Distribution(a) (gal)
Average Daily Use (gpd)
Peak Daily Use (gpd)
Number of Regeneration Cycles
Regeneration Frequency (day/regeneration)
System Service Flowrate(c) (gpm)
Empty Bed Contact Time (min)
Hydraulic Loading (gpm/ft2)
Pressure Loss Across IX Vessel (psi)
Pressure Loss Across System (psi)
Study Period I
09/27/06-01/14/08
4,440
466
9.5
127,904,500(b)
274,473
497,751
278
1.7
490-576 (534)
2.4-2.8 (2.6) (d)
11.3-13.3(12.3)
Vessel A 6-15 (11)
Vessel B 6-17 (11)
30-47 (40)
Study Period II
02/16/09-02/12/10
3,215
337
9.5
93,569,200
277,653
524,463
144
2.3
542-557 (536)
2.6-3.3 (2.8) (e)
10.4-12.9 (12.4)
Vessel A 7-13 (10)
Vessel B 7-24 (11)
33-42 (40)
(a) Based on wellhead totalizer readings, excluding water used for regeneration.
(b) Throughput from 09/27/06 to 10/25/06 estimated due to lack of totalizer readings.
(c) Based on flowmeter on system effluent; excluding lower flowrate during system regeneration.
(d) Based on 186 ft3 of Arsenex II in two IX vessels.
(e) Based on 197 ft3 of dual resins in two IX vessels.
Figures in parentheses representing average values.
Key operational parameters, including product water flowrate, EBCT, hydraulic loading rate, and pressure
loss across each IX vessel and across the system, are similar between the two study periods and
comparable to the respective design values, as discussed below.
• System service flowrates ranged from 490 to 576 gpm and averaged 534 gpm in Study Period
I, and ranged from 542 to 557 gpm and averaged 536 gpm in Study Period II. These values
compared well with the system design flow of 540 gpm. When one vessel was being
regenerated, water continued to be treated by the other vessel at 251 to 298 gpm in Study
Period I and 260 to 288 gpm in Study Period II.
41
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• Average EBCTs were 2.6 min and 2.8 min for Study Periods I and II, respectively;
comparable to the design value of 3 min.
• Average hydraulic loading rates were 12.3 and 12.4 gpm/ft2 for Study Periods I and II,
respectively, close to the design value of 12.5 gpm/ft2.
• The pressure loss across each IX vessel ranged from 6 to 17 psi and averaged 11 psi in Study
Period I, and ranged from 7 to 24 psi and averaged 11 psi in Study Period II. Such headless
was expected for a 5-ft deep resin bed because 1 foot of resin normally causes 1 to 2 psi of
pressure loss.
• The pressure loss across the IX system averaged 40 psi in both study periods. Based on
observations made for other EPA demonstration systems, including the IX system at
Fruitland, ID, high pressure losses across the IX system was caused primarily by the 270-gpm
flow restrictor installed on each vessel outlet. Similar flow restrictors had been found to
overly restrict the flow and had to be removed for the Fruitland system. The flow restrictors
were not removed at Vale because the wellhead booster pump was capable of overcoming the
high pressure losses experienced, supply the water to the IX system at the design flowrate,
and maintain the effluent pressure at 10 to 12 psi in the 200,000-gal atmospheric storage tank.
4.4.2 Regeneration. The system PLC initiated an automatic regeneration cycle based on a
throughput setpoint. The duration of each regeneration step, e.g., brine draw, slow rinse, and fast rinse,
was controlled by a timer in the PLC. In Study Period I, a total of 278 regeneration cycles took place,
corresponding to a regeneration frequency of once every 1.7 days. In Study Period II, a total of 144
regeneration cycles took place, corresponding to a frequency of once every 2.3 days. The regeneration
setpoints, monitoring parameters, and salt usage during the entire study period are discussed as follows.
4.4.2.1 Regeneration Setpoints. The PLC OIP contains a screen of regeneration setpoints as shown
in Figure 4-18. A summary of regeneration setpoints for both study periods is presented in Table 4-11.
During the initial system startup in July 2006, the system was set to regenerate every 600,000 gal of
volume throughput. The regeneration cycle consisted of a 10-min spent brine draw and a 17-min fresh
brine draw with an 11% brine (to achieve a salt level [a.k.a salt loading or regeneration level] of 12 lb/ft3
of resin), followed by a 30-min slow rinse and a 15-min fast rinse. Changes were made several times to
the volume throughput, spent and fresh brine draw time, and brine concentration in Study Period I to
ensure good effluent water quality and proper salt loading. The adjustments were made based on results
of two run length studies performed during September 19 through 22, 2006, and October 24 through 26,
2007, and observations/measurements made during regeneration.
• On September 13, 2006, just one week before Run Length Study 1, the volume throughput
setpoint was extended to 905,300 gal to be closer to Purolite's simulation of 1,119,280 gal.
• Based on Run Length Study 1 results (Section 4.5.3), the volume throughput setpoint was
reduced to 600,000 gal on October 5, 2006. When a Kinetico technician returned to the site
on October 20, 2006, to address a high salt usage issue, spent and fresh brine draw times were
reduced to 7 and 8 min, respectively, and the brine concentration was reduced to 6%. These
changes, however, overly adjusted the salt usage, causing the salt loading to drop to 5.9 lb/ft3
based on the data obtained on November 21, 2006. Low salt loadings apparently had
impacted the performance of the IX system.
• On December 5, 2006, the brine concentration was adjusted back to 11% and the fresh brine
draw time increased to 13 min. These changes increased the salt loading back up to 25 lb/ft3
as measured on January 31, 2007.
42
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1
1
17
30
1 SLOW RINSE
JTIMF (MIN )
15
BOODOO
I TIME (MIN,)
1 TOTAL VOLUME
JREGEN TRIGGER (GAL.)
BRINESATURATORA
HIGH ALARM LEVEL (FT)
BRINESATURATORA
LOW ALARM LEVEL (FT)
BRINE SATURATOR B
HIGH ALARM LEVEL (FT)
BRINE SATURATOR B
LOW ALARM LEVEL (FT)
CONTROL DATA
,, . BRINE DRAW (NEW)
TO WASTE TIME (MIN.)
SLOW RINSE
TIME (MIN.)
FAST RINSE
TIME (MIN.)
REGEN TRIGGER (GAL.)
BRINESATURATORA
HIGH ALARM LEVEL (FT)
BRINESATURATORA
LOW ALARM LEVEL (FT)
BRINE SATURATOR B
HIGH ALARM LEVEL (FT)
BRINE SATURATOR B
LOW ALARM LEVEL (FT)
Figure 4-18. PLC Regeneration Setpoints Shown on OIP
(top-Study Period I; bottom-Study Period II)
To better control fresh brine injection, Kinetico installed a brine injection pump to replace the
Venturi eductor during a site visit by the end of February 2007. Meanwhile, the technician
inadvertently reset the system for counter-current regeneration. The mistake was corrected
later during another site visit on March 5, 2007. The fresh brine draw time was increased to
15 min while the brine concentration was reduced to 6%. A salt loading close to the target of
12 lb/ft3 was achieved based on the data collected in March 2007.
On April 13, 2007, the volume throughput setpoint was reduced to 370,000 gal based on the
arsenic breakthrough data to ensure that arsenic concentrations in system effluent were below
its MCL.
43
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Table 4-11. IX System Regeneration Setpoints at Vale, OR
Setting
ID
Startup
Date of
Change
07/23/06
Regen.
Trigger
gal
600,000
Run
Length
BV(a)
431
Spent
Brine
Draw
Min
10
Fresh
Brine
Draw
min
17
Slow
Rinse
min
30
Fast
Rinse
min
15
Brine
sp. gr.
1.08
Brine
Cone.
%
11
Study Period I
1
2
3
4(b)
5
6
09/13/06
10/05/06;
10/20/06
12/05/06
03/05/07
04/13/07
10/22/07
905,300
600,000
600,000
600,000
370,000
600,000
651
431
431
431
266
431
10
7
7
7
7
Q(0
17
8
13
15
15
23
30
30
30
30
30
30
15
15
15
15
15
15
1.08
1.042
1.08
1.042
1.042
1.042
11
6
11
6
6
6
Study Period II
7
02/13/09
600,000
491
Discont'd
21
45
15
1.06
8
(a) Based on 186 and 163.3 ft of IX resin(s) in Study Periods I and II, respectively.
(b) After a brine injection pump installed to replace eductor.
(c) Spent brine draw discontinued due to concern over resin fouling caused by DOM in spent brine.
sp. gr. = specific gravity
• On October 22, 2007, after resin cleaning, the volume throughput setpoint was returned to
600,000 gal, spent brine draw was discontinued, and the fresh brine draw time was increased
to 23 min to compensate for the spent brine.
In Study Period II, the regeneration setpoints for the dual IX resin system were established by Battelle
according to resin specifications and the experience gained through system operations at Fruitland, ID.
The target salt loading was 10 lb/ft3. To achieve this level, brine draw was set at 60 gpm for 21 min using
an 8% brine. The brine draw rate used in Study Period I ranged from 73 to 145 gpm, which exceeded the
recommended draw rate of 0.2 to 0.8 gpm/ft3 according to the resin specification sheet. Since slow rinse
used the same flow as the brine makeup water, its duration was increased to 45 min to compensate for the
lower flowrate. The regeneration setpoints remained unchanged throughout Study Period II.
4.4.2.2 Regeneration Monitoring. Regeneration of Vessels A and B were monitored and recorded
on log sheets nine times in Study Period I and twice in Study Period II. Since data recorded for both
vessels were rather similar, averages between the two vessels are presented in Table 4-12 for all
regeneration steps. The volume of water used for each regeneration step was recorded from a totalizer
located upstream of the eductor. Volumes of spent and fresh brines were recorded from individual brine
totalizers on the outlet of both brine tanks. The volume of fresh brine draw (i.e., diluted brine) was
calculated using Equation 1:
where:
'brine, d (ybrine, s ' brine,s * * water)"^brine, d
ne, d= volume of diluted brine (gal)
ne, s= volume of saturated brine (gal)
ter= volume of brine make-up water (gal)
, s= specific gravity of saturated brine, e.g. 1.176 for 23% brine
e, d= specific gravity of diluted brine, e.g. 1.074 for 10% brine
(1)
44
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Table 4-12. IX System Regeneration Monitoring at Vale, OR
Study
Period
I
II
Date
Setting
ID
Design Value
09/21/06
11/21/06
01/31/07
03/05/07
03/07/07
03/20/07
11/27/07
12/13/07
08/15/08
1
9
3
4
4
4
6
6
6
Design Value
02/13/09
06/29/09
7
7
Stepl
Spent Brine Draw
Draw
Time
min
15
10
7
7
7
7
7
Draw
Volume
gal
750
760
579
515
525
530
528
Flow
Rate
gpm
50
76
83
74
75
77
75
Discontinued
Discontinued
Discontinued
Discontinued
Discontinued
Discontinued
Stepl
Fresh Brine Draw
Draw
Time
min
17
17
8
13
15
15
15
23
23
23
21
21
21
Makeup
Water
Volume
gal
518
1,239
636
1,027
856
1,111
1,230
1,932
1,730
2,000
924
924
924
Saturated
Brine
Volume
gal
336
648
123
856
301
286
324
525
530
629
420
400
329
Dilute
Brine
Volume
gal
850
1,853
749
1,883
1,161
1,389
1,534
2,457
2,260
2,592
1,334
1,324
1,253
Flow
Rate
gpm
50
109
94
145
73
93
102
107
113
113
64
63
60
Step 3
Slow Rinse
Rinse
Time
min
40
30
30
30
30
30
30
30
30
30
45
45
45
Rinse
Volume
gal
2,000
2,267
2,400
2,385
2,637
2,303
2,475
2,520
2,565
2,497
1,980
1,980
1,980
Flow
Rate
gpm
50
76
80
80
88
77
83
84
86
83
44
44
44
Step 4
Fast Rinse
Rinse
Time
min
20
15
15
15
15
15
15
15
15
15
75
15
15
Rinse
Volume
gal
4,400
3,527
3,900
3,893
3,296
3,384
3,378
3,720
3,900
3,533
J,900
3,945
3,998
Flow
Rate
gpm
220
235
260
260
220
226
225
248
260
236
260
264
267
Total
Waste
Production
Per Regen
Cycle
gal
7,250
7,646
7,048
8,160
7,093
7,075
7,387
8,697
8,725
8,622
7,274
7,257
7,230
Note: All values refer to one IX vessel using averages of Vessel A and B.
-------
In Study Period I, as shown in Table 4-12, spent brine draw rates ranged from 74 to 83 gpm and averaged
77 gpm, which was over 50% higher than the design value of 50 gpm. Shortening the draw duration from
the design value of 15 min to 10 min, then to 7 min, helped to correct for the high draw rate issue.
The fresh brine draw step was problematic during the early part of the study. Fresh brine draw rates
ranged from 73 to 145 gpm, which was two to three times the design value of 50 gpm and exceeded the
upper limit of the suggested regeneration rate of 0.8 gpm/ft3. A higher brine draw rate would mean more
salt consumption. To maintain a lower salt level, a shorter brine draw time may be used but not desirable
because it may not provide enough time for exchange reactions to occur throughout the resin bed. As
such, the brine draw rate was purposely reduced to 64 gpm in Study Period II.
At the beginning of the study, the saturated brine volume drawn during the fresh brine draw step was 648
gal, which almost doubled the design value of 336 gal. Follow-on adjustments performed either under- or
over-corrected the problem, resulting in 123 and 856 gal of saturated brine under Settings 2 and 3,
respectively. The vendor suggested that the problem might have been caused by an incorrectly sized
Venturi eductor (oversized in this case) and that it would be better off to replace the eductor with a brine
injection pump. Since the installation of a brine injection pump in late February 2007, the saturated brine
volume was better controlled to just below or above the target value at 286 to 324 gal (under Setting 4), as
monitored on March 5, 7, and 20, 2007. Under Setting 6, saturated brine volumes were higher, ranging
from 525 to 629 gal due to the use of an extended draw time (i.e., 23 min) to make up the loss due to
discontinuation of spent brine draw.
In Study Period I, slow rinse rates ranged from 76 to 88 gpm and averaged 82 gpm, which was over 60%
higher than the design value of 50 gpm. Fast rinse rates ranged 220 to 260 gpm and averaged 241 gpm,
which is close to the design value of 220 gpm. Regeneration of each IX vessel produced 7,048 to 8,725
gal of wastewater during Study Period I, but averaged at 8,681 gal under Setting 6.
In Study Period II, all regeneration parameters monitored were similar to the design values and appeared
to be adequate based on results of the elution study (see Section 4.5.5). Regeneration of each IX vessel
generated an average of 7,244 gal of wastewater, which is 20% less than that under Setting 6 in Study
Period I.
4.4.2.3 Salt Usage. The amount of salt used by each regeneration cycle was calculated based on
concentrations and volumes of spent and/or fresh brines according to Equation 2. The salt loading was
then calculated by dividing the weight of salt by the volume of resin. The results of the calculations are
presented in Table 4-13.
Wsait = Vj,rine X Jbrine x dwater X Csait (2)
where:
Wsait = weight of salt (Ib)
Vbrine = volume of brine used (gal)
Jbrine = specific gravity of brine
dwater= density of water, e.g., 8.34 (Ib/gal)
Csau= percent of salt i
The specific gravity of saturated brine at 23% was 1.176. Specific gravities of spent brines measured by a
hydrometer ranged from 1.039 (5.4%) to 1.066 (8.9%), which were affected by concentrations of diluted
fresh brines used for previous regeneration cycles. Specific gravities of diluted brine measured in Study
Period I ranged from 1.042 (6%) to 1.080 (11%), depending on regeneration settings. The specific
gravity of diluted brine measured in Study Period II was 1.060 (8.1%), close to the target of 8%.
46
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Table 4-13. Vale, IX System Salt Loading Calculations
Study
Period
I
II
Date
Setting
ID
Design Value
09/21/06
11/21/06
01/31/07
03/05/07
03/07/07
03/20/07
11/27/07
12/13/07
08/15/08
1
2
3
4
4
4
6
6
6
Design Value
02/13/09
06/29/09
7
7
Spent Brine
Spent
Brine
Volume
gal
750
760
579
515
525
360
528
sp. gr.
of
Spent
Brine
1.067
1.047
1.039
1.066
1.060
1.045
1.050
Spent
Brine
Cone.
%
9.0
6.5
5.4
8.9
8.1
6.2
6.9
Weight
of
Salt
Ib
600
429
272
406
377
195
318
Discontinued
Discontinued
Discontinued
Discontinued
Discontinued
Discontinued
Fresh Brine
Saturated
Brine
Volume
gal
336
648
123
856
301
286
324
525
530
629
420
400
329
sp. gr.
of
Diluted
Brine
1.074
1.080
1.042
1.080
1.042
1.042
1.050
1.051
1.042
1.057
1.059
1.060
1.060
Diluted
Brine
Cone.
%
10.0
10.8
5.9
10.8
5.9
5.9
6.9
7.0
5.9
7.8
8
8.1
8.1
Weight00
of
Salt
Ib
760
1,462
276
1,931
678
645
731
1,184
1,196
1,419
945
902
741
Total
Total
Salt
Weight^
Ib
1,346
1,891
548
2,337
1,055
840
1,049
1,184
1,196
1,419
945
902
741
Total
Salt
Loading(c)
lb/ft3
12
20.3
5.9
25.1
11.3
9.0
11.3
12.7
12.9
15.3
10
9.3
7.6
(a) Based on saturated brine.
(b) Sum of spent brine and fresh brine.
(c) Based on actual resin volume in each vessel, i.e., 93 ft3 of Arsenex II and 97.5 ft3 of dual resin.
sp. gr. = specific gravity
-------
As shown in Table 4-13, the salt loading was 20.3 lb/ft3 on September 21, 2006, approximately 70%
higher than the design value of 12 lb/ft3. This higher loading was mainly caused by the higher brine
volume used in regeneration. The salt loading was reduced to 5.9 lb/ft3, then increased back to 25.1 lb/ft3
following the adjustments made in October and December 2006, respectively. After the installation of the
brine injection pump, salt loadings ranged from 9.0 to 11.3 lb/ft3 (under Setting 4) from 12.7 to 15.3 lb/ft3
(under Setting 6), indicating a better control of the salt use. In Study Period II, the average salt loading
was 8.5 lb/ft3, about 15% lower than the design value of 10 lb/ft3.
4.4.3 IX Resin Fouling. Deteriorating resin performance was observed over the course of Study
Period I, as evidenced by a decreasing trend in resin run length. For example, shortly after system startup
in September 2006, the system treated approximately 600,000 gal of water before arsenic in system
effluent reached 10 (ig/L. The amount of water treated was reduced to 450,000 gal in early January 2007
based on weekly water sampling data (Section 4.5.1.2). After seven months into system operation, the
useful run length was further reduced to 376,940 gal in April 2007 (Section 4.5.1.2), which was 63% of
the initial value.
To determine the causes for the shortened run lengths, resin core samples were collected from both IX
vessels in March 2007 and sent to Purolite for analyses (along with resin samples collected from the
Fruitland FX system). Purolite reported that some resin beads were visibly fouled by particulates and
likely DOM when viewed under a microscope. These samples were cleaned in Purolite's laboratory with
a 10% brine and a mixture of 2% caustic/10% brine, respectively, and analyzed after each cleaning. The
results are presented in Table 4-14 and compared with the specifications of virgin Arsenex II resin.
Table 4-14. Resin Analyses After Laboratory or Field Cleaning
Resin
Sample
Arsenex II-virgin
Moisture
(%)
40-45
Volumetric
Capacity
(eq/L)
1.2
Percent
Volumetric
Capacity
(%)(a)
100
Percent
Strong
Base
Capacity
(%)
100
TOC
(mgof
C/
gof
resin)
NA
Iron
Content
(mg/g)
NA
Silica
Content
(mg/g)
NA
10% Brine Cleaning in Purolite Laboratory (March 2007)
Vessel A
Vessel B
35.5
35.0
0.83
0.94
69
78
92
81
12.0
15.4
26
13
129
204
2% Caustic/10% Brine Cleaning in Purolite Laboratory (March 2007)
Vessel A
Vessel B
38.0
38.9
.13
.16
94
97
93
87
9.6
6.0
NA
NA
NA
NA
5% Caustic/10% Brine Cleaning at Vale Treatment Plant (October 2007)
Vessel A-top
Vessel A-middle
Vessel A-bottom
Average
43.2
39.9
38.7
40.6
.05
.14
.15
.11
88
95
96
93
81
77
79
79
10.7
8.0
8.6
9.1
157
122
14
98
NA
NA
NA
NA
Six Months after Field Cleaning (August 2008)
Vessel A
Vessel B
38.7
37.7
0.96
1.08
80 1 NA
90 | NA
61.0
46.0
120
100
NA
NA
(a)% = actual volumetric capacity/virgin volumetric capacity.
After cleaning with 10% brine, samples collected from Vessels A and B contained 12.0 and 15.4 mg of
C/g of resin, respectively, indicating organic built-up. The extent of TOC fouling was considered severe
by Purolite and the primary cause for the deteriorating performance and shortened run lengths observed.
48
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Organic fouling resulted in significant losses (i.e., 22 to 31%) in volumetric capacity. The reduction in
resin capacity also was reflected by a lower moisture content and a lower strong base capacity. It was
suspected that some SBA exchange sites were converted to a weak base type, which would not be as
useful for removing arsenic or nitrate. Iron and silica levels also increased, suggesting that they also
O 5 OO O J
acted as foulants.
The laboratory cleaning with a mixture of 2% caustic/10% brine was able to remove a significant amount
of foulants, achieving a noticeable recovery of the resin's capacities. For example, the volumetric
capacity was restored to 94 to 97% of the virgin resin level and the strong base capacity restored to 87 to
93%. Increases in moisture content and strong base capacities reflected the recovery of exchange sites
blocked by organic matter before resin cleaning. The TOC content on the resin was reduced to 6.0 to 9.6
mg of C/g of resin (although lower than what would be expected considering the significant gain in
overall capacities), suggesting reduction in TOC fouling by caustic/brine cleaning.
Prompted by the promising results of the laboratory cleaning at Purolite and the field cleaning at
Fruitland, ID, the IX system at Vale underwent a similar cleaning process using a mixture of 5%
caustic/10% brine in October 2007 (Section 3.6). After cleaning, a core resin sample was collected from
Vessel A and shipped to Purolite for analyses. Meanwhile, Run Length Study 2 was conducted from
October 24 through 26, 2007, to determine cleaning effectiveness. Results of the laboratory analyses
showed the highest levels of TOC and iron and the lowest volumetric capacity in the top section (see
Table 4-14), suggesting that the resin was the most severely fouled by DOM and iron at the top. The
resin in the middle and bottom sections contained, on average, 22% less TOC and 57% less iron, thus
having 9% more volumetric capacity. The strong base capacity at the middle and the bottom was similar
to that at the top. Based on the results of Run Length Study 2, the resin run length was improved by
approximately 20% to 445,700 gal.
In August 2008, resin samples after field cleaning were collected from both vessels and sent to Purolite
for analyses. The data showed that TOC had continued to accumulate on the resin at levels up to 61 mg
of C/g of resin, approximately six times the TOC level right after the field cleaning in October 2007. In
December 2008, about 10 months after the October 2007 cleaning (not including the five month well
rehabilitation extending from January through May 2008), the useful run length was further reduced to
323,530 gal (Section 4.5.3, Run Length Study 3), which was 27% lower than that observed right after the
caustic/brine cleaning in October 2007.
4.4.4 Dual IX Resin Approach. Since the caustic/brine cleaning failed to effectively strip off all
TOC from Arsenex II resin and restore its run length back to 600,000 gal, the possibilities of either
converting the system into an AM or C/F system or replacing Arsenex II with other types of resin were
contemplated. Because the IX system could not be easily converted to an AM or C/F system according to
the equipment vendor and because the City of Vale preferred an IX system due to concerns over possible
increases in nitrate concentration in the future, the investigation was focused on the search of other types
of resin. In May 2008, Professor Dennis Clifford of the University of Houston recommended the use of
an acrylic IX resin, such as Purolite A850, as a TOC scavenger. Meanwhile, Purolite recommended the
use of dual IX resins such as PFA300E (for arsenic/nitrate removal) overlain by a layer of A850END (for
TOC removal). The volume ratio between PFA300E and A850END would be 85:15. For a total of 110
ft3 of resin, one vessel would contain approximately 95 ft3 of PFA300E and 15 ft3 of A850END.
Purolite's simulation software generated an estimated run length of 523 BV in June 2008 or 604 BV in
January 2009 based on additional source water quality data (see Figure 4-5). The revised projection
corresponded to a throughput of 993,940 gal (1 BV = 220 ft3).
Due to the high silica and TOC levels in source water, it was recommended that a 5% caustic/10% brine
wash be performed every four months as a precautionary measure.
49
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4.4.4.1 Dual Resin Options. On July 15, 2008, a meeting was held at Battelle with EPA, the City of
Vale, and two technical consultants - Professor Dennis Clifford and Mr. Glen Latimer, to discuss options
for implementing the dual resin approach. Because the City expressed its desire to continue with the IX
technology for any future issues with nitrate, alternative treatment technologies were not further pursued.
Three options regarding system configuration were explored, which are summarized as follows:
• The first option was to remove the old resin and replace it with 15 ft3 (8-in depth) of
A850END underlain by 95 ft3 (~52-in depth) of PFA300E in each vessel. No changes to
system configuration would be needed and each vessel would retain the EBCT of 3 min. The
estimated cost of the media would be approximately $50,000. This option was considered the
most acceptable and most time- and cost-effective option.
• The second option was to add a third vessel in front of the two existing vessels. The
additional vessel would be of 72-in diameter and contain 113 ft3 (48-in depth) of A850END
for TOC scavenging. The existing 63-in vessels would each be rebedded with 110ft3 of
PFA300E for arsenic/nitrate removal. The EBCT of the 72-in vessel would be approximately
1.5 min while the EBCT of the 63-in vessel would remain at 3 min. Significant changes to
the system would have to be made to accommodate the additional vessel. The cost of media
for this option was estimated to be approximately $81,765. This option could be costly and
would require significant engineering support and perhaps approval by the state drinking
water program.
• The third option was to change the configuration of the two existing 63-in vessels from
parallel to series. Under this configuration, the first vessel would contain 110 ft3 of
A850END for TOC removal followed by the second vessel containing 110 ft3 of A300E for
arsenic/nitrate removal. The change in configuration would require cutting back the system
flow to maintain an acceptable loading rate and pressure drop. The system would be
regenerated by running a 10% brine solution through the PFA300E vessel followed by the
A850END vessel, then discharging the wastewater to the evaporation pond. The cost of
media for this option would be approximately $57,200. This option might also have required
regulatory approval.
The meeting concluded that the first option of replacing the old resin from the existing vessels with dual
IX resins was acceptable to all parties involved and should be pursued immediately.
4.4.4.2 Concerns over Solids in IX Resin Beds. Since the beginning of the resin fouling discussion,
Purolite had expressed concerns over the lack of backwashing in the Vale system operation and suspected
that iron/organic complex in source water could have contributed to the resin fouling. It recommended
that either a pre-filter be added ahead of the IX vessels or a backwashing step be incorporated into the
regeneration cycle. Since the iron levels in raw water were consistently below the reporting limit of 25
(ig/L and manganese levels were below 1 (ig/L, the existing sediment filtration using 5-(im bag filters
should be sufficient as long as the bag filters were changed out whenever needed. During a trip to Vale
on August 15, 2008, Battelle staff performed a visual inspection of the inside of each IX vessel and saw
no signs of solids accumulation on the bed surface. Therefore, the pre-filter option was deemed
unnecessary.
When onsite, a measurement taken on Vessel A from the top of the flange to the top of the resin bed and
showed 19.75 in of freeboard in each IX vessel. This freeboard measurement indicated that there was not
enough freeboard in the vessels to support IX resin backwashing. This, in conjunction with the fact that
little or no iron was present in source water, led to the decision not to include a backwashing step into the
IX resin regeneration cycle. The freeboard measurement was later used to estimate the actual resin
volume in the vessel.
50
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4.4.4.3 Special Study at McCook, NE. A dual IX resin system was installed by the McCook Water
Treatment Plant (WTP) in McCook, NE for the removal of arsenic, nitrate, and uranium from water
containing high TOC (Boodoo et al., 2008). To learn more about McCook's experience with the dual IX
resin approach, Battelle staff members visited the McCook WTP on August 26 and 27, 2008, and
conducted an elution study on the effectiveness of the regeneration process and a run length study on the
dual IX resin system. Results of the special study along with a description of the facility water quality,
water treatment process, and major activities conducted onsite were documented in a technical
memorandum. A brief summary is provided herein.
The McCook water treatment plant, rated at a 7 million gallon per day (MOD) production capacity, began
operation in February 2006. Source water quality varied depending on which groundwater wells were
supplying water. Typical water quality is profiled as: pH 7.2, 382 mg/L of alkalinity, 226 mg/L of
sulfate, 525 mg/L of hardness (as CaCO3), 100 ug/L of phosphorus, 850 mg/L of TDS, 12.5 ug/L of
arsenic (soluble As[V] as predominating species), 13 ug/L of nitrate, 31.1 ug/L of uranium, and 3.5 mg/L
of TOC. The treatment process consists of six 10-ft * 15-ft (straight-side-height) cation vessels and six
9.5-ft x 15-ft (straight-side-height) anion vessels. Each anion vessel contained 66 in of A300E (392 ft3)
resin top-dressed with 12 in of A850END (69 ft3) resin for simultaneous removal of multiple
contaminants (see Figure 4-19). Approximately 50% of raw water bypassed the entire treatment system
and only 50% of softened water was treated by the AIX vessels. Most of the time, only two or three
anion vessels were placed online; each anion vessel was set to regenerate every 579,000 gal (168 BV) of
water treated for nitrate control. Co-current regeneration with a salt dosage of 10 lb/ft3 was conducted in
four steps: 10-min backwash, 52-min brine draw, 45-min slow rinse, and 40-min fast rinse.
Hpral
Figure 4-19. McCook, NE Water Treatment Plant
51
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A complete regeneration and service cycle of one anion vessel (i.e., Vessel 5) was monitored in a two-day
period. Grab and composite samples were collected from each step of the regeneration cycle (see Figure
4-20). Following regeneration, time-series influent and effluent samples were collected during the Vessel
5 service cycle. In addition, a resin core sample was collected from a freshly regenerated Vessel 6 for
visual inspection and analysis.
Figure 4-20. Sample Collection and pH/TDS Monitoring during
Regeneration of AIX Vessel 5 at McCook, NE
Figure 4-2 la plots elution curves of arsenic, uranium, nitrate, sulfate, TOC, TDS, and bicarbonate versus
time during the regeneration cycle. The percent recovery of each contaminant (i.e., arsenic, uranium,
nitrate, and TOC) from the regeneration cycle was calculated by dividing the amount of contaminant in
the spent brine and rinse water by the amount removed from raw water. Figure 4-2 Ib presents the
exhaustion breakthrough curves for arsenic and nitrate. The main observations and findings from the
McCook study are briefly summarized as follows:
• Due to the long freeboard over the resin bed (i.e., 8 to 9 ft), it took over 40 min for brine to
emerge from the vessel to the discharge line, as indicated by TDS reading. TDS readings
reached the maximum level of 117 g/L approximately 10 min before the end of the slow
rinse.
• Resin regeneration achieved 99% recovery for TOC, 86% for arsenic, 130% for uranium, and
55% for nitrate. The spent brine had a distinctive yellowish or tea color, indicating the
presence of DOM.
• TOC levels in the effluent water were below detection during the run length study (576,000
gal). Arsenic and nitrate breakthrough at their respective MCLs occurred at 445,000 gal (129
BV) and 550,000 gal (161 BV), respectively. Uranium was almost completed removed.
52
-------
4,000
3,500
120
100
0 10 20 30 40 50
70 80 90 100 110 120 130 140 150
Time(min)
-As -»-NO3-N -O-TOC Bicarb -B-TDS -»-U
SO4
(a) Regeneration Curves
Run Length (BV)
in o
50
40
1
c
•S 30
ro
is
01
o
o
O 20
10
100,000 200,000 300,000 400,000
Volume of Water Treated (gal)
500,000
Inlet-As
-Outlet-As --A- Inlet-Nitrate
-Outlet-Nitrate
(b) Exhaustion Curves
Figure 4-21. Results of McCook AIX Vessel 5
30
25
in
ra
20
15
O)
o
•
10
600,000
53
-------
• The resin core sample did not show two distinctive layers; A850END and A300E resins
appeared to be mixed. Purolite's laboratory could not find enough A850END sample for
separate resin analyses. Per Purolite, resin capacities were "acceptable" after 2.5 years of
service.
Findings at McCook suggest that A850END can be effective at removing TOC from raw water, thus
preventing the underlying resin from being fouled. Based upon these findings, a decision was made to
replace Arsenex II with A850END/PFA300E at Vale.
4.4.4.4 Dual Resin Installation. Rebedding of the two IX vessels was performed during February
10 and 13, 2009, by Accurate Water Solutions, a subcontractor to Battelle. Arsenex II resin was removed
from the vessels using a vacuum truck, but the gravel underbedding remained in the vessels to be reused.
Freeboard measurements were then made from the top of the flange to the top of the gravel. Purolite
PFA300E and A850END IX resins were then loaded sequentially into each vessel with freeboard
measurements taken immediately after loading of each IX resin. It was noted that the top of the
A850END layer had already reached the bottom of the top diffuser, indicating maximum loading in the
two resin vessels. Calculations of resin volumes based on the freeboard measurements resulted in 197 ft3
of resins in both vessels, compared to the design volume of 220 ft3. Freeboard measurements and resin
volumes are presented in Table 4-15.
Table 4-15. Freeboard Measurements during Dual Resin Rebedding
Freeboard
Measurement
To top of Gravel (in)
TotopofPFA300E(in)
To top of A850END(in)
DepthofPFA300E(in)
Depth of A850END(in)
Volume of PFA300E (ft3)
Volume of A850END (ft3)
Total Resin Volume (ft3)
Vessel A
70.75
25.5
16.0
45.25
9.5
81.6
17.1
98.7
Vessel B
71.25
26.0
17.0
45.25
9.0
81.7
16.2
97.9
Total Resin
Volume
(ft3)
-
-
-
-
-
163.3
33.3
196.6
Once the IX resins had been loaded, each vessel underwent a regeneration cycle. Based on the results
from the first regeneration of each vessel, the regeneration settings were adjusted to achieve the target salt
loading of 10 lb/ft3.
4.4.5 Residual Management. Residuals produced by the IX system included spent brine and rinse
water, which were discharged to the evaporation pond adjacent to the treatment building. FeCl3 was
added to spent brine in an attempt to precipitate arsenic and allow the iron sludge to settle in the
evaporation pond. The design and construction of the evaporation pond and the FeCl3 treatment system
were performed by the City's contractors and described in Sections 4.2.2 and 4.3.2.
The volume of wastewater produced was determined by the regeneration frequency and the volume of
wastewater generated per regeneration cycle. Table 4-12 presents relevant calculations of wastewater
production under different regeneration settings. Reclaiming spent brine could save salt use and reduce
wastewater production. Comparing amounts of wastewater produced under Regeneration Setting 6
(without brine reclaim) and Regeneration Setting 4 (with brine reclaim), 17% less wastewater was
54
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produced (reduced from an average of 8,622 to 7,185 gal) when spent brine was reused per vessel when
reused brine was applied. The use of spent brine, however, was discontinued on December 10, 2007 due
to concerns over resin fouling by TOC.
The evaporation pond was designed based on the Purolite-projected resin run length and regeneration
frequency. Shorter run lengths and higher regeneration frequencies experienced caused the pond to fill
faster than originally designed. In April 2008, the City obtained one-time approval from the Oregon DHS
to use the pond water as a dust suppressant in the nearby area. This helped to lower the water level in the
pond.
To characterize the water quality of the residuals, samples were collected from the waste stream from
each regeneration step as well as the pond water. The results are provided in Sections 4.5.5 and 4.5.6.
Prior to dual resin installation, a sample of the old Arsenex II resin was collected on August 15, 2008, and
sent to Belmont Labs for the Toxicity Characteristic Leaching Procedure (TCLP) test. The results
showed less than MDL of arsenic, cadmium, chromium, selenium, mercury and silver, 0.25 mg/L of
barium, and 0.058 mg/L of lead. After passing the TCLP, the spent Arsenex II resin was disposed of as a
non-hazardous waste.
4.4.6 System Operation Requirement
4.4.6.1 Required System Operation and Operator Skills. The required system operation and
operator skills are further discussed below according to pre- and post-treatment requirements, levels of
system automation, operator skill requirements, preventive maintenance activities, and frequency of
chemical/media handling and inventory requirements
Pre- and Post-Treatment Requirements. Pretreatment included filtration with two banks of bag filters
(each containing five) to remove sediment from source water. Filter bags were replaced when differential
pressure (Ap) readings across the bag filter assembly were greater than 12 to 15 psi. Filter bags were
replaced five times from September 27, 2006 to January 14, 2008 in Study Period I; and twice from
February 16, 2009 to March 22, 2010 in Study Period II. It took approximately two hours each time to
replace all 10 filter bags. The only post-treatment was post-chlorination for disinfection.
System Automation. The IX system was fully automatic and controlled by the PLC in the central control
panel. The control panel contained a touch screen OIP that allowed the operator to monitor system
flowrate and throughput since last regeneration. The OIP also allowed the operator to change system
setpoints, as needed, and check alarm status. Setpoint screens were password-protected so that changes
could be made only by authorized personnel. Typical alarms were for no flow, storage tank high/low, and
regeneration failure. The IX system was regenerated automatically based on a throughput setpoint, except
during regeneration sampling events when regeneration was initiated manually to record log sheets and
capture spent regenerant and rinse samples. It is a good practice to periodically check on relevant
parameters during a complete regeneration cycle, including specific gravity of dilute brine and volumes of
spent and/or fresh brines used, to ensure adequate salt loadings and identify operational issues, if any, at
an early stage.
Operator Skill Requirements. Operating and maintaining an IX system required minimal additional
operator skills beyond those required for small system operators, such as solid work ethic, basic
mathematical skills, abilities to understand chemical properties, familiarities with electronic and
mechanical components, and abilities to follow written and verbal instructions. Understanding of and
compliance with all occupational and chemical safety rules and regulations also were required. Since all
major system operations were automated and controlled by the PLC, the operator was required to
55
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understand and learn how to use the PLC and OIP to perform tasks after receiving training from the
vendor.
Oregon state law requires owners of public and private drinking water and wastewater systems to have
their systems under the responsible control and direction of certified operators. Oregon DHS
DWP administers the certification program for drinking water system operators. DHS DWP classifies
water distribution systems and treatment plants according to their complexity and size:
• Water systems with 149 and fewer connections and utilizing groundwater as their only source
or purchasing all their water from another public water system without adding any additional
treatment require a small water system "S" certification.
• Water systems with 150 or more connections require certification at Levels 1 to 4 in either
treatment and/or distribution. Distribution systems are classified as Levels 1 to 4 according
to the population served by the system. Treatment plants are classified as Levels 1 to 4,
depending on factors such as system complexity, size, and source water.
The plant operator at Vale, OR had a treatment plant Level 1 license. After receiving proper training
from the vendor during system startup, the operator understood the PLC, knew how to use the OIP, and
worked with the vendor and Battelle to troubleshoot and perform minor on-site repairs.
4.4.6.2 Preventive Maintenance Activities. Preventive maintenance tasks recommended by the
vendor included daily to monthly visual inspection of the piping, valves, vessels, flow meters, and other
system components. Routine maintenance also may be required on an as-needed basis for the air
compressor motor and the replacement of o-ring seals or gaskets on automated or manual valves and the
brine transfer pump. During the demonstration study, maintenance activities performed by the operator
included replacing filter bags periodically, checking the brine concentration using a hydrometer, and
adjusting regeneration frequency and setpoints as instructed by the vendor or Battelle.
4.4.6.3 Chemical/Media Handling and Inventory Requirements. Routine regeneration requires
sodium chloride and periodically, caustic soda for resin cleaning. The IX system has fully automated
controls with IX resin regeneration triggered by volume throughput. A salt truck delivered salt on a
monthly or as-needed basis with the operator's presence. The salt saturators were sized to hold 22 tons of
salt supply. Assuming that the system regenerated 13 times per month (based on regeneration frequency
in Study Period II, Table 4-10) and used 1,633 Ib of salt per event (as designed for Study Period II), it
would require 21,229 Ib or 9.5 tons of salt per month. Therefore, the salt saturators held about two
months of salt supply.
Because the salt saturators were situated in the same room as the treatment system, excessive salt dust
was generated during salt delivery. The salt is corrosive to the electrical/mechanical components of the
treatment system. Placing the salt saturators in a separate room would minimize the salt dust and
corrosion issues.
4.5 System Performance
The performance of the IX system was evaluated based on analyses of water samples collected across the
treatment train, during regeneration, and from the distribution system. In addition, special run length
studies and an elution study were conducted to provide additional insight into system performance.
4.5.1 Treatment Plant Sampling. In Study Period I, Arsenex II performance was evaluated
through sampling across the treatment train on 31 occasions, including two duplicate sampling events and
56
-------
eight speciation events. Regular weekly sampling was discontinued after April 16, 2007; only TT
samples were collected for total arsenic and nitrate analyses between July 16, 2007 and January 14, 2008.
In Study Period II, A850END/PFA300E were evaluated through sampling across the treatment train on
32 occasions. No duplicate sampling or speciation sampling took place in Study Period II. Table 4-16
summarizes arsenic and nitrate analytical results in both study periods. Tables 4-17 and 4-18 summarize
results of other water quality parameters in Study Periods I and II, respectively. Appendix D contains a
complete set of analytical results. The results obtained are discussed in the following subsections.
Table 4-16. Summary of Arsenic and Nitrate Analyses in Study Periods I and II
Parameter
Unit
Sampling
Location'3'
Count
Minimum
Maximum
Average
Standard
Deviation
Study Period I
As (total)
As
(soluble)
As
(paniculate)
As (III)
As(V)
Nitrate
(asN)
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
mg/L
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
31
30
29
30
8
8
7
8
8
8
7
8
8
8
7
8
8
8
7
8
31
30
29
30
18.3
0.5
0.4
0.7
19.2
1.6
1.8
1.6
<0.1
<0.1
<0.1
<0.1
0.4
0.4
0.3
0.3
17.8
0.8
1.0
0.9
1.4
O.05
O.05
0.4
31.8
45.8
33.8
48.7
22.9
42.1
29.8
35.9
3.7
3.6
3.0
3.4
2.3
2.5
2.8
2.7
22.5
39.6
27.0
33.1
7.6
9.9
8.9
7.1
22.6
_(b)
_(b)
_(b)
21.0
_(b)
_(b)
_(b)
1.9
0.7
1.2
1.0
1.0
0.9
0.9
0.9
20.0
_(b)
_(b)
_(b)
5.4
_(b)
_(b)
_(b)
3.1
_(b)
_(b)
_(b)
1.1
_(b)
_(b)
_(b)
1.3
1.2
1.3
1.2
0.6
0.7
0.9
0.8
1.5
_(b)
_(b)
_(b)
1.5
_(b)
_(b)
_(b)
Study Period II
As (total)
Nitrate
(asN)
Hg/L
mg/L
IN
TA
TB
TT
IN
TA
TB
TT
32
31
31
32
32
31
31
32
16.0
0.1
<0.1
<0.1
4.0
0.1
0.6
0.1
23.3
34.7
31.1
31.4
7.5
9.9
9.9
9.3
19.6
_(b)
_(b)
_(b)
5.6
_(b)
_(b)
_(b)
1.8
_(b)
_(b)
_(b)
0.7
_(b)
_(b)
_(b)
(a) See Figure 3-1 for sampling locations.
(b) Not meaningful for concentrations related to breakthrough, see Figures 4-23 through 4-25
and Appendix D for results.
One-half of detection limit used for non-detect samples for calculations.
Duplicate samples included in calculations.
57
-------
Table 4-17. Summary of Other Water Quality Parameters in Study Period I
Parameter
Alkalinity
Fluoride
Sulfate
Phosphorus
(asP)
Silica
(as SiO2)
Turbidity
TOC
TDS
pH
Temperature
DO
ORP
Total
Hardness
Unit
mg/L
mg/L
mg/L
ug/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
mg/L
Sampling
Location'50
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
Count
31
30
29
8
8
8
7
8
30^>
30
29
8
31
30
29
8
31
30
29
8
31
30
29
8
1
31
30
29
8
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
9
8
7
8
Minimum
254
171
143
194
0.5
0.5
0.5
0.5
63.9
<1
<1
<1
212
<10
<10
<10
46.1
53.6
10.3
54.6
0.2
0.1
0.1
0.4
2.0
434
412
432
430
7.2
7.1
7.0
7.0
14.6
14.4
14.3
14.0
1.6
2.0
1.8
2.0
127
126
120
118
120
140
142
137
Maximum
358
432
427
400
1.1
1.1
1.4
1.3
97.0
38.0
38.0
40.0
337
664
458
559
59.2
60.0
59.8
59.9
0.9
1.2
1.6
1.1
2.0
766
606
550
554
8.0
8.3
8.2
8.2
17.5
17.9
18.2
16.8
6.3
6.5
6.9
6.5
295
262
252
252
251
240
241
229
Average
329
_(<0
_(<0
_(<0
0.7
0.7
0.8
0.7
81.8
_(°>
_(<0
_(°>
278
_(<0
_(°>
_(<0
55.6
56.1
54.2
56.4
0.5
0.5
0.6
0.6
2.0
514
485
486
483
7.4
7.5
7.5
7.4
15.5
15.4
15.4
15.3
3.7
4.0
3.9
4.1
253
222
214
216
165
171
173
171
Standard
Deviation
23.8
_(<0
_(<0
_(<0
0.2
0.3
0.3
0.3
7.7
_(<0
(c)
_(<0
33.4
(c)
_(c)
(c)
2.1
1.4
8.6
1.9
0.2
0.2
0.3
0.2
-
61.7
40.8
32.1
42.5
0.2
0.3
0.3
0.3
0.8
0.8
0.9
0.7
1.4
1.5
1.6
1.5
33.1
32.1
33.2
36.3
36.0
30.4
33.2
28.7
58
-------
Table 4-17. Summary of Other Water Quality Parameters in Study Period I (Continued)
Parameter
Ca Hardness
Mg
Hardness
Fe (total)
Fe (soluble)
Mn (total)
Mn
(soluble)
V (total)
V (soluble)
Unit
mg/L
mg/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
Sampling
Location00
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
Count
9
8
7
8
9
8
7
8
31
30
29
8
8
8
7
8
31
30
29
8
8
8
7
8
9
8
7
9
8
8
7
8
Minimum
75.0
96.2
98.0
92.8
44.0
43.9
43.6
43.7
<25
<25
<25
<25
<25
<25
<25
<25
O.01
O.01
0.01
0.01
0.01
0.2
O.01
O.01
46.5
0.6
0.7
0.6
48.5
0.5
0.6
0.7
Maximum
187
178
179
169
63.9
61.8
61.6
59.8
<25
<25
<25
<25
<25
<25
<25
<25
2.1
2.3
1.4
0.6
0.5
0.6
0.5
0.6
60.5
3.6
4.5
3.9
61.2
3.5
4.5
3.5
Average
115
120
121
120
50.1
50.9
51.7
51.0
<25
<25
<25
<25
<25
<25
<25
<25
0.4
0.5
0.4
0.4
0.4
0.4
0.3
0.4
54.1
2.0
2.2
2.1
54.2
2.0
2.1
2.1
Standard
Deviation
30.5
25.4
28.0
24.0
6.5
6.2
6.2
5.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.4
0.4
0.3
0.2
0.1
0.1
0.2
0.2
5.5
.0
.3
.0
5.1
.0
.3
0.9
(a) See Figure 3-1 for sampling locations.
(b) Excluding an outlier on 10/02/2006.
(c) Not meaningful for concentrations related to breakthrough, see Figures 4-26 and 4-27;
and Appendix D for results.
One-half of detection limit used for non-detect samples for calculations.
Duplicate samples included in calculations.
59
-------
Table 4-18. Summary of Other Water Quality Parameters in Study Period II
Parameter
Alkalinity
Sulfate
Phosphorus
(asP)
Silica
(as SiO2)
Turbidity
TOC
TDS
Fe (total)
Mn (total)
V (total)
Unit
mg/L
mg/L
ug/L
mg/L
NTU
mg/L
mg/L
ug/L
ug/L
ug/L
Sampling
Location'3'
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
IN
TA
TB
TT
Count
32
31
31
32
32
31
31
32
31
30
30
31
32
31
31
32
32
31
31
32
32
31
31
32
32
31
31
32
32
31
31
32
32
31
31
32
32
31
31
32
Minimum
279
76.0
26.4
52.8
63.6
<0.1
<0.1
<0.1
249
<10
<10
<10
54.5
54.9
54.4
53.6
0.1
0.1
0.1
0.1
1.4
<1
<1
<1
434
416
420
368
<25
<25
<25
<25
0.2
0.1
0.2
0.2
46.9
0.1
O.I
0.1
Maximum
346
402
390
400
83.2
61.7
16.0
21.3
345
452
447
457
66.2
65.2
67.2
64.6
2.6
1.3
4.2
2.1
2.2
<1
<1
<1
588
606
724
650
<25
<25
<25
<25
5.3
3.2
3.3
3.0
59.4
7.3
14.5
11.5
Average
309
_(b)
(b)
_(b)
74.0
_(b)
_(b)
_(b)
275
_(b)
_(b)
_(b)
59.4
59.8
60.1
59.8
0.3
0.4
0.5
0.4
1.8
<1
<1
<1
498
476
484
478
<25
<25
<25
<25
0.7
0.5
0.5
0.5
51.3
2.3
2.9
2.7
Standard
Deviation
15.1
(b)
_(b)
(b)
4.4
_(b)
_(b)
_(b)
19.7
_(b)
_(b)
_(b)
2.6
2.3
2.8
2.5
0.5
0.4
0.7
0.4
0.2
0.0
0.0
0.0
32.1
41.6
62.4
51.7
0.0
0.0
0.0
0.0
1.1
0.6
0.6
0.6
3.1
2.0
3.5
2.7
(a) See Figure 3-1 for sampling locations.
(b) Not meaningful for concentrations related
One-half of detection limit used for nondetect
to breakthrough, see Appendix D for results.
samples for calculations.
4.5.1.1 Arsenic Speciation. Eight speciation sampling events were conducted in Study Period I.
Figure 4-22 presents arsenic speciation results at the IN, TA, TB, and TT sampling locations. Soluble
As(V) was the predominant species in raw water, ranging from 17.8 to 22.5 ug/L and averaging 20.0 ug/L
(Table 4-16). Trace amounts of particulate As and soluble As(III) also existed with concentrations
60
-------
D As(particualte)
• As(V)
• As(III)
09/20/06 10/18/06 11/14/06 12/13/06 01/10/07 02/12/07 03/12/07 04/10/07
50
As Species after Vessel A (TA) ° As(particulate)
•As(III)
216,079 gal | | | | | | 114,230 gal
^_^^^=i
09/20/06 10/18/06 11/14/06 12/13/06 01/10/07 02/12/07 03/12/07 04/10/07
50
40
As Species after Vessel B (TB)
dAs(particulate)
•As(V)
•As(III)
543,862 gal
,750 gal
^=1
09/20/06 10/18/06 11/14/06 12/13/06 01/10/07 02/12/07 03/12/07 04/10/07
50
40
30
20
10
0
As Species after Vessels A and B Combined (TT)
543,862 gal
475,337 gal
I I 125,750 gal
I | l^~^~I
407,330 gal
DAs(p articulate)
•As(V)
•As(III) 451,996 gal
09/20/06 10/18/06 11/14/06 12/13/06 01/10/07 02/12/07 03/12/07 04/10/07
Figure 4-22. Concentrations of Arsenic Species across Treatment System
61
-------
averaging 1.9 and 1.0 ug/L, respectively. After the IX treatment, a small amount of participate As
(0.9 ug/L [on average]) was removed by either the bag filters or the IX resin beds. Soluble As(III)
concentrations, however, remained essentially unchanged at 0.9 ug/L. This was as expected because the
IX process does not remove neutral species such as arsenite. Speciation sampling was not conducted in
Study Period II.
For each sampling event, the volume throughput at the time of sampling is marked on Figure 4-22 to
relate treatment results with the run length. As shown on the figure, arsenic was removed to below the
10-ug/L MCL during the early stage of service cycles. Elevated arsenic concentrations (i.e., >10 ug/L)
were measured in IX vessel effluent on September 20, 2006, and January 10, February 12, and March 12,
2007, when samples were collected at a throughput of 653,391, 451,996, 475,337, and 543,862 gal,
respectively, indicating that the IX system needed to be regenerated before reaching 450,000 gal.
4.5.1.2 Arsenic Removal. Arsenic and nitrate were the two primary contaminants of concern in
source water; thus, their removal was key to assessing the performance of the IX system. Figures 4-23
and 4-24 present total arsenic concentrations across the treatment train for Study Periods I and II,
respectively. Figure 4-23 plots the concentration data against either sampling dates ("temporal plot") or
volume throughputs at the time of sampling ("reconstructed breakthrough curves"). Because the temporal
plot does not explain why arsenic exceeds the MCL, the reconstructed breakthrough curves provide more
insight into system performance. Typically, a breakthrough curve is constructed with data collected from
one complete service cycle. Because the IX system was regenerated once every two to three days, routine
weekly treatment plant water samples were collected from different service cycles. Collectively, these
data, after being sorted by volume throughput (from low to high), can exhibit breakthrough behaviors
similar to those one would expect in a service cycle. Therefore, "reconstructed breakthrough curves"
were used to discuss nitrate, sulfate, and other parameters in the following sections (Note that the
September 25 and October 31, 2006 data were not plotted due to lack of throughput data).
Study Period I. As shown in Table 4-16, total arsenic concentrations in source water varied from 18.3 to
31.8 ug/L and averaged 22.6 ug/L in Study Period I. These concentrations were slightly higher than
those (i.e., 16.7 and 20 ug/L [see Table 4-2]) sampled previously during the initial site visit on December
2, 2004.
The temporal plot in Figure 4-23a can be divided into three sub-periods: from startup to April 13, 2007;
from April 13, 2007, to October 22, 2007; and after October 22, 2007. The volume throughput setpoint
was 600,000 gal for the first sub-period, shortened to 370,000 gal for the second sub-period, and returned
to 600,000 gal for the sub-third period (after resin cleaning). Arsenic had been consistently removed to
below the MCL in the second sub-period, but its concentrations were erratic in the first and third sub-
periods. The "reconstructed breakthrough curves" in Figure 4-23b showed that, except for three TT
samples collected on November 14, November 19, and December 3, 2007, all other TA, TB, and TT
samples collected prior to a volume throughput 370,000 gal contained <10 ug/L of arsenic. In contrast,
all but one sample collected after 370,000 gal had arsenic concentrations exceeding the MCL. In addition
to sampling time, operational issues such as low salt loadings (between October 20 and December 5,
2006) and counter-current regeneration (set by mistake in late February 2007) also had contributed to the
high effluent concentrations observed (such as those collected on November 6, 14, and 28, 2006, and on
March 5 and 12, 2007).
The IX system performance was deteriorating with time as evidenced by the weekly arsenic monitoring
data and special run length study results. The run length to 10-ug/L arsenic breakthrough was reduced
from 562,300 gal at startup in September 2006 to 449,702 gal in early January 2007, and then to 376,940
62
-------
50
-1^
o
Ł
io
L*J
o
e
01
:j
a
8
<*i
<
"3
I
K>
o
' — '
o
) TA
A TB
D TT
Re gen at 600,000 gal
(before 04/13/07)
D
O
A
"dr
Regen at 370,000 gal
(04/13/07-10/22/07)
Regen at 600,000 gal
(afteV 10/22/07)
0
09/01/06 11/30/06 02/28/07 05/29/07 08/27/07 11/25/07 02/23/08
Sampling Date
50
40
a
o
u
c
o
<
"3
30
20
10
Study Period I: Purolite Arsenex II Resin
TAregen by-passed on
11/14/07, 11/19/07,
100,000 200,000
300,000 400,000 500,000
Water Treated (gal)
600,000
700,000
Figure 4-23. Total Arsenic Concentrations Measured During Study Period I
(a) Temporal Plot; (b) Reconstructed Breakthrough Curves
63
-------
50
40
30
OS
-«-j
a
o 20
<
~Ł
10
Study Period II: Purolite Dual Resin A850END/PFA300E
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
Figure 4-24. Total Arsenic Concentrations Measured During Study Period II
gal in early April 2007. As discussed in Section 4.4.3, shortened run lengths most likely were caused by
organic matter buildup, which could block exchange sites and reduce resin capacities.
Immediately after resin cleaning on October 22, 2007, A TT sample collected at a volume throughput of
377,889 gal contained 2.1 (ig/L, which was significantly lower than the 11.1 (ig/L measured in another
TT sample collected at 376,940 gal on April 2, 2007 (see data in Appendix D). However, all of the six
subsequent TT samples collected between October 29 and December 10, 2007 exceeded the arsenic MCL.
Three of the samples were collected at high volume throughputs of 595,337, 533,870, and 530,622 gal,
with arsenic concentrations of 33.5, 33.8, and 48.7 (ig/L, respectively. The other three were collected at
low volume throughputs of 131,979, 50,196, and 51,996 gal, with lower arsenic concentrations of 11.8,
10.2, and 11.9 (ig/L, respectively, all of which were over the MCL. According to Run Length Study 2
conducted on October 24 to 26, 2007, throughput to 10-(ig/L arsenic breakthrough was approximately
445,700 gal, which explained why the high-throughput samples contained high arsenic concentrations.
Puzzled by the low-throughput sample results, the operator observed a regeneration cycle on November
27, 2007, and noticed that while in the automatic mode, Vessel A skipped regeneration and only Vessel B
was regenerated. During troubleshooting, Kinetico discovered that because the spent brine draw time was
set to zero after the caustic wash on October 22, 2007, the PLC did not work properly as the software
could not accept zero as a setpoint. Once the draw time was temporarily set to 1 min on December 10,
2007, the PLC worked correctly to regenerate both vessels. (Note that the spent brine draw step was
removed from the PLC in February 2009 after installation of dual resins.) The subsequent two TT
samples collected at 200,373 gal on December 17, 2007, and at 195,150 gal on January 7, 2008, contained
64
-------
1.3 and 2.2 (ig/L of arsenic, respectively. However, the TT sample collected at 418,136 gal on January
14, 2008 contained 20.6 (ig/L of arsenic, indicating that the run length to 10 (ig/L was shortened again,
compared with the 445,700 gal established right after resin cleaning in October 2007. Because the IX
system was shut down for well rehabilitation during January 14 and May 1, 2008, another resin cleaning
was not performed.
As the IX system was allowed to operate beyond the 10-|o,g/L breakthrough, effluent arsenic
concentrations became significantly higher than influent arsenic concentrations, a phenomenon
commonly known as chromatographic peaking or dumping. This arsenic dumping was caused by more
preferred anions such as sulfate, which displaced previously exchanged arsenic from the resin. In
addition, because sulfate concentrations were more than three orders of magnitude higher than those of
arsenic, these concentration effects further accelerated displacement. Arsenic dumping is a major
drawback of the IX technology, but can be mitigated by controlling the timing of regeneration to prevent
overrun.
Study PeriodII. Total arsenic concentrations in raw water ranged from 16.0 to 23.3 (ig/L and averaged
19.6 (ig/L in Study Period II. Run Length Study 4 performed in April 2009 indicated a useful run length
of approximately 436,350 gal. Based on the "reconstructed breakthrough curves" in Figure 4-24, arsenic
breakthrough at 10 (ig/L occurred at TT between 444,200 gal (3.2 (ig/L on July 20, 2009) and 487,900 gal
(13.7 (ig/L on September 2, 2009) and was estimated to be 472,500 gal. The average of the two values
(i.e., 436,350 and 472,500 gal) was 454,400 gal, which was 51% of the projected run length by the
Purolite simulation. The run length for Vessel B was slightly longer than that of Vessel A, i.e., by
approximately 20,000 to 40,000 gal. Arsenic dumping also was observed in Study Period II as samples
were collected at a throughput higher than 487,900 gal.
Unlike the Fruitland IX system where elevated arsenic concentrations were measured in effluent up to
50,000 to 60,000 gal (67 to 80 BV) after the system had just been regenerated, arsenic leakage was not
noticeable at Vale, OR. Because co-current regeneration was employed at both Fruitland and Vale, it was
not clear what had caused the difference between the two sites.
4.5.1.3 Nitrate Removal. As shown in Table 4-16, nitrate concentrations in source water ranged from
1.4 to 7.6 mg/L (as N) and averaged 5.4 mg/L (as N) in Study Period I; and ranged from 4.0 to 7.5 mg/L
(as N) and averaged 5.6 mg/L (as N) in Study Period II. Figures 4-25a and 4-25b present "reconstructed
breakthrough curves" of nitrate for Study Periods I and II, respectively. While consistently below the
nitrate MCL of 10 mg/L (as N) in both study periods, effluent nitrate concentrations exhibited an
increasing trend and approached or even exceeded influent nitrate concentrations towards the end of a
service cycle. For example, effluent nitrate concentrations reached or exceeded coresponding influent
concentrations at a volume throughput of approximately 380,000 gal in Study Period I and 480,000 gal in
Study Period II. Because these volume throughput values were longer than those to the 10-(ig/L arsenic
breakthrough, useful run lengths for both the ArseneX II and dual resin systems were controlled by
arsenic breakthrough, not nitrate breakthrough.
The original intent of system design was to control system operations based on nitrate breakthrough
because it was easier and cheaper to monitor nitrate using a Hach test kit and because the regular resin is
cheaper than the nitrate selective resin. The facility reported a higher nitrate concentration of 8 to 12
mg/L (as N) for technology selection and computer simulation. The facility also indicated that it
preferred the IX system over other technologies because of its ability to remove both arsenic and nitrate.
65
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12
10
I
I 6
a H
OJ
-*^
I
i 2
(a)
Study Period I: Purolite Arsenex II Resin
100,000 200,000 300,000 400,000
Water Treated
500,000 600,000 700,000
Ł
tt
cS
12
10
"M 8
o
U 4
a
(b)
Study Period II: Purolite Dual Resins A850END & A300E
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
Figure 4-25. Reconstructed Breakthrough Curves for Nitrate
(a) Study Period I; (b) Study Period II
66
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4.5.1.4 TOC, Sulfate, Phosphate, and Vanadium Removal.
TOC. In Study Period I, TOC was measured only once on April 16, 2007, at a concentration of 2.0 mg/L
in raw water. After it was identified as a foulant, TOC concentrations were monitored across the dual
resin system in 32 sampling events throughout Study Period II. Raw water TOC concentrations ranged
from 1.4 to 2.2 and averaged 1.8 mg/L, which were consistent with the 2.1 mg/L measured on December
2, 2004 during the initial source water sampling. At the TA, TB, and TT locations, TOC concentrations
were consistently reduced to below the MDL of 1 mg/L, suggesting effective removal by the dual resin
system throughout the entire service cycle of 600,000 gal.
Sulfate. Figure 4-26 presents "reconstructed breakthrough curves" for sulfate in Study Periods I and II.
Sulfate concentrations in raw water averaged 82 mg/L in Study Period I and 74 mg/L in Study Period II.
Sulfate was removed to less than 1 mg/L most of the time in both periods until reaching a volume
throughput of 376,940 gal in Study Period I and 487,940 gal in Study Period II. Afterwards, sulfate
concentrations began to rise as more water was treated and reached 1/3 to 1/2 of its influent concentration
by the end of the 600,000-gal service cycle. Because of its higher selectivity than arsenate and nitrate,
sulfate continued to be removed even when arsenate and nitrate had reached their respective MCL in the
effluent. Displacement of arsenate and nitrate by sulfate would result in higher effluent arsenate and
nitrate concentrations than the respective influent concentrations, as discussed in Sections 4.5.1.2 and
4.5.1.3.
Deteriorating resin performance also was reflected by sulfate concentrations in system effluent. For
example, in Study Period I at system startup on September 20, 2006, the sulfate concentration at TT was 9
mg/L at a volume throughput of 653,391 gal. After six months into system operation on March 19, 2007,
the average of sulfate concentrations at TA and TB was 9 mg/L at a volume throughput of only 415,021
gal, indicating a 36% reduction in run length for sulfate.
Phosphate. Figures 4-27 presents "reconstructed breakthrough curves" for total phosphorus. Raw water
contained 212 to 345 ug/L of total phosphorus, which averaged 278 ug/L in Study Period I and 275 ug/L
in Study Period II. Total phosphorus concentrations in effluents were reduced to less than 10 ug/L most
of the time, but rose rapidly and exceeded influent levels after reaching a volume throughput of
approximately 415,000 gal in Study Period I and 488,000 gal in Study Period II. The pre-adsorbed
phosphate was displaced by more preferred sulfate.
Vanadium. Total vanadium concentrations in raw water measured in both study periods were similar,
ranging from 46.5 to 60.5 ug/L. Figure 4-28 presents "reconstructed breakthrough curves" of total
vanadium in Study Period I and II. Arsenex II reduced vanadium concentrations to <5 ug/L throughout
Study Period I. PFA300E/A850END also reduced vanadium concentrations to <5 ug/L on all but four
occasions on March 25, April 2, September 30, and December 10, 2009, when TT samples collected at
59,084, 551,090, 56,986, and 27,963 gal of volume throughput contained total vanadium concentrations
of 11.5, 6.0, 7.4, and 9.8 ug/L, respectively. Chromatographic peaking was not observed for vanadium in
either period, suggesting that vanadium ions, such as VO43 , HVO42 and/or H2VO4 , may have an
equivalent or even higher selectivity than sulfate and/or uranium ions.
4.5.1.5 Other Water Quality Parameters. Figures 4-29 and 4-30 present a "reconstructed pH plot"
and "reconstructed breakthrough curves" for pH and total alkalinity, respectively. Raw water pH values
ranged from 7.2 to 8.0 and averaged 7.4 in Study Period I. pH was not measured in Study Period II.
Total alkalinity concentration in raw water ranged from 254 to 358 and averaged 329 mg/L (as CaCO3) in
Study Period I; and ranged from 279 to 346 and averaged 309 mg/L (as CaCO3) in Study Period II.
67
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120
100
(a)
Study Period I: Purolite Arsenex II Resin
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
120
100
80
40
20
-e- IN
O TA
A TB
n TT
(b)
Study Period II: Purolite Dual Resins A850END/PFA30QE
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water treated (gal)
Figure 4-26. Reconstructed Breakthrough Curves for Sulfate
(a) Study Period I; (b) Study Period II
68
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700
600
^ 500
X 400
a.
|
pT 300
H 200
100
(a)
Study Period I: Purolite Arsenex II Resin
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated
700
600
500
(b)
Study Period II: Purolite Dual Resins A850END & A300E
A
$*
3
PH
"«
400
300
200
100
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated
Figure 4-27. Reconstructed Breakthrough Curves for Total Phosphorus
(a) Study Period I; (b) Study Period II
69
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-1
•Sfc
3.
o
o
>
"«
-M
&
70
60 -
50 -
40 -•
30 -•
20 -•
^u
10 -t
(a)
Study Period I: Purolite Arsenex II Resin
0 a 8
9
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
70
60 -
50 -
40 -
a
o
• 30
aj
u
a
20
10
(b)
Purolite Dual Resins A850END & A300E
O
a
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
Figure 4-28. Reconstructed Breakthrough Curves for Total Vanadium
(a) Study Period I; (b) Study Period II
70
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8.5
6.5
Study Period I: Purolite Arsenex II Resin
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
Figure 4-29. pH Measured During Study Period I
Slight reductions in pH values were observed for a short period immediately after the IX system had been
freshly regenerated. For example, pH values at the IN, TA, TB, and TT locations were 7.3, 7.2, 7.1, and
7.2, respectively, on October 18, 2006, after 125,800 gal of water had been treated; and 7.3, 7.1, 7.0, and
7.1, respectively, on April 10, 2007 after 114,200 gal of water had been treated. Although pH changes
were small, i.e., no more than 0.3 pH unit, corresponding reductions in total alkalinity across the FX
system were quite significant, i.e., 306, 209, 190, and 194 mg/L (as CaCO3), respectively, on October 18,
2006; and 357, 286, 251, and 282 mg/L (as CaCO3), respectively, on April 10, 2007. The most
significant decrease in total alkalinity was observed on December 4, 2006 after 69,595 gal of water had
been treated: i.e., 326, 171, and 145 mg/L at the IN, TA, and TB locations, respectively. This 50%
reduction in total alkalinity could not be verified by corresponding pH values because they were
measured the next day. Reductions in total alkalinity also were observed in Study Period II in samples
collected immediately after regeneration up to 173,000 gal of volume throughput. For example, over 90%
of reduction in total alkalinity was observed on March 25 and September 30, 2009, after 59,084 and
56,986 gal of water had been treated, respectively.
The reduction in pH and alkalinity immediately after regeneration was attributed to the removal of
bicarbonate ions by the AFX resin. As reported in the literature, one disadvantage of the FX process is the
production of low pH and corrosive water during the initial 50 to 100 BV of a service cycle (Clifford,
1999). Afterwards, the pH value of treated water returned to the raw water level due to the complete
breakthrough of bicarbonate ions, which had a lowest selectivity by the SBA AFX resin.
71
-------
o
u
a
tt
OS
-i
•
_g
"«
500
400
300
200
100
(a)
Study Period I: Purolite Arsenex II Resin
500
O 400
OS
U
OS
300
._S 200
"3
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
o
4
(b)
Study Period II: Purolite Dual Resins A850END & A30.0E
f J
o TA
A TB
n TT
100,000 200,000 300,000 400,000 500,000 600,000 700,000
Water Treated (gal)
Figure 4-30. Reconstructed Breakthrough Curves for Total Alkalinity
(a) Study Period I; (b) Study Period II
72
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4.5.2 Real-Time Arsenic Monitoring by ArsenicGuard™. The ArsenicGuard™ analyzer was
installed on November 19, 2008, to provide real-time monitoring of arsenic in raw and treated water.
ArsenicGuard™ took one measurement every 45 min (even when the well pump was off and the system
was not in operation) with data displayed as strip charts, which can be downloaded from the computer for
further processing. Figure 4-31 shows two examples of real-time total arsenic plots using data
downloaded from ArsenicGuard™. The top graph plotted data from January 16 through February 9,
2009, right before Arsenex II replacement in February 2009. The bottom graph plotted data from August
6 through 30, 2009, after dual resins installation. The plots clearly showed reoccuring service/
regeneration cycles as arsenic concentrations in system effluent cycled between a few (ig/L and higher
than corresponding influent concentrations. As shown in Table 4-11, system regeneration was set at a
volume throughput of 600,000 gal during applicable operating periods shown in Figure 4-31 (under
Setting 6 in Study Period I and Setting 7 in Study Period 7). Arsenic breakthrough to 10 (ig/L occurred
before reaching 600,000 gal for both Arsenex II and PFA300E/A850END and continuning operations
resulted in arsenic dumping in every regeneration cyle. Because ArsenicGuard™ continued analyzing
"samples" even when the system was not in operation, the plots shown in Figure 4-31 do not represent
actual arsenic breakthrough curves or reflect actual run lengths.
TT - ArsenicGuard
0 IN-ArsenicGuard
A TT-ICP/MS
• IN-ICP/MS
Figure 4-31. Examples of Real-Time Arsenic Monitoring by ArsenicGuard
73
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For comparsion purposes, Figure 4-31 also plotted three sets of influent/effluent weekly arsenic data
measured by ICP-MS during the period from August 6 through August 30, 2009. The ArsenicGuard™
and ICP-MS data appeared to be consistent with each other both at low ppb and around 20 ug/L levels.
In addition to arsenic monitoring, the ArsenicGuard™ was equipped with a nitrate sensor for real-time
nitrate monitoring. However, the nitrate sensor failed about one week after installation. Inspections of
the unit revealed coating and/or clogging of the sample chamber, all Teflon® lines, and other assoicated
parts with a white powdery film/deposit. After cleaning and/or replacing of all affected parts, the nitrate
sensor resumed functioning normally, but this normalcy could not be sustained. The salty, corrosive
environment was thought to have affected the nitrate measurements. The nitrate monitoring was
abandoned afterwards.
4.5.3 Run Length Studies. Three run length studies (1 to 3) were conducted on Arsenex II in
Study Period I and two (4 and 5) on A850END/PFA300E in Study Period II. Results of these studies are
discussed below. Note that all throughput readings were taken from the totalizer on the combined
effluent even though samples were collected from individual vessel effluent or combined effluent.
Run Length Study 1 (September 19 to 22, 2006). Run Length Study 1 was conducted on Vessel A
shortly after system startup in September 2006 to establish baseline system performance. Raw water
samples collected on September 20, 2006 contained 24.8 ug/L of total arsenic, 3.5 mg/L of nitrate (as N),
73 mg/L of sulfate, 325 ug/L of total phosphorus, 60 ug/L of total vanadium, and 301 mg/L (as CaCO3)
of alkalinity (See Appendix D). Figure 4-32 presents total arsenic, nitrate, sulfate, total vanadium, total
phosphorus, and total alkalinity breakthrough curves from Vessel A. The first sample collected at 10,700
gal contained slightly elevated total arsenic, total phosphorus, and total vanadium at 11, 117, and 6.9
ug/L, respectively, indicating leakage from the freshly regenerated resin bed. Total arsenic
concentrations decreased to <1 ug/L, stayed at this low level through 500,000 gal, and then peaked at 10
ug/L between 550,000 and 600,000 gal (approximately 562,300 gal based on linear interpolation).
Afterwards, the effluent arsenic concentration reached the influent level at approximately 650,000 gal,
then continued to increase to 60.8 ug/L in the last sample collected at 904,350 gal. Arsenic dumping
resulted in an effluent concentration almost 2.5 times the influent level, the highest level ever detected at
this plant throughout the entire study. Therefore, the regeneration setpoint was reduced to 600,000 gal on
October 5, 2006 as soon as the sample results became available.
Nitrate was below detection before reaching 550,000 gal and gradually increased to 5.2 mg/L (as N) at
904,350 gal by the end of this special study period. This effluent nitrate level exceeded the influent level
but was lower than the 10-mg/L (as N) MCL. Sulfate stayed below 1 mg/L until 550,000 gal, and then
increased sharply to 42.8 mg/L (or 60% of the influent level) at 904,350 gal. Total phosphorus also rose
sharply after 550,000 gal and reached 766 ug/L (or 2.4 times the influent level) at 904,350 gal. Total
vanadium was below 3 ug/L throughout the entire cycle (except for the initial spike mentioned above),
suggesting that it might have a higher selectivity than sulfate. Total alkalinity concentrations started off
low at 10 mg/L (as CaCO3) at 10,700 gal, rose steadily to its influent level at 323,700 gal, and then
leveled off between 312 and 368 mg/L (as CaCO3) through the end of this special study period.
Run Length Study 2 (October 24 to 26, 2007). Run Length Study 2 was conducted on Vessel A two days
after resin cleaning using a mixture of 5% caustic/10% brine in October 2007 to assess the effectiveness
of the cleaning. Figure 4-33 presents total arsenic, nitrate, sulfate, and total alkalinity breakthrough
curves, which are similar to those shown in Figure 4-32, except that the first breakthrough point for total
As, nitrate, and sulfate occurred at approximately 400,000 gal, shorter than the 550,000 gal observed in
Run Length Study 1. The run length to 10-ug/L of arsenic breakthrough was approximately 445,720 gal,
which was 20% more than the pre-cleaning level, but only 80% of the baseline level. The highest arsenic
74
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80
70 -
3
~W)
> 60
«
50 -
Run Length Study 1
Vessel A
September 19 to 22, 2006
At System Startup
800
-- 700
-- 600 S
-- 500
-- 400
-- 300
J
s
-- 200 =
-- 100
0 100,000 200,000 300,000 400,000 500,000 600,000 700,000 800,000 900,000 1,000,000
Throughput (gal)
Figure 4-32. Vessel A Breakthrough Curves from Run Length Study 1
40
35
Run Length Study 2
Vessel A
October 24 to 26, 2007
(After Caustic Wash)
400
--- 350
--- 300
--- 250
--- 200
--- 150
100,000 200,000 300,000 400,000 500,000
Throughput, (gal)
Figure 4-33. Vessel A Breakthrough Curves from Run Length Study 2
--- 100
--- 50
600,000
75
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concentration was 35.7 ug/L in the last sample collected at 565,000 gal. Nitrate concentrations were
below 10 mg/L (as N) throughout this run length study. Sulfate concentrations stayed below 1 mg/L until
400,000 gal, and then increased sharply to 23 mg/L at the end of this special study. Total vanadium
concentrations were <3 ug/L throughout this run length study (data not shown in the graph). Total
alkalinity concentrations started off at 24 mg/L (as CaCO3) at 5,000 gal, increased rapidly to 345 mg/L
(as CaCO3) at 300,000 gal, and then leveled off between 335 and 364 mg/L (as CaCO3) thereafter.
Run Length Study 3 (December 8 to 10, 2008). Run Length Study 3 was conducted on Vessel A to
assess the condition of the resin following nine months of system operation after the October 2007
caustic/brine cleaning. Raw water samples collected at the beginning of the study contained 24.0 ug/L of
total arsenic, 53.3 ug/L of total vanadium, and 57.7 mg/L (as SiO2) of silica. As shown in Figure 4-34,
the run length to 10-ug/L of arsenic breakthrough was shortened significantly from the previous 445,720
gal to approximately 323,530 gal. The deteriorating performance also was reflected by the total
vanadium breakthrough curve, which showed a concentration of 11.3 ug/L at 600,000 gal, compared to
<1 ug/L in both Run Length Studies 1 and 2. Silica concentrations stayed constant throughout this
special study, ranging from 58.0 to 59.3 mg/L (as SiO2).
Run Length Study 3
Vessel A
December 8 to 10, 2008
100,000
200,000 300,000
Throughput (gal)
400,000
500,000
600,000
Figure 4-34. Vessel A Breakthrough Curves from Run Length Study 3
Run Length Study 4 (April 21 to 22, 2009). To establish baseline performance of the dual resins at the
beginning of Study Period II, combined effluent samples were collected mostly between 400,000- and
600,000-gal volume throughput. Raw water samples collected on April 22, 2009 at 162,061 gal of water
76
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treated contained 23.3 ug/L of total arsenic, 308 ug/L of total phosphorus, 59.4 ug/L of total vanadium,
6.8 mg/L of nitrate (as N), and 2.0 mg/L of TOC (See Appendix D).
As shown in Figure 4-35, arsenic breakthrough at 10 (ig/L occurred between 403,000 and 450,000 gal and
estimated to be 436,350 gal using linear interpolation, which was consistent with the results of weekly
sampling discussed in Section 4.5.1.2 (Figure 4-24). Arsenic peaking occurred after 500,000 gal with the
highest concentration measured at 30 (ig/L. Similarly, total phosphorus began to exceed its influent level
around 500,000 gal with the highest concentration measured at 438 (ig/L. Total vanadium was removed
to <5 (ig/L in all but the first sample. Nitrate was below its MCL for the entire study period, reaching its
influent concentration by the end of the study. TOC was removed to below the reporting limit of 1 mg/L
consistently throughout, suggesting that A850END had worked well as a TOC scavenger.
Run Length Study 4
Vessel s A and B
April 21 and 22, 2009
-- 700
800
0
0 100,000 200,000 300,000 400,000 500,000 600,000
Throughput (gal)
Figure 4-35. Combined Effluent Breakthrough Curves from Run Length Study 4
Run Length Study 5 (June 29 to July 1, 2009). Resin cleaning was performed one week prior to this run
length study. Figures 4-36a and 4-36b show breakthrough curves of arsenic, nitrate, sulfate, total
phosphorus, and total vanadium for Vessels A and B, respectively. pH and alkalinity data were plotted
for both vessels on Figure 4-37. TOC and silica data were not plotted.
As shown in Figure 4-36, effluent from Vessels A and B reached 10-(ig/L arsenic breakthrough at
approximately 443,000 and 493,000 gal, respectively, or 468,000 gal (on average). Nitrate did not reach
the 10 mg/L MCL in either vessel. TOC stayed below the MDL of 1 mg/L throughout the study,
indicating good removal by the TOC scavenger. Total phosphorus rose sharply around 400,000 gal for
both vessels. Sulfate and total vanadium remained low throughout the study period while silica
concentrations in the treated water were similar to the raw water level (i.e., 58.7 mg/L [as SiO2]).
77
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400
(a)
Run Length Study 5
VesselA
June 29 to July 1,2009
100,000
200,000
300,000 400,000
Throughput (gal)
500,000
0
600,000
100,000
200,000
300,000
400,000
500,000
Throughput (gal)
Figure 4-36. Breakthrough Curves from Run Length Study 5
400
• 350
• 300
• 250
(b)
Run Length Study 5
Vessel B
June 29 to July 1,2009
ex
3
o
600,000
78
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9.0
8.5 --
8.0 --
7.5 --
7.0 --
6.5 --
6.0
Run Length Study 5
June 29 to July 1,2009
-Vessel A: pH
- Vessel B:pH
-Vessel A: Alkalinity
-Vessel B: Alkalinity
400
- 250
200
- 150
- 100
- 50
0
600,000
0 100,000 200,000 300,000 400,000 500,000
Through put (gal)
Figure 4-37. pH and Alkalinity Breakthrough Curves from Run Length Study 5
Similar to the re-constructed plot (Figure 4-29) based on weekly samples, decreases in pH values were
observed at the beginning of the run length study after the IX system had been freshly regenerated. pH
values were at 6.2 at throughput up to 70,000 gal, and increased to 7.1 and 7.0 at 178,360 and 175,240 gal
for Vessels A and B, respectively. The decreases in pH corresponded to the decreases in total alkalinity,
i.e., from 26.7 mg/L initially to 283 mg/L at 178,360 gal for Vessel A; and from 29 mg/L initially to
216 mg/L at 175,240 gal for Vessel B. Alkalinity for both vessels remained steady at 370 mg/L after
300,000 gal of water treated.
4.5.4 Regeneration Elution Study. The results of the elution study conducted on June 29, 2009
are discussed as follows.
Elution Curves. Figure 4-38 presents elution curves of arsenic, nitrate, total phosphorus, alkalinity,
sulfate, vanadium, silica, and TOC for Vessels A and B. Figure 4-39 shows similar curves for TDS and
pH. All figures have a primary and a secondary y-axis to accommodate all intended analytes on the same
graphs. TDS concentration reflects salt concentration in the eluent. As the brine solution entered an IX
vessel, arsenic, nitrate, sulfate, TOC, and other analytes of concern on the exhausted resin were displaced
into the eluent by highly concentrated chloride ions. The highest concentrations of arsenic, sulfate, and
TOC from Vessel A were measured at 6,963 (ig/L, 33,560 mg/L, and 327 mg/L, respectively,
approximately 11 min into the brine draw step. Nitrate did not peak until 18 min into brine draw at 942
mg/L (as N). Peak concentrations of arsenic, nitrate, sulfate, and TOC from Vessel B occurred between 5
min and 15 min into the brine draw step and were measured at 6,882 (ig/L, 900 mg/L (as N), 40,000
mg/L, and 308 mg/L, respectively. Maximum TDS concentrations for each vessel occurred
approximately 6 min into the slow rinse step. After 41 min into the 45 min slow rinse step, arsenic and
nitrate concentrations decreased to below their respective MCLs while TOC was below its detection limit.
Sulfate concentrations fell below its secondary MCL (250 mg/L) at 36 and 28 min into the slow rinse step
for Vessels A and B, respectively. TDS concentrations for both vessels exceeded its secondary MCL
(500 mg/L) during the entire regeneration cycle.
79
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Vale, OR Anion Tank A Regeneration
120,000
100,000^
Q
ra j
60,000 E. =)
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
-As -X-NO3-N -• Alkalinity TOC
-V -5K-SO4 —1— Silica IDS
Vale, OR Anion Tank B Regeneration
14,000
120,000
35 40 45
Time (min)
-As
NO3-N «-Alk
-TOC
-SO4 •
-Silica
-TDS
Figure 4-38. Vessels A and B Elution Curves
80
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Vale, OR Tank A Regeneration
Time(min)
Vale, OR Tank B Regeneration
120,000
100,000 - -
0.0
Figure 4-39. Vessels A and B Elution Curves for TDS and pH
81
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As shown on Figure 4-39, starting pH values were approximately neutral, i.e., 7.1 for TA and 7.0 for TB.
During brine draw, pH values continued to rise until peaking at 8.4 after 16 min into the slow rinse step
for Vessel A and 8.6 after 13 min into the slow rinse step for Vessel B. By the end of the fast rinse, pH
values in each vessel had decreased to approximately 6.2.
Regeneration Flowrate and Wastewater Volume. As part of the June 29, 2009 elution study,
regeneration flowrates were monitored during the regeneration of each vessel. Flowrates for Vessel A
were 44 gpm for brine draw, 42 to 44 gpm for slow rinse, and 260 to 261 for fast rinse, compared to the
target values of 64, 44, and 260 gpm. Flowrates for Vessel B varied from 40 to 43 for brine draw, 43 to
44 gpm for slow rinse, and 263 to 277 gpm for fast rinse. The average flowrate for brine draw was 43
gpm, which was about 33% lower than the target value of 64 gpm. The lower brine draw flowrate
resulted in lower salt usage and lower salt loading as discussed below under "Saturated Brine Usage."
The volume of wastewater produced was 6,363 gal by Vessel A and 6,491 gal by Vessel B and 12,900 gal
by both vessels. The wastewater produce was discharged to the evaporation pond.
Saturated Brine Usage. The amount of 23% saturated brine used was tracked by the brine totalizer.
Regeneration Vessels A and B used 338 and 319 gal of saturated brine, respectively, equivalent to 760
and 718 Ib of salt, respectively. Salt loadings for Vessels A and B were 7.7 and 7.33 lb/ft3, which were
23% and 27% lower than the target loading of 10 lb/ft3.
Mass Recovered During Regeneration. Concentrations of arsenic, nitrate, vanadium, and TOC were
measured in composite samples collected at the conclusion of each of the three regeneration steps and the
respective volumes of the waste stream were used to calculate the mass of each contaminate recovered
from regeneration. The amount of each contaminant removed from influent water was calculated based
on concentrations of influent and effluent samples collected prior to the regeneration and a volume
throughput of 403,000 gal. Because only one set of influent and effluent samples were collected prior to
regeneration, the amounts of contaminants removed from influent water could be erroneous. The percent
recovery of arsenic, nitrate, vanadium, and TOC from regeneration was calculated using Equation 3:
%R = Mrecmered IMmmoved x 100% (3)
where:
%R = percent recovery
Mrecovered = mass of contaminate in regenerant waste (mg or g)
Mremoved = mass of contaminate removed from influent water (mg or g)
As shown in Table 4-19, the regeneration waste stream contained 17.3 g of arsenic, 4.2 kg of nitrate, 50.1
g of vanadium, and 1.1 kg of TOC per regeneration cycle. The percent recoveries were 112% for arsenic,
131% for nitrate, 113% for vanadium, and 98.5% for TOC. The majority of arsenic, nitrate, vanadium,
and TOC were removed during the brine draw step and the early stage of the slow rinse step. A rather
small amount was removed during the fast rinse step.
4.5.5 Regeneration Residual Sampling. During regeneration of Vessels A and B in Study Period
I, the operator collected composite samples from the waste stream from each regeneration step on
December 20, 2006; January 31, 2007; and March 20, 2007. Composite samples also were collected on
June 29, 2009, as part of the elution study on the dual resin system. Table 4-20 summarizes analytical
results of the four residual sampling events. As expected, the majority of arsenic and nitrate was eluted
during the brine draw step (both reused and fresh brine) for both Arsenex II and PFA300E/A850END.
For Arsenex II, total arsenic concentrations in the reused brine, fresh brine, slow rinse, and fast rinse
samples averaged 2,678, 2,221, 527, and 11.3 (ig/L, respectively; the corresponding concentrations for
82
-------
Table 4-19. Mass Balance Calculations for Total Arsenic, Nitrate, Vanadium, and TOC
Parameter
Volume of Water Treated
Unit
gal
Vessel
Concentration in Composite Brine Draw Waste
Concentration in Composite Slow Rinse Waste
Concentration in Composite Fast Rinse Waste
Brine Draw Volume
Slow Rinse Volume
Fast Rinse Volume
Mass Recovered from Brine Draw Step
Mass Recovered from Slow Rinse Step
Mass Recovered from Fast Rinse Step
Total Mass Recovered
Mass Removed from Influent Water(b)
Percent Recovery
ug/L
ug/L
ug/L
gal
gal
gal
mg
mg
mg
mg
mg
%
Concentration in Composite Brine Draw Waste
Concentration in Composite Slow Rinse Waste
Concentration in Composite Fast Rinse Waste
Brine Draw Volume
Slow Rinse Volume
Fast Rinse Volume
Mass Recovered from Brine Draw Step
Mass Recovered from Slow Rinse Step
Mass Recovered from Fast Rinse Step
Total Mass Recovered
Mass Removed from Influent Water(b)
Percent Recovery
mg/L
mg/L
mg/L
gal
gal
gal
g
g
g
g
g
%
Values
403,000
Arsenic Mass Balance
A
1,471
152
3.0
924
1,980
3,900
5,144
1,140
43.8
6,328
B
2,935
148
3.8
882
1,980
4,080
9,798
1,106
59.0
10,963
Total
2,203 w
150W
3.4W
1,806
3,960
7,980
14,941
2,246
103
17,291
15,482
112%
Nitrate Mass Balance
498
84.7
2.6
1,980
3,900
8,279
1,742
635
38.1
2,415
401
51.9
2.6
1,980
4,080
10,387
1,339
389
39.5
1,767
450(a)
68W
2.6(a)
3,960
7,980
18,665
3,080
1,024
78
4,182
3,203
131%
Vanadium Mass Balance
A
5,981
918
12.8
924
1,980
3,900
20,917
6,876
188
27,981
B
4,705
829
14.6
882
1,980
4,080
15,706
6,216
225
22,147
Total
5,343W
873W
13.7W
1,806
3,960
7,980
36,623
13,092
413
50,128
44,388
113%
TOC Mass Balance
83.8
20.8
<1.0
1,980
3,900
8,279
293
156
7.4
456
158
18.0
<1.0
1,980
4,080
10,387
527
135
7.7
670
12 lw
19.4W
<1.0W
3,960
7,980
18,665
821
291
15
1,126
1,144
98.5%
(a) Average concentrations from both vessels used for calculations.
(b) Calculated using concentrations in raw and treated water.
Note: One-half the detection limit used in calculations.
PFA300E/A850END were 2,203, 150, and 3.4 (ig/L. Similarly, nitrate concentrations averaged 122, 517,
194, and 3.6 mg/L (as N) for Arsenex II and 450, 68, and 2.6 mg/L (as N) for PFA300E/A850END.
Comparing the data of spent and fresh brine samples, the TDS of spent brine was 36% of that of fresh
brine, indicating dilution of spent brine during the previous regeneration cycle. Therefore, spent brine
had a lower strength than fresh brine. Because it was difficult to estimate carryovers of arsenic and
nitrate from the previous regeneration cycle, percent recoveries of arsenic and nitrate were not calculated
for Arsenex II to assess the regeneration efficiency.
Fast rinse samples contained low levels of arsenic, nitrate, sulfate, and TDS, indicating that resin beds had
been rinsed thoroughly and were ready to be put online for a service cycle. This also explained why there
was little or no arsenic/nitrate leakage at the beginning of a service cycle following regeneration. The
lower pH value of the fast rinse water, i.e., ranging from 6.4 to 6.9, was caused by bicarbonate removal by
the freshly regenerated resin, which continued through the beginning of the service cycle.
83
-------
Table 4-20. Regeneration Residual Sampling Results
Sampling Event
Date
Vessel
Reused Brine Draw
4s (total)
ug/L
Nitrate
mg/L
(asN)
Sulfate
mg/L
s
mg/L
B
s.u.
Fresh Brine Draw
"«
"8
X
-^
Hg/L
v
1
g
mg/L
(asN)
Sulfate
mg/L
s
mg/L
D.
S.U.
Slow Rinse
4s (total)
Hg/L
Nitrate
mg/L
(asN)
Sulfate
mg/L
s
mg/L
D.
S.U.
Fast Rinse
4s (total)
Hg/L
Nitrate
mg/L
(asN)
Sulfate
mg/L
8
mg/L
D.
S.U.
Study Period I
12/20/06
01/31/07
03/20/07
A
B
A
B
A
B
Average
43.8)
0>)
21,000
22,800)
28,600
8.7(a)
8.7
8.6
8.6
-------
4.5.6 Analysis of Evaporation Pond Water. Table 4-21 presents analytical results of the pond
water samples. With a pH of 9.3 to 9.8, the pond water contained 4,560 mg/L of total alkalinity, 16 to
25.6 g/L of chloride, 13 to 30.2 g/L of sodium, and 38.2 to 60.1 g/L of TDS, indicating a highly alkaline
and saline water. The pond water also contained as high as 1.3 mg/L of total arsenic, 7.3 g/L of sulfate,
9.2 mg/L (as N) of nitrate, 13.3 mg/L of total phosphorus (as P), and 4.1 mg/L of vanadium.
Table 4-21. Analytical Data for Pond Water at Vale, OR
Sample
Parameter
pH
Total Alkalinity
Sulfate (as SO4)
Nitrate (as N)
Total P (as P)
Phosphate (as PO4)
Silica (SiO2)
Chloride
Turbidity
TDS
TSS
As (total)
As (soluble)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
Na (total)
Na (soluble)
Unit
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
mg/L
mg/L
Pond Water
07/16/07
NA
NA
7,380
NA
NA
37.3
34.6
16,000
NA
38,200
NA
1,070
NA
574
NA
NA
NA
3,730
NA
16,550
NA
09/17/07
NA
NA
NA
NA
NA
58.4
18.8
NA
NA
NA
NA
1,330
1,320
<1,500
NA
NA
NA
4,100
4,070
15,410
15,712
03/15/08
-------
corresponding to Fe to As mass ratios of 15:1 to 1,216:1 at a pH value of 6.9 to 7.2. Analytical results
showed that final arsenic concentrations in the supernatant ranged from 106 to 904 (ig/L and generally
decreased with increasing iron dosages, as shown in Figure 4-40. However, the concentration reduction
leveled off after the first 320 mg/L of iron addition. Even with the 320 mg/L of iron addition, arsenic in
supernatant remained high at 200 (ig/L, indicating ineffective treatment by FeCl3. In contrast, the spent
regenerant from an AM system containing up to 200 mg/L of arsenic (but no salt) was effectively treated
to below 10 (ig/L with FeCl3 at a mere 30:1 Fe/As mass ratio under a neutral pH condition. As shown in
Figure 4-40, total phosphorus and total vanadium also were removed, suggesting that these anions might
compete with arsenic and exert a negative effect on arsenic removal. It was believed that the high salt
contents along with the presence of competing anions rendered the FeCl3 treatment of the pond water
ineffective.
1,400
1,200
14,000
12,000
1,000
I
•d
B
800 -•-
600 -•-
400 —
200
250
500
750 1,000
Iron Dosage (mg/L as Fe)
1,250
1,500
Figure 4-40. Results of Vale Pond Water Jar Tests
4.5.7 Distribution System Water Sampling. Table 4-22 summarizes results of the distribution
system sampling. Prior to system startup, four monthly baseline distribution water samples were
collected from June through September 2005 at three locations within the distribution system. These
three locations included two LCR residences and one non-residence. Following system startup,
distribution system sampling continued on a monthly basis at the same locations until April 2007. No
distribution water samples were collected during Study Period II. All stagnation time for the first draw
samples met the minimum 6 hr requirement, except for one occasion at DS2 on August 23, 2005 (4.8 hr).
86
-------
Table 4-22. Distribution System Sampling Results in Study Period I at Vale, OR
No.
BL1
BL2
BL3
BL4
1
0
3
4
5
6
7
Location
Address
Sample
Type
Flushed/Is
t Draw
Sampling
Date
06/15/05
07/13/05
08/23/05
09/21/05
10/10/06
11/14/06
12/05/06
01/10/07
02/08/07
03/07/07(1)
04/10/07
DS1
6291 5th St North
LCR
1st Draw
Stagnation Time
(hr)
8.5
6.6
7.5
7.0
6.5
14.8
15.0
15.3
14.8
14.8
15.0
D.
7.4
7.5
7.4
7.6
7.6
7.5
7.5
7.7
7.7
7.8
7.7
Alkalinity
484
308
308
299
280
325
321
334
327
329
344
<
21 .4
17.5
25.6
14.7
9.7
10.3
11.8
10.6
11.7
18.6
'3
1
<
484
308
308
308
288
347
323
338
335
342
334
<
20.7
16.2
26.2
14.0
11.1
8.7
10.6
10.4
14.2
24 0<->
16.5
Ł
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
1
1.4
0.1
0.1
0.2
0.4
0.2
<0.1
0.1
1.0
<0.1
0.3
.D
0*
1.4
1.9
0.3
2 2
1.6
2.8
0.9
0.5
0.6
1.0
0.8
3
U
154
390
341
492
501
891
223
134
234
381
479
DS3
252 B Street West
Non-Residence
1st Draw
Stagnation Time
(hr)
7.2
9.8
14.5
15.3
11.1
14.9
12.0
14.0
NA
15.0
14.5
D.
7.3
7.5
7.3
7.6
7.5
7.4
7.4
7.6
7.6
7.7
7.6
Ł>
'3
1
<
431
308
308
308
291
296
323
326
318
327
365
<
22.4
16.1
24.9
14.7
9.8
7.1
12.4
9.7
10.9
16.9("
12.8
Ł
<25
<25
<25
<25
193
34
<25
<25
<25
<25
<25
c
0.7
0.8
0.6
0.7
12.8
13.7
0.4
1.0
1.3
1.1
1.6
.D
0*
1.7
0.7
0.5
1.8
2.5
5.1
0.2
0.3
0.4
0.4
0.3
3
U
381
96.1
85.8
106
75.3
66.9
84.4
141
100
141
108
BL = baseline sampling.; Lead action level =15 ug/L; copper action level =1.3 mg/L
jj,g/L as unit for all analytes except for pH and alkalinity (mg/L [as CaCO3]).
(a) System not functioning properly due to inadvertent switching to counter-current regeneration.
-------
Because treated water from the IX plant was stored in the 200,000-gal reservoir before supplying the
distribution system, the water quality of the distribution samples would reflect the general quality of the
plant effluent after being blended in the reservoir.
Arsenic concentrations of the four baseline sampling events were comparable among all three locations,
ranging from 14.0 to 26.2 ug/L and averaged 19.5 ug/L. After system startup, arsenic concentrations at
all three locations ranged from 7.1 to 24.0 ug/L and averaging 12.6 ug/L. Arsenic concentrations were
reduced significantly, but not to the low level (i.e., < 5 ug/L) that would be expected from an IX treatment
plant because the IX system was allowed to operate beyond 10 ug/L. In five of seven sampling events,
arsenic concentrations in distribution water were close to or slightly higher than the MCL of 10 ug/L. For
the sampling event on March 7, 2007, the arsenic concentration in distribution water increased to as high
as 24.0 ug/L, corresponding to the high levels in the plant effluent on March 5, 12, and 19, 2007, caused
by the inadvertent switching to counter-current regeneration. For the sampling event on April 10, 2007,
arsenic concentrations were 17.0, 16.5, and 12.8 ug/L at the DS1, DS2, and DS3 locations, respectively,
significantly higher than the 1.6 ug/L in the plant effluent. Examination of the sampling logs revealed
that plant effluent samples were collected in the middle of the day after the system had just been
regenerated while distribution "first draw" samples were collected early in the morning when the
reservoir was filled with water containing high levels of arsenic before regeneration.
There was no obvious change to the pH value before and after system startup: the values ranged from 7.3
to 7.6 and averaged 7.5 before startup and ranged from 7.4 to 7.8 and averaged 7.6 after system startup.
Alkalinity also stayed essentially the same, with concentrations ranging from 299 to 484 mg/L (as
CaCO3) before startup and from 280 to 365 mg/L (as CaCO3) after startup. Although occasionally, some
low pH and low alkalinity were measured in treated water samples collected from freshly regenerated
vessels (see Section 4.5.2), the blending effect in the reservoir had mitigated any potential pH or
alkalinity swing. Therefore, low pH and low alkalinity were never measured in distribution system water
samples.
Lead levels at DS2 and DS3 were similar to those in baseline samples. The average concentrations were
1.4 ug/L at DS2 and 1.2 ug/L at DS3 before system startup; and were 1.2 ug/L at DS2 and 1.3 ug/L at
DS3 after system startup. Lead level at DS1, however, increased after system startup to an average of 8.3
ug/L, compared to 1.2 ug/L in baseline samples. On December 5, 2006, lead concentrations at DS1
reached 21.9 ug/L, exceeding the action level of 15 ug/L. The reason for the elevated lead concentrations
at DS1 is unknown since the pH and alkalinity appeared normal. Baseline copper concentrations varied
from 83.7 to 492 ug/L and averaged 239 ug/L. After system startup, copper concentrations decreased
slightly to an average of 224 ug/L, with no samples exceeding the 1,300 ug/L action level.
Total iron concentrations in all samples were <25 ug/L and total manganese <2 ug/L, as expected, except
for two occasions at DS3 on October 10 and November 14, 2006 when total iron concentrations were
measured at 193 and 34 ug/L, respectively, and total manganese concentrations measured at 12.8 and 13.7
ug/L, respectively.
4.6 System Cost
The cost of the IX system was evaluated based on the capital cost per gpm (or gpd) of design capacity and
the O&M cost per 1,000 gal of water treated. This required tracking of the capital cost for the treatment
equipment, site engineering, and installation and the O&M cost for salt supply, electricity consumption,
and labor. The cost associated with the design and construction of the evaporation pond, the new
building, and FeCl3 addition system was not included in the capital cost because it was out of the scope of
the demonstration project, and was funded separately by the City of Vale. Information on the
construction cost is included in Section 4.3.2 at the courtesy of the City of Vale.
-------
4.6.1 Capital Cost. The capital investment for the Vale IX system was $395,434, which included
$260,194 for equipment, $49,840 for site engineering, and $85,400 for installation. Table 4-23 presents
breakdowns of the capital cost provided by Kinetico. The equipment cost included the cost for the IX
resin, filter skid, vessels, brine system, pre-filters, air compressor, instrumentation and controls, shipping,
and labor. The equipment cost was 66% of the total capital investment.
Table 4-23. Cost Breakdowns of Capital Investment for Vale IX System
Description
Quantity
Cost
% of Capital
Investment Cost
Equipment Cost
Welded Stainless Steel Frame
Fiberglass IX Vessels
Distributors
Arsenex II Resin
Brine System
Process Valves and Piping
Air Compressor
Pre-treatment Filters
Instrumentation & Controls
Initial Salt
Sample Taps and Totalizer/meters
Shipping
Labor
Equipment Total
1
2
2
220 ft3
-
-
-
-
-
22 Tons
-
-
-
-
$8,030
$16,134
$2,718
$64,400
$43,784
$24,868
$1,500
$8,800
$13,090
$5,808
$1,728
$17,000
$52,334
$260,194
-
-
-
-
-
-
-
-
-
-
-
-
-
66%
Engineering Cost
Vendor Labor
Subcontractor Labor
Engineering Total
-
-
-
$42,840
$7,000
$49,840
-
-
12%
Installation Cost
Vendor Labor
Subcontractor Labor
Travel
Installation Total
Total Capital Investment
-
-
-
-
$15,400
$65,750
$4,250
$85,400
$395,434
-
-
-
22%
100%
The site engineering cost included the cost for preparing a process design report and the required
engineering plans and obtaining the required permit approval from Oregon DHS DWP. The engineering
plans included a general arrangement drawing, piping and instrumentation diagrams (P&IDs), inter-
connecting piping layouts, vessel fill details, a schematic of the PLC panel, an electrical on-line diagram,
and other associated drawings. The engineering cost of $49,840 was 12% of the total capital investment.
The installation cost included the cost for travel and labor to perform system unloading and anchoring,
plumbing, mechanical and electrical connections, resin loading, system shakedown and startup, and
operator's training. The installation cost was 22% of the total capital investment.
The total capital cost of $395,434 was normalized to the system's rated capacity of 540 gpm (777,600
gpd), which resulted in $732 per gpm ($0.51 per gpd). The capital cost also was converted to an
annualized cost of $37,325/yr using a capital recovery factor of 0.09439 based on a 7% interest rate and a
20-year return. Assuming that the system operates 24 hr/day, 7 day/wk at the design flowrate of 540 gpm
89
-------
to produce 283.8 million gal of water per year, the unit capital cost would be $0.13/1,000 gal. In reality,
the system operated an average of 9.5 hr/day at 534 gpm (in Study Period I, see Table 4-10), producing
111.1 million gal of water per year. At this reduced rate of operation, the unit capital cost increased to
$0.34/1,000 gal.
4.6.2 Operation and Maintenance Cost. The O&M cost included primarily the cost associated
with salt supply, electricity consumption, and labor, as summarized in Table 4-24. Salt supply was a
major operating cost. Coarse solar salt manufactured at the North American Salt's Ogden, Utah facility,
was used for the resin regeneration. This salt is NSF-certified for drinking water treatment. Over the first
year of demonstration study, a total of 397,100 Ib of salt was consumed. The salt delivery charge totaled
$30,180 for the same period. Based on an annual water production of 111.1 million gal, the average salt
use was 3.6 lb/1,000 gal, corresponding to a salt cost of $0.27/1,000 gal. This salt cost was almost 50%
lower than that ($0.49/1,000 gal) at Fruitland, ID. The lower salt use rate and the cheaper salt unit price
are the two factors contributing to the lower salt cost at Vale. The average salt use rate was 3.6 lb/1,000
gal at Vale vs 4.4 lb/1,000 gal at Fruitland (due to an improper flow control of brine draw at Fruitland).
The unit salt price was $0.076/lb at Vale vs $0.11/lb at Fruitland because Vale purchased salt in bulk
quantities (i.e., half a truck load for two 11-ton saturators), which was cheaper than smaller quantities. If
more storage capacity is added to allow delivery of a full truck load, then the overall salt cost can be
further reduced. In addition, the Vale IX system adopted a caustic cleaning procedure every four months
to prevent resin fouling. Each cleaning consumed two 55-gal drums of caustic soda (each 700 Ib), which
cost $882. Based on three cleanings in a year, the cost of the caustic soda is $2,646 or $0.02/1,000 gal.
Therefore, the sum of salt and caustic cost is $0.29/1,000 gal.
Table 4-24. O&M Cost for Vale, OR Treatment System
Cost Category
Volume Processed (1000 gal/year)
Value
111,100
Assumptions
Based on 9.5 hr/day and 534 gpm flowrate
Salt Usage
Salt Unit Price ($/lb)
Total Salt Usage (Ib/year)
Salt Use (lb/1,000 gal)
Total Salt cost ($/year)
Unit Salt Use Cost ($/l,000 gal)
Caustic Soda Unit Price ($/lb)
Total Caustic Usage (Ib/year)
Total Caustic cost ($/year)
Unit Caustic Cost ($/l,000 gal)
Sum of Salt and Caustic Cost ($/l,000 gal)
0.076
397,100
3.6
30,180
0.27
0.63
4,200
2,646
0.02
0.29
-
Quantity delivered
-
-
-
Delivery charge included
Three cleanings, each using 1,400
Ib of caustic
-
-
-
Electricity Consumption
Power Use ($/l, 000 gal)
0.028
Monthly electric bill increased by
$250
Labor
Average Weekly Labor (hr/wk)
Total Labor Hours (hr/year)
Total Labor Cost ($/year)
Labor Cost ($/l, 000 gal)
Total O&M Cost/1,000 gal
3.33
173.33
3,640
0.034
0.35
40 min/day; 5 day/wk
52 week a year
Labor rate = $2 1/hr
-
-
Incremental electricity consumption associated with the IX system was estimated based on the monthly
electricity bill before and after the system startup. For example, the electricity bill at the treatment plant
90
-------
was approximately $850 a month in 2006 and increased by 29% to $1,100 a month in 2007. Thus, the
annual increase was $3,000, or $0.028/1,000 gal.
The routine, non-demonstration related labor activities consumed about 40 min/day, five days a week.
Based on this time commitment and a labor rate of $21/hr, the annual labor cost was $3,640, or
$0.034/1,000 gal. In sum, the total O&M cost was approximately $0.35/1,000 gal.
91
-------
5.0 REFERENCES
Battelle. 2004. Revised Quality Assurance Project Plan for Evaluation of Arsenic Removal Technology.
Prepared under Contract No. 68-C-00-185, Task Order No. 0029, for U.S. Environmental
Protection Agency, National Risk Management Research Laboratory, Cincinnati, OH.
Battelle. 2006. Study Plan for Evaluation of Arsenic Removal Technology at Vale, OR. Prepared under
Contract No. 68-C-00-185, Task Order No. 0029, for U.S. Environmental Protection Agency,
National Risk Management Research Laboratory, Cincinnati, OH.
Boodoo, F. 2004. "Multi -Contaminant Control with Ion Exchange." Water Technology Magazine ,
5(27).
Boodoo, F., G. Schreiber, T. Satchell, L. Benton, B. Szczesny, E. Woo, D. Mielke. 2008. "Simultaneous
Ion Exchange Removal of Arsenic, Nitrate, Uranium, and TOC at City of McCook, NE." AWWA
Inorganic Contaminants Workshop, Albuquerque, NM.
Chen, A.S.C., L. Wang, J.L. Oxenham, and W.E. Condit. 2004. Capital Costs of Arsenic Removal
Technologies: U.S. EPA Arsenic Removal Technology Demonstration Program Round 1.
EPA/600/R-04/20 1 . U.S. Environmental Protection Agency, National Risk Management
Research Laboratory, Cincinnati, OH.
Clifford, D. A. 1999. "Ion Exchange and Inorganic Adsorption." Chapter 9 in R. Letterman (ed.), Water
Quality and Treatment Fifth Edition. McGraw Hill, Inc., New York, NY.
Clifford, D.A., C.C. Lin, L.L. Horng, and J.V. Boegel. 1987. Nitrate Removal from Drinking Water in
Glendale, Arizona. EPA/600/52-86/107, U.S. Environmental Protection Agency, National Risk
Management Research Laboratory, Cincinnati, OH.
Clifford, D.A, G. Ghurye, and A.R. Tripp. 2003. "Arsenic Removal from Drinking Water Using Ion-
Exchange with Spent Brine Recycling." JAWWA, 95(6): 119-130.
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." JAWWA, 90(3): 103-1 13.
Ghurye, G.L., D.A. Clifford, and A.R. Tripp. 1999. "Combined Arsenic and Nitrate Removal by Ion
:' JAWWA, 91(10): 85-96.
Kinetico, 2006. Operation and Maintenance Manual, IX-263-As/N Arsenic/Nitrate Removal System,
Kinetico.
EPA. 2001. National Primary Drinking Water Regulations: Arsenic and Clarifications to Compliance
and New Source Contaminants Monitoring. Federal Register, 40 CFR Parts 9, 141, and 142.
EPA. 2002. Lead and Copper Monitoring and Reporting Guidance for Public Water Systems .
EPA/816/R-02/009. U.S. Environmental Protection Agency, Office of Water, Washington, D.C.
EPA. 2003. Minor Clarification of the National Primary Drinking Water Regulation for Arsenic. Federal
Register, 40 CFR Part 141.
92
-------
Wang, L., W.E. Condit, and A.S.C. Chen. 2004. Technology Selection and System Design: U.S. EPA
Arsenic Removal Technology Demonstration Program Round 1. EPA/600/R-05/001. U.S.
Environmental Protection Agency, National Risk Management Research Laboratory, Cincinnati,
OH.
Wang , L., A.S.C. Chen, T.J. Sorg, and K.A. Fields. 2002. "Field Evaluation of As Removal by IX and
AA".JAWWA, 94(4): 161-173.
Wang, L., and A.S.C. Chen. 2010. U.S. EPA Arsenic/Nitrate Removal Technology Demonstration at
Fruitland, ID. EPA/600/R-10/152. U.S. Environmental Protection Agency, National Risk
Management Research Laboratory, Cincinnati, OH.
93
-------
APPENDIX A
Vale Arsenic System IX Resin Cleaning Procedure
-------
VALE ARSENIC SYSTEM IX RESIN CLEANING PROCEDURE
Original (Revision 2) provided by Kinetico on September 21, 2007
Revision 3 provided by Battelle in June 2009
Revision 4 provided by Battelle in February 2010
Step 1: Add sodium hydroxide (NaOH) to brine day tank
a. Make sure that brine day tank level is between low and low-low float so that there is enough
room for adding NaOH.
b. Using a drum pump to add two 55-gal drums of 50% NaOH to the day tank. Be sure to add
all 110 gal of NaOH to the tank. To assist in mixing, turn on brine refill valve and pump
while NaOH is being added. Slow down brine refill as needed to ensure that all NaOH is
used.
c. After brine day tank is full, close brine refill valve and turn off brine transfer pump.
Step 2: Verify flow configuration
a. Verify that valves and the PLC are set to co-current regeneration (valve #HV9 is open and
valve #HV 10 is closed).
Step 3: Update/change slow rinse setpoint
a. Change slow rinse time from 45 to 75 min using touch screen. The extra 30 min is provided
for resin soak in Step 5. Go to setpoint screen, touch the box next to slow rinse time, type in
75, and press enter key.
Step 4: Begin cleaning Vessel (A or B)
a. Start a regeneration using pushbutton for the selected vessel
Step 5: Soak resin bed
a. When brine draw on the selected vessel is finished (21 min), manually close valve #HV9.
b. Using slow rinse timer on the screen as the clock, allow resin to soak in caustic/brine solution
for 30 min.
Step 6: Rinse resin bed
a. After 30 min have elapsed, 45 min will be showing on slow rinse timer, manually open valve
#HV9 to allow slow rinse and fast rinse to proceed automatically.
Step 7: Repeat for other vessel
a. When the selected vessel regeneration is finished, repeat steps 4 to 6 for the other vessel.
Step 8: Reset slow rinse setpoint
a. When both vessels have been regenerated, change slow rinse time back to 45 min. Using
touch screen to go to setpoint screen and touch box next to slow rinse time. Another box will
appear, type in 45 and press enter key.
Step 9: Check brine draw setpoint, (fresh brine only, no brine recycle)
a. While in setpoint screen, make sure that second (fresh) brine draw time is set at 21 min. This
will provide approximately 500 gal of fresh brine during regeneration.
Step 10: Reset total volume setpoint
A-l
-------
a. Go to filter setpoint screen, press box next to total volume regen button and type in desired
setpoint (e.g., 600,000 gal) and press enter key.
Step 11: Perform back to back regeneration
a. Repeat regeneration using pushbutton for each vessel; let both vessels regenerate
automatically.
Step 12: Return system to service.
Step 13: Continue sampling
a. Sample effluent for arsenic and nitrate from each vessel during first 30,000 to 80,000 gal and
again at 400,000 to 480,000 gal.
A-2
-------
APPENDIX B
Vale, OR Project Chronology
-------
VALE, OR PROJECT CHRONOLOGY
09/19/06: Study data collection begun.
09/19/06 - 09/22/06: Run length special study showed significantly lower than designed run
length to As 10-(ig/L breakthrough at 600,000 gal and higher than designed salt usage during
regeneration events.
09/27/06: Punch list items issued to Kinetico for resolution.
02/21/07: Meeting with Kinetico and EPA at Battelle to discuss performance issues and punch
list items.
02/28/07 - 03/07/07: Kinetico was onsite to collect ion exchange resin samples for Purolite's
analysis, install a fresh brine pump in place of the eductor system, and address punch list items.
Ion exchange system was unexpectedly changed to counter-current mode by technician (not
planned).
03/09/07: Kinetico indicated no record of vessel fill with polymer beads, which was required for
counter-current mode and agreed to change back to co-current mode. Action items resolved were
fresh brine pump installation and fresh brine totalizer replacement.
03/12/07: System was returned to co-current operation and continued to exhibit short run lengths
to 10 (ig/L breakthrough after this visit even though design salt loading had been achieved.
04/16/07: Regular weekly sampling was discontinued until performance issues resolved. Battelle
requested reduced regeneration frequency from 600,000 gal to 370,000 gal on April 16, 2007 to
maintain ion exchange performance to below 10 (ig/L MCL.
05/18/07: Kinetico and Purolite discussed that tests on Vale and Fruitland resin indicated organic
matter buildup on the IX resin, which might have affected the IX resin performance. Kinetico
and Purolite tested a caustic/brine cleaning procedure in the laboratory and recommended
implementing the procedure in the field at Fruitland and then at Vale.
06/19/07: Fruitland caustic wash was conducted, Vale operators invited to attend for observation
purposes, decision was made to wait on results of Fruitland wash before moving forward at Vale.
07/10/07: Operator replaced fresh brine pump that failed.
07/16/07: Limited weekly sampling (at TT location only) resumed at Vale per EPA request.
10/22/07: Caustic wash was performed at Vale by Kinetico, post-caustic wash resin samples
were collected, and reused brine was turned off
10/24/07 to 10/26/07: Post-caustic wash run length special study was conducted immediately on
first run after caustic wash. Run length at 445,722 gal.
12/10/07: PLC updates were made to allow for reused brine regeneration to be turned off.
12/14/07: Post-caustic wash resin sample results were received from Purolite.
01/14/08: Ion exchange system was shut down for well rehabilitation and weekly limited
sampling efforts were discontinued.
02/14/08: After reviewing Purolite's resin analyses and run length study results, Kinetico
recommended further caustic washing to reduce fouling of the IX resin and suggested that the
reused brine system components be used for a periodic, manual cleaning cycle.
B-l
-------
04/11/08: Battelle held a conference call with Kinetico and requested that it look into alternate
IX resin selection (including TOC scavenging resin) and the feasibility of converting the system
to adsorption and/or coagulation filtration.
04/22/08: The City of Vale initiated pumping from lagoon after one-time approval from the State
of Oregon to pump the wastewater in the lagoon to the airport grounds in order to lower the water
level in the pond.
05/01/08: The City of Vale informed Battelle that the treatment system would be restarted on
May 1, 2008 at the 600,000-gal regeneration interval.
05/07/08: Kinetico responded that they would not be able to provide services to reconfigure the
treatment system to another process per EPA request and that they were willing to provide a
credit in lieu of one more trip to the site for a caustic wash.
05/09/08: Battelle contacted Purolite to provide a run length simulation for the Purolite resin
A850 suggested by Dennis Clifford of University of Houston.
05/15/08: Francis Boodoo of Purolite responded with an alternate suggestion for replacing the
resin bed with new PFA300E and atop protective layer of a special grading of A850 known as
A850END.
06/04/08: Battelle received a revised run length simulation and cost quote from Purolite for its
proposed new resin design configuration of $50,000 including 95 ft3 of PFA300E (for
arsenic/nitrate removal) and 15 ft3 of A850End (for TOC scavenging) in one vessel. The
estimated run length was equivalent to 639,000 gal (523 BV adjusted based on 163.3 ft3 of
A300E resin).
07/15/08: Battelle held a meeting with EPA, Kinetico, and the City in Columbus, OH to discuss
next steps for the project and to troubleshoot IX treatment system performance. Dennis Clifford
and Glen Latimer were in attendance to provide consultation support.
07/23/08: The city collected additional source water samples on July 23, 2008, from the
combined inlet and each of the individual seven wells for analysis of key parameters. These
results were later provided to Purolite to update the IX simulation.
08/15/08: Battelle visited Vale and worked with the operator to view the inside of the IX vessels
and collect IX resin samples and spent filter samples. Battelle also observed a regeneration cycle
and recorded salt usage parameters.
08/25/08: Battelle visited McCook to collect IX resin samples from the dual resin vessels and
perform an elution study on both service and regeneration cycles for arsenic, nitrate, and more.
11/07/08: Purolite provided a quote for the new IX resin resins on November 7, 2008 and
Battelle coordinated with Purolite to set up the purchase order.
11/19/08: TraceDetect installed the ArsenicGuard system.
11/19/08: Purolite reported that the Vale IX resin samples had moderate fouling by silica with
Vessel A at 1,375 ppm SiO2 and Vessel B at 2,500 ppm SiO2.
11/20/08: A Purolite local rep, Steve Soldatek, visited Vale on November 20, 2008, to inspect the
system and investigate optimizing salt usage and wastewater regeneration. However, Steve
Soldatek indicated that he did not have a chance to run any elution tests because the city was
having some issues with the wellhead pumps.
12/08/08: A special run length study was performed on the fouled IX resin from December 8 to
10, 2008. The results of this study indicated that 10-(ig/L arsenic breakthrough continued to
B-2
-------
occur at a relatively low bed volume (323,531 gal), which is 27% lower than the post-caustic
wash run length of 445,722 gal in October 2007. The operator continued to operate the treatment
system through 600,000 gal due to wastewater generation issues.
02/19/08: Purolite shipped A300E and A850END IX resins to Vale, which arrived on December
26, 2008.
01/14/09: Purolite issued an updated run length simulation for the dual IX resin beds based on
the water quality samples collected in July 2008. The simulation results were comparable to the
simulation results provided based on previous water quality samples in June 2008. Purolite run
length estimate was 738,000 gal (604 BV adjusted based on 163.3 ft3 of A300E resin).
02/10/09 to 02/13/09: Tom Jadach of Accurate Water Solutions was onsite to remove original IX
resin, load new resins, and restart the system. Tom Jadach reported lower-than-designed IX resin
volumes.
02/13/09 to 03/02/09: Monitored effluent arsenic levels via ArsenicGuard system.
03/2/09 to 03/4/09: Battelle was onsite to conduct an elution study and a run length study. Due
to an incident that occurred during the salt loading, the studies were compromised and had to be
postponed until later.
03/25/09: Weekly sampling resumed.
04/21/09: The run length study was conducted by the operator starting on this date.
04/23/09: The operator informed Battelle that the City was switching salt suppliers from Handy
Wholesale to Western Step Savers.
06/24/09: One week prior to a scheduled visit by Battelle, the operator performed a caustic wash
on the dual IX resin beds.
06/28/09 to 06/30/09: Battelle was onsite to conduct the elution and run length studies originally
scheduled for March 2009.
07/13/09: Eight drums of A300E (including two off-color drums) were picked-up by Smith's
Pack & Ship to be returned to Pulrolite's warehouse in Santa Fe Springs, CA, for refund.
07/21/09: Drums arrived at Purolite warehouse in Santa Fe Springs, CA
08/12/09: Battelle received notification from Steve Soldatek that the refund payment for the
returned resin would be issued that week.
10/16/09: The operator performed a caustic wash on the dual IX resin beds.
12/22/09: The operator informed Battelle that the treatment system was bypassed because of a
faulty flow sensor. The operator was in contact with Tom Jadach of Accurate Water Solutions to
place an order for the new sensor.
01/15/10: The operator replaced the main flow sensor and put the system back online.
B-3
-------
APPENDIX C
OPERATIONAL DATA
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period I)
Parameters
Unit
1
2
3
4
5
6
7
8
9
10
11
12
13
09/18/06
09/19/06
09/20/06
09/21/06
09/22/06
09/25/06
09/26/06
09/27/06
09/28/06
10/02/06
10/04/06
10/05/06
10/06/06
10/09/06
10/10/06
10/11/06
10/12/06
10/13/06
10/16/06
10/17/06
10/18/06
10/20/06
10/23/06
10/25/06
10/26/06
10/27/06
10/30/06
11/01/06
1 1/02/06
1 1/03/06
1 1/06/06
1 1/07/06
1 1/08/06
1 1/09/06
11/13/06
11/14/06
11/15/06
11/16/06
11/17/06
1 1/20/06
11/21/06
1 1/27/06
1 1/28/06
1 1/29/06
12/04/06
12/05/06
12/06/06
12/07/06
12/08/06
12/11/06
12/12/06
12/13/06
Pump
Hour
Meter
hr
NR
NR
NR
NR
NR
NR
NR
1,467
1,476
1,519
1,540
1,550
1,560
1,585
1,599
1,607
1,615
1,628
1,655
1,661
1,671
1,675
1,704
1,723
1,731
1,739
1,768
1,783
1,792
1,803
1,822
1,831
1,844
1,852
1,879
1,885
1,889
1,898
1,908
1,932
1,934
1,987
1,997
2,008
2,045
2,053
2,062
2,066
2,078
2,102
2,115
2,118
Daily
Hour
hr/day
NR
NR
NR
NR
NR
NR
NR
NR
7.3
11.1
9.9
11.3
9.9
8.6
13.4
8.5
7.6
13.0
8.9
5.9
10.6
2.1
10.0
8.3
8.7
7.8
9.5
8.1
8.6
11.8
6.3
8.8
11.7
7.0
7.0
7.5
3.5
10.8
8.7
8.0
1.9
9.1
9.5
10.7
7.6
8.0
8.5
4.3
11.5
7.9
13.8
4.0
Master
Totalizer
kgal
NR
NR
NR
NR
NR
NR
NR
562
562
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
450
721
1,063
1,789
NR
2,520
2,904
3,478
3,734
4,163
4,383
5,248
5,435
5,580
5,838
6,166
6,887
6,962
8,588
8,895
9,237
10,362
10,627
10,873
11,016
11,363
12,119
12,492
12,611
Daily
Volume
gP
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period I) (Continued)
I
15
16
19
20
22
24
25
26
'arameters
Unit
12/14/06
12/15/06
12/18/06
12/19/06
12/20/06
12/21/06
12/26/06
12/27/06
12/29/06
01/02/07
01/03/07
01/05/07
01/08/07
01/10/07
01/11/07
01/12/07
01/16/07
01/17/07
01/18/07
01/19/07
01/22/07
01/23/07
01/24/07
01/30/07
01/31/07
02/02/07
02/06/07
02/07/07
02/08/07
02/09/07
02/12/07
02/13/07
02/14/07
02/15/07
02/16/07
02/19/07
02/20/07
02/21/07
02/23/07
02/26/07
02/27/07
02/28/07
03/01/07
03/02/07
03/06/07
03/08/07
03/09/07
03/12/07
03/14/07
03/16/07
03/19/07
03/20/07
Pump
Hour
Meter
hr
2,126
2,134
2,161
2,170
2,176
2,185
2,227
2,235
2,248
2,279
2,290
2,304
2,328
2,343
2,354
2,361
2,395
2,401
2,412
2,421
2,450
2,461
2,468
2,516
2,524
2,544
2,575
2,584
2,593
2,601
2,625
2,635
2,642
2,651
2,658
2,682
2,691
2,702
2,715
2,741
2,747
2,758
2,766
2,774
2,809
2,827
2,835
2,858
2,875
2,894
2,919
2 925
Daily
Hour
hr/day
7.7
7.1
9.0
7.9
8.0
7.6
8.7
6.6
7.1
7.6
10.3
7.5
7.9
8.1
9.0
6.3
9.0
5.6
9.8
8.9
10.2
9.6
9.7
8.0
6.8
9.3
8.2
10.1
6.4
9.5
8.1
11.3
5.9
10.5
6.0
8.3
8.6
9.4
7.6
8.9
6.0
8.6
11.6
7.6
8.5
8.4
8.2
8.0
8.6
9.5
8.4
5.6
Master
Totalizer
kgal
12,880
13,084
13,901
14,212
14,402
14,673
15,968
16,223
16,633
17,599
17,930
18,403
19,115
19,605
19,923
20,098
21,140
21,326
21,698
21,972
22,857
23,187
23,439
24,940
25,148
25,799
26,786
27,099
27,337
27,622
28,353
28,666
28,898
29,186
29,480
30,138
30,453
30,768
31,202
31,995
32,191
32,536
32,795
33,046
34,133
34,664
34,920
35,648
36,173
36,759
37,514
37,709
Daily
Volume
gP
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period I) (Continued)
I
30
31
34
35
37
38
'arameters
Unit
03/21/07
03/23/07
03/26/07
03/27/07
03/29/07
03/30/07
04/02/07
04/03/07
04/05/07
04/06/07
04/09/07
04/10/07
04/1 1/07
04/12/07
04/13/07
04/16/07
04/17/07
04/18/07
04/19/07
04/20/07
04/23/07
04/24/07
04/26/07
04/27/07
05/01/07
05/02/07
05/03/07
05/04/07
05/07/07
05/08/07
05/09/07
05/10/07
05/1 1/07
05/14/07
05/16/07
05/18/07
05/21/07
05/22/07
05/24/07
05/25/07
05/29/07
05/30/07
05/31/07
06/04/07
06/05/07
06/06/07
06/07/07
06/08/07
06/1 1/07
06/12/07
06/14/07
06/15/07
Pump
Hour
Meter
hr
2,937
2,954
2,981
2 992
3,007
3,020
3,047
3,056
3,079
3,091
3,119
3,126
3,135
3,146
3,153
3,178
3,189
3,199
3,209
3,217
3,248
3,259
3,283
3,291
3,343
3,354
3,363
3,374
3,405
3,421
3,430
3,446
3,459
3,497
3,526
3,556
3,600
3,612
3,639
3,653
3,710
3,719
3,735
3,797
3,812
3,825
3,836
3,849
3,884
3,893
NR
NR
Daily
Hour
hr/day
10.8
9.0
9.2
10.1
7.8
10.4
9.8
9.2
10.2
12.6
9.3
8.5
8.2
9.0
9.4
8.5
10.7
9.7
9.3
8.9
10.4
10.5
12.2
8.1
12.2
13.3
9.3
9.1
11.2
14.2
10.9
14.7
13.5
12.6
14.9
15.0
13.4
14.8
14.1
14.4
13.3
11.9
16.8
15.6
15.1
12.9
11.8
11.8
11.6
9.8
NR
NR
Master
Totalizer
kgal
38,076
38,587
39,441
39,761
40,231
40,621
41,461
41,722
42,393
42,786
43,648
43,824
44,096
44,427
44,656
45,422
45,722
45,997
46,282
46,544
47,472
47,755
48,456
48,715
50,223
50,521
50,806
51,118
52,038
52,490
52,744
53,218
53,627
54,734
55,575
56,450
57,761
58,106
58,899
59,320
60,985
61,259
61,717
63,553
64,015
64,387
64,700
65,076
66,103
66,377
67,197
67,569
Daily
Volume
gP
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period I) (Continued)
Parameters
Unit
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
06/18/07
06/19/07
06/20/07
06/21/07
06/22/07
06/25/07
06/27/07
06/28/07
06/29/07
07/02/07
07/03/07
07/05/07
07/06/07
07/09/07
07/10/07
07/1 1/07
07/12/07
07/13/07
07/16/07
07/18/07
07/19/07
07/20/07
07/23/07
07/25/07
07/26/07
07/30/07
08/01/07
08/02/07
08/03/07
08/06/07
08/07/07
08/08/07
08/09/07
08/10/07
08/14/07
08/15/07
08/17/07
08/21/07
08/24/07
08/28/07
08/29/07
08/30/07
09/04/07
09/1 1/07
09/12/07
09/14/07
09/17/07
09/24/07
09/26/07
10/01/07
10/04/07
10/08/07
Pump
Hour
Meter
hr
3,974
3,989
4,005
4,019
4,031
4,067
4,101
4,112
4,125
4,170
4,182
4,212
4,228
4,269
4,287
4,301
4,314
4,326
4,365
4,391
4,404
4,418
4,452
4,471
4,483
4,530
4,550
4,562
4,576
4,608
4,623
4,632
4,644
4,649
NR
4,704
4,722
4,754
4,786
4,823
4,835
4,845
4,883
4,945
4,957
4,974
4,997
5,048
5,065
5,100
5,126
5,161
Daily
Hour
hr/day
12.9
15.1
16.5
14.6
14.5
11.8
15.6
12.3
15.1
13.9
13.3
16.1
16.7
13.4
15.4
14.6
14.7
12.1
12.7
12.9
13.9
13.4
11.0
10.5
11.2
11.4
11.1
9.6
18.2
10.7
11.7
12.2
9.4
7.6
NR
10.6
8.8
8.5
10.5
9.3
10.1
8.8
7.6
9.2
10.2
8.6
8.1
7.3
7.5
7.4
8.1
9.3
Master
Totalizer
kgal
68,722
69,155
69,646
70,036
70,370
71,458
72,410
72,758
73,136
74,425
74,759
NR
76,095
77,267
77,757
78,175
78,553
78,917
80,035
80,806
81,204
81,597
82,623
83,153
83,522
84,899
85,494
85,994
86,270
87,204
87,641
87,886
88,238
88,409
89,581
89,999
90,520
91,430
92,359
93,456
93,807
94,067
95,161
96,937
97,276
97,760
98,398
99,858
100,324
101,328
102,063
103,087
Daily
Volume
gP
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period I) (Continued)
Parameters
Unit
57
58
59
61
62
63
64
65
66
67
68
69
70
10/09/07
10/11/07
10/17/07
10/18/07
10/19/07
10/22/07
10/26/07
10/29/07
10/31/07
11/13/07
11/14/07
11/15/07
11/16/07
11/19/07
1 1/20/07
1 1/26/07
1 1/27/07
1 1/30/07
12/03/07
12/04/07
12/05/07
12/06/07
12/07/07
12/10/07
12/11/07
12/13/07
12/14/07
12/17/07
12/18/07
12/19/07
12/20/07
12/21/07
12/24/07
12/26/07
12/27/07
12/28/07
12/31/07
01/02/08
01/03/08
01/04/08
01/07/08
01/08/08
01/09/08
01/10/08
01/11/08
01/14/08
Pump
Hour
Meter
hr
5,172
5,195
5,257
5,266
5,277
5,301
5,329
5,353
5,371
5,427
5,433
5,444
5,450
5,473
5,481
5,527
5,533
5,559
5,579
5,586
5,596
5,603
5,608
5,633
5,641
5,655
5,663
5,685
5,696
5,705
5,711
5,718
5,741
5,757
5,768
5,776
5,797
5,815
5,820
5,831
5,855
5,862
5,870
5,878
5,885
5,907
Daily
Hour
hr/day
11.1
10.7
10.5
9.6
9.4
8.4
6.9
8.4
8.7
4.2
7.9
9.0
7.8
7.6
8.5
7.6
5.9
8.3
6.9
8.1
8.5
6.5
7.0
8.0
8.8
6.9
7.6
7.5
8.8
8.9
7.5
7.5
7.6
8.1
10.6
7.7
7.1
8.8
5.7
10.2
8.2
5.7
8.8
8.9
7.0
7.5
Master
Totalizer
kgal
103,377
104,032
105,798
106,060
106,390
107,113
107,853
108,624
109,183
110,543
110,713
111,069
111,243
111,921
112,180
113,568
113,747
114,523
115,114
115,350
115,601
115,815
115,966
116,671
116,897
117,359
117,596
118,258
118,605
118,887
119,068
119,293
0
119,998
120,306
120,543
121,160
121,687
121,865
122,162
122,907
123,128
123,351
123,575
123,796
124,475
Daily
Volume
gpd
310,253
300,478
300,596
273,391
273,103
258,985
181,688
263,402
273,796
102,803
224,587
281,670
225,730
230,809
262,648
230,799
179,000
245,053
205,565
248,967
215,143
192,000
211,107
230,727
233,290
234,667
212,636
228,879
283,909
259,476
242,456
240,000
NR
NR
289,882
237,000
211,795
261,683
178,000
290,939
246,621
181,851
272,136
250,047
219,476
224,928
Booster
Pump
Pressure
(PT4)
psig
59
0
58
58
58
2
58
58
57
0
58
58
58
8
58
10
58
58
58
10
58
NM
10
9
59
2
57
3
3
57
57
3
10
59
3
59
3
4
3
59
59
6
2
10
10
9
System
Inlet
Pressure
(PT1)
psig
47
0
53
53
53
2
52
52
52
0
48
47
43
7
47
10
47
47
44
10
43
NM
10
9
42
2
52
2
2
52
52
2
9
53
2
53
2
4
2
48
49
6
1
10
10
9
Tank A
Outlet
Pressure
psig
37
3
42
42
42
1
42
42
42
0
38
38
37
1
38
4
38
37
38
2
34
NM
12
2
35
3
40
0
0
40
40
0
11
42
0
38
4
6
4
38
38
7
0
10
12
0
TankB
Outlet
Pressure
psig
37
3
42
42
42
4
42
42
42
0
38
38
37
0
38
4
32
32
38
2
33
NM
12
0
32
3
39
0
0
40
40
0
11
42
0
38
4
6
4
37
40
7
4
12
12
0
Product
Water
Pressure
psig
11.5
2.0
11.5
12.0
11.5
0.0
12.5
12.5
12.5
0.0
12.5
12.5
12.5
9.0
12.0
11.0
12.0
12.0
12.5
11.0
11.0
NM
11.0
10.0
12.5
3.0
12.5
2.5
2.5
12.0
12.0
12.0
11.0
11.5
4.0
12.0
4.0
6.0
4.0
11.5
12.0
6.5
3.0
12.0
11.5
10.0
Finished
Water
Flowrate
gpm
518
NR
549
513
543
NR
529
535
540
NR
531
520
518
NR
520
NR
515
500
490
NR
513
520
NR
NR
510
NR
530
NR
NR
525
545
NR
NR
560
NR
530
NR
NR
NR
545
515
NR
NR
NR
NR
NR
Finished
Water
Volume
Since Last
Regen
gal
192,807
22,197
313,849
170,643
90,330
377,889
481,370
595,337
514,266
573,610
131,979
461,098
22,399
50,196
289,615
368,683
533,870
109,755
51,996
267,669
162,353
359,550
498,457
530,622
124,577
553,516
202,940
200,373
521,946
167,120
334,440
542,942
577,116
580,390
247,665
467,584
420,181
292,510
457,264
118,761
195,150
399,702
606,504
197,588
403,332
418,136
BV
Treated
Since Last
Regen.
BV
138.6
16.0
225.6
122.7
64.9
271.6
346.0
427.9
369.6
412.3
94.9
331.4
16.1
36.1
208.2
265.0
383.7
78.9
37.4
192.4
116.7
258.4
358.3
381.4
89.5
397.8
145.9
144.0
375.2
120.1
240.4
390.2
414.8
417.2
178.0
336.1
302.0
210.2
328.7
85.4
140.3
287.3
435.9
142.0
289.9
300.5
Regen.
Counter
226
228
232
233
234
236
243
244
245
2
3
3
4
5
5
7
7
9
10
10
15
15
15
16
17
17
18
19
19
20
20
20
21
21
22
22
23
24
24
25
26
26
27
27
27
28
Regen
Water
Totalizer
(Per Event)
gal
13,735
13,687
13,656
14,298
14,296
707
15,508
7,802
7,833
7,644
7,646
7,646
7,607
7,683
NM
7,663
7,663
7,637
7,582
7,582
14,721
14,721
14,721
14,748
14,664
14,664
15,543
15,638
15,638
15,647
NM
NM
15,652
15,652
14,282
NM
15,134
15,251
15,251
15,235
15,164
15,160
2,078
15,346
15,346
15,396
Fresh Brine
Day Tank
Totalizer
gal
102,580
103,924
106,622
107,295
107,974
108,835
111,987
112,505
113,040
114,160
114,725
114,725
115,275
115,850
NR
116,995
NR
118,068
118,625
NR
120,265
NR
120,265
120,800
121,860
121,860
122,915
123,972
NR
125,030
NR
NR
126,084
126,084
126,610
NR
127,652
128,662
128,662
129,706
130,750
130,750
131,280
131,790
131,790
132,815
Reused
Brine Day
Tank
Totalizer
gal
315,762
317,818
321,460
322,505
323,541
325,081
325,628
323,605
325,610
325,610
325,601
325,607
325,607
323,610
NR
323,610
NR
NR
323,625
NR
325,608
NR
325,608
325,610
NR
325,609
NR
325,610
NR
325,610
NR
NR
325,609
325,609
325,609
NR
325,610
325,610
325,610
325,610
325,610
325,610
325,610
325,610
325,610
325,610
NR = not recorded
1 BV= 186ft3
o
-------
US EPA Arsenic Demonstration Project at Vale, OR - Daily System Operation Log Sheet (Study Period II)
Parameters
Unit
1
3
4
5
6
7
8
10
11
12
13
14
15
16
17
20
21
02/16/09
02/17/09
02/18/09
03/02/09
03/03/09
03/04/09
03/05/09
03/09/09
03/1 1/09
03/12/09
03/18/09
03/25/09
03/26/09
03/31/09
04/01/09
04/02/09
04/03/09
04/06/09
04/07/09
04/08/09
04/20/09
04/21/09
04/22/09
04/23/09
04/24/09
04/28/09
04/30/09
05/01/09
05/04/09
05/05/09
05/06/09
05/08/09
05/12/09
05/13/09
05/14/09
05/19/09
05/22/09
05/26/09
05/27/09
05/28/09
05/29/09
06/03/09
06/05/09
06/08/09
06/09/09
06/10/09
07/01/09
07/02/09
07/06/09
07/08/09
07/09/09
07/10/09
Pump Hour
Meter
hr
8,739.8
8,746.7
8,754.1
8,846.9
8,847.5
8,855.5
8,859.0
8,887.6
8,901.5
8,909.6
8,953.1
9,005.9
9,017.9
9,050.9
9,061.9
9,066.6
9,073.8
9,097.9
9,121.7
9,128.4
9,229.6
9,238.9
9,254.6
9,268.8
9,275.9
9,320.1
9,341.5
9,352.0
9,377.9
9,387.3
9,393.1
9,409.6
9,451.5
9,461.0
9,474.1
9,528.1
9,570.4
9,585.3
9,599.6
9,615.0
9,633.0
9,694.9
9,720.5
9,748.6
9,755.5
9,767.2
9,993.7
9,996.3
10,053.3
10,082.8
10,097.0
10,116.1
Daily
Hour
hr/day
NR
8.5
6.2
7.9
0.6
8.8
2.8
7.1
7.0
11.3
6.7
7.7
9.4
6.9
9.1
6.4
7.4
7.8
26
6.8
8.3
11.7
15.7
12.4
7.7
11.2
10.3
11.0
8.6
7.8
7.5
8.2
10.0
8.8
12.8
11.4
13.0
4.0
14.5
17.0
14.4
13.0
12.8
9.3
7.2
10.2
10.7
3.0
14.4
14.7
14.7
15.9
Master
Totalizer
kgal
208,128
208,342
208,583
211,433
211,452
211,612
211,786
212,676
213,085
213,347
214,675
216,260
216,647
217,630
217,987
218,136
218,330
219,068
219,794
220,010
223,092
223,453
223,861
224,318
224,509
225,856
226,509
226,847
227,643
227,907
228,093
228,586
229,856
230,156
230,538
232,153
233,873
234,573
234,993
235,450
235,989
237,900
238,640
239,499
239,720
240,055
246,822
246,907
248,600
249,502
249,915
250,487
Daily
Volume
gal/ day
NR
263,385
202,947
243,416
19,683
175,878
141,559
220,966
205,213
364,522
205,958
231,246
302,049
206,495
295,448
204,343
200,258
238,545
220,596
252,020
456,000
408,000
398,836
208,364
342,095
315,015
352,696
265,333
220,383
241,297
244,800
304,293
276,923
374,204
340,997
526,979
185,635
424,421
504,276
431,200
400,559
370,000
284,359
230,609
292,364
320,964
99,512
427,705
448,663
426,323
477,496
Booster
Pump
Pressure
(FT 4)
psig
60
11
58
59
20
59
9
59
58
58
59
59
9
10
58
58
10
9
10
9
58
10
5
10
NA
10
58
10
58
58
59
58
59
NA
NA
9
59
2
59
9
59
9
10
11
10
9
59
NA
NA
8
59
NA
System
Inlet
Pressure
(PT1)
psig
58
10
53
53
19
53
9
53
53
53
53
53
8
10
53
53
9
9
9
9
52
9
5
10
NA
10
52
10
52
52
52
52
52
NA
NA
9
54
1
52
9
52
8
9
10
9
9
52
NA
NA
8
51
NA
Tank A
Outlet
Pressure
psig
48
12
42
43
16
43
11
43
43
43
43
42
10
11
42
41
11
10
11
11
43
11
8
11
NA
8
41
NA
41
43
43
43
42
NA
NA
11
42
NA
43
11
42
10
11
11
10
11
40
NA
NA
10
40
NA
TankB
Outlet
Pressure
psig
1
12
40
42
16
42
11
43
43
42
42
42
10
11
41
41
11
11
11
11
44
11
8
11
NA
2
40
NA
41
42
43
42
42
NA
NA
11
42
NA
42
11
42
10
11
12
11
11
38
NA
NA
10
40
NA
Product
Water
Pressure
psig
11.5
12.0
12.0
12.0
11.0
11.5
11.0
12.5
12.5
12.5
12.5
12.5
10.0
11.0
12.0
12.0
11.0
11.0
11.0
10.0
12.0
11.0
8.0
11.5
NA
11.0
12.0
12.0
13.0
12.5
12.5
12.5
12.5
NA
NA
11.0
12.5
NA
12.5
11.0
11.0
10.0
11.0
11.0
10.0
11.0
12.0
NA
NA
11.0
12.5
NA
Finished
Water
Flowrate
gpm
288
NR
547
545
260
532
NR
547
544
542
538
542
NR
NR
542
540
NR
NR
NR
NR
544
NR
NR
NR
NR
NR
545
NR
541
535
521
530
546
530
535
NR
530
NR
557
NR
530
NR
NR
NR
NR
NR
540
545
NR
NR
535
540
Finished
Water
Volume
Since Last
Regen
gal
11,619
207,050
428,634
564,199
581,683
184,164
284,169
480,300
236,500
476,392
457,846
59,084
416,060
84,260
414,217
551,090
109,993
171,948
22,448
424,882
70,972
404,067
162,061
584,472
140,650
145,268
126,680
440,049
557,387
181,123
353,486
189,355
125,277
402,920
138,366
434,234
381,710
806,720
769,698
172,559
52,930
587,423
34,114
212,475
417,977
108,900
344,380
412,530
138,378
357,543
122,440
33,650
BV
Treated
Since Last
Regen.
BV
8
141
291
383
395
125
193
326
161
324
311
40
283
57
281
375
75
117
15
289
48
275
110
397
96
99
86
299
379
123
240
129
85
274
94
295
259
548
523
117
36
399
23
144
284
74
234
280
94
243
83
23
Regen.
Counter
19
19
19
23
23
24
24
25
26
26
28
31
31
33
33
33
34
35
36
36
41
41
42
42
43
45
46
46
47
48
48
49
51
51
52
54
56
58
58
59
60
62
64
65
65
66
5
5
8
9
10
11
Regen Water
Totalizer (Per
Event)
gal
8,245
12,789
12,789
12,699
12,699
13,051
13,051
12,725
12,668
12,668
12,699
12,682
12,682
12,655
12,655
12,655
12,697
12,701
12,678
12,678
12,767
12,767
12,679
12,679
12,701
12,659
12,635
NR
12,622
12,632
12,632
12,613
12,640
NR
12,623
1,267
1,268
37,156
49,741
12,668
12,677
12,692
12,660
12,666
NR
12,630
1,842
NR
12,710
12,700
12,783
12,726
Fresh
Brine Day
Tank
Totalizer
gal
251,980
251,980
251,980
254,962
254,962
255,682
255,682
256,439
257,170
257,170
258,661
260,844
260,845
262,293
262,293
262,293
263,030
263,768
264,505
264,505
268,095
268,095
268,792
268,792
269,500
270,975
271,685
NR
272,420
273,168
273,168
273,908
275,382
276,110
277,567
279,035
279,775
280,452
281,170
281,890
283,340
284,721
285,424
286,104
293,400
295,490
296,160
296,835
297,525
o
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period II) (Continued)
Parameters
Unit
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
07/13/09
07/17/09
07/20/09
07/21/09
07/22/09
07/28/09
07/30/09
07/31/09
08/04/09
08/05/09
08/06/09
08/07/09
08/1 1/09
08/12/09
08/17/09
08/18/09
08/19/09
08/26/09
08/28/09
08/31/09
09/02/09
09/10/09
09/1 1/09
09/14/09
09/15/09
09/16/09
09/21/09
09/22/09
09/23/09
09/25/09
09/28/09
09/29/09
09/30/09
10/01/09
10/02/09
10/05/09
10/06/09
10/07/09
10/09/09
10/14/09
10/15/09
10/16/09
10/20/09
10/22/09
10/27/09
10/28/09
10/29/09
1 1/02/09
1 1/03/09
1 1/04/09
1 1/05/09
1 1/06/09
Pump Hour
Meter
hr
10,155.3
10,212.8
10,241.0
10,258.6
10,276.5
10,367.9
10,396.8
10,414.3
10,466.0
10,476.8
10,487.0
10,497.4
10,545.0
10,556.3
10,627.2
10,641.3
10,655.4
10,740.0
10,769.1
10,800.4
10,828.0
10,926.1
10,938.7
10,973.0
10,984.4
10,996.2
11,053.3
11,066.2
11,074.9
11,094.8
11,127.1
11,139.3
11,148.2
11,158.1
11,165.7
11,192.6
11,204.0
11,210.5
11,229.4
11,271.4
11,278.8
11,283.0
11,316.0
11,330.0
11,368.8
11,377.2
11,387.4
11,417.9
11,420.8
11,429.0
11,435.3
11,444.4
Daily
Hour
hr/day
14.1
13.6
10.2
16.1
15.8
15.9
13.4
17.7
13.0
9.0
12.6
11.6
11.2
13.2
14.5
12.9
14.4
12.2
12.8
11.2
12.8
12.6
10.9
11.7
10.1
13.8
11.6
11.9
9.5
8.8
11.8
12.0
9.0
10.0
7.4
9.0
11.2
6.4
9.5
8.3
7.5
4.7
NR
NR
7.4
8.5
9.5
7.6
4.0
8.7
6.0
9.2
Master
Totalizer
kgal
251,697
253,402
254,259
254,779
255,307
258,038
258,916
259,435
260,698
261,299
261,626
261,916
263,362
263,722
265,322
266,276
266,635
269,221
269,815
270,781
271,630
274,561
274,961
275,974
276,333
276,670
278,403
278,773
279,050
279,599
280,537
280,924
281,163
281,472
281,712
282,477
282,835
283,041
283,593
284,833
285,064
285,151
286,138
286,542
287,723
287,954
288,273
289,151
289,252
289,508
289,704
289,944
Daily
Volume
gal/ day
435,056
403,153
309,293
475,429
465,028
475,819
407,188
524,463
317,126
503,163
402,462
323,721
340,235
421,463
326,115
872,229
366,638
372,757
261,578
344,743
392,475
377,517
345,946
346,078
319,111
394,537
350,987
341,538
302,182
244,000
343,695
379,102
241,516
312,253
235,102
255,000
350,694
201,796
278,905
243,934
232,615
96,369
NR
NR
225,250
232,615
295,979
220,150
140,522
273,067
188,160
241,678
Booster
Pump
Pressure
(FT 4)
psig
59
59
NA
NA
59
10
59
59
10
59
NA
10
59
NA
10
59
10
10
59
59
59
10
59
59
59
59
59
9
10
10
59
9
10
10
9
10
10
4
57
54
57
8
10
System
Inlet
Pressure
(PT1)
psig
51
51
NA
NA
50
10
49
49
7
49
NA
9
53
NA
9
53
9
9
53
54
54
9
53
54
54
53
-
-
53
9
10
10
53
9
9
10
9
10
-
-
9
4
50
-
45
49
8
9
Tank A
Outlet
Pressure
psig
40
41
NA
NA
40
11
40
42
2
38
NA
2
40
NA
2
40
2
2
40
45
45
11
43
45
45
45
-
-
43
11
11
11
45
10
11
11
11
11
-
-
11
5
40
-
35
38
10
11
TankB
Outlet
Pressure
psig
40
41
NA
NA
40
12
40
42
2
40
NA
2
40
NA
2
40
2
2
40
45
45
11
43
45
45
45
42
11
12
11
45
11
11
12
11
12
11
6
38
34
38
10
11
Product
Water
Pressure
psig
12.5
12.0
NA
NA
12.0
10.0
12.0
12.0
11.0
12.0
NA
11.0
12.0
NA
11.0
12.0
11.0
11.0
12.0
12.0
12.0
10.0
12.0
12.0
12.0
12.0
12.0
11.0
12.0
11.0
12.0
11.0
11.0
11.5
11.0
11.5
11.0
6.0
12.0
12.0
12.0
10.0
11.0
Finished
Water
Flowrate
gpm
542
534
NR
NR
531
NR
550
550
NR
525
545
NR
535
520
NR
542
NR
NR
535
536
543
NR
537
540
545
542
530
NR
NR
532
NR
NR
NR
530
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
517
530
505
452
NR
526
NR
NR
Finished
Water
Volume
Since Last
Regen
gal
539,420
267,078
444,177
308,249
180,895
241,137
439,340
300,669
236,355
177,010
480,240
129,315
233,175
568,210
46,305
464,470
229,445
104,715
45,035
321,775
487,940
112,792
486,293
188,347
522,690
216,000
522,700
313,059
570,142
462,186
94,673
454,437
56,986
344,480
566,402
37,083
368,575
559,404
150,513
359,668
572,792
NR
309,229
66,654
540,850
138,260
431,740
18,001
103,182
339,549
519,590
125,456
BV
Treated
Since Last
Regen.
BV
367
181
302
209
123
164
299
204
161
120
326
88
158
386
31
316
156
71
31
219
332
77
330
128
355
147
355
213
387
314
64
309
39
234
385
25
250
380
102
244
389
NR
210
45
368
94
293
12
70
231
353
85
Regen.
Counter
12
15
16
17
18
NA
23
24
26
27
27
28
30
30
34
34
35
39
40
41
42
47
47
49
49
50
52
53
53
54
56
56
57
57
57
59
59
59
60
62
62
63
1
2
3
4
4
6
6
6
6
7
Regen Water
Totalizer (Per
Event)
gal
12,696
12,738
12,725
12,721
12,672
12,677
12,695
12,746
12,776
12,685
NR
12,708
12,857
NR
12,879
NR
12,907
12,911
12,935
12,934
12,914
12,889
12,889
12,916
NR
12,915
12,872
12,874
12,874
12,856
12,821
12,821
12,725
12,725
12,725
12,614
12,614
12,614
12,634
12,569
12,569
NR
11,109
11,147
11,115
11,100
11,100
11,031
11,031
11,031
11,031
11,037
Fresh
Brine Day
Tank
Totalizer
gal
298,190
300,245
300,920
301,570
302,200
304,536
305,400
306,160
307,470
308,110
NR
308,780
310,210
NR
313,140
NR
313,870
316,775
317,510
318,239
318,965
322,664
322,604
324,100
NR
324,840
326,316
327,063
327,063
327,809
329,270
329,270
330,021
330,021
330,021
331,550
331,550
331,550
332,300
333,780
NR
NR
335,250
335,492
336,727
337,462
337,462
338,927
338,927
338,927
338,927
339,655
-------
US EPA Arsenic Demonstration Project at Vale, OR- Daily System Operation Log Sheet (Study Period II) (Continued)
Parameters
Unit
42
44
48
50
51
52
12/02/09
12/03/09
12/16/09
12/17/09
01/15/10
01/25/10
01/28/10
01/29/10
02/02/10
02/03/10
02/08/10
02/10/10
02/12/10
Pump Hour
Meter
hr
11,635.7
11,646.0
11,752.2
11,762.9
11,809.0
11,828.4
11,849.6
11,856.6
11,884.0
11,892.6
11,925.9
11,939.1
11,954.5
Daily
Hour
hr/day
7.4
9.5
8.2
10.6
1.9
7.1
6.9
7.0
6.6
7.1
6.4
7.9
Master
Totalizer
kgal
295,917
296,213
298,780
299,028
299,195
299,835
300,501
300,699
301,561
301,837
302,816
303,214
303,674
Daily
Volume
gal/ day
229,608
272,358
198,896
245,443
5,740
64,134
222,000
193,959
219,696
213,105
208,083
193,622
236,150
Booster
Pump
Pressure
(FT 4)
psig
56
9
10
55
9
9
56
56
56
57
2
10
System
Inlet
Pressure
(PT1)
psig
26
-
9
9
49
9
9
50
51
51
52
1
9
Tank A
Outlet
Pressure
psig
20
-
11
11
38
10
10
39
39
39
40
0
11
TankB
Outlet
Pressure
psig
20
11
11
37
10
10
36
35
33
28
3
11
Product
Water
Pressure
psig
12.0
11.0
11.0
12.0
10.0
10.0
12.0
12.0
12.0
12.0
3.0
11.0
Finished
Water
Flowrate
gpm
360
NR
NR
NR
554
NR
NR
540
557
545
515
NR
NR
Finished
Water
Volume
Since Last
Regen
gal
82,236
356,930
319,637
553,145
10,605
590,149
579,044
143,810
316,110
571,244
246,140
12,356
421,067
BV
Treated
Since Last
Regen.
BV
56
243
217
376
7
401
394
98
215
388
167
8
286
Regen.
Counter
16
16
20
20
22
22
23
24
25
25
27
28
28
Regen Water
Totalizer (Per
Event)
gal
8,748
NR
9,984
9,984
9,907
9,907
11,364
11,178
11,153
11,153
10,928
7,155
11,380
Fresh
Brine Day
Tank
Totalizer
gal
345,515
NR
348,208
348,208
349,540
349,540
350,225
350,870
351,518
351,518
352,815
353,141
353,665
NR = Not Recorded
1 BV=197ft3
O
-------
APPENDIX D
ANALYTICAL DATA
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Mg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
Unit
gal
mg/L
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
ug/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
ug/L
Hg/L
09/20/06
IN
TA
TB
TT
653,391
301
0.6
73.0
3.5
-
325
-
57.3
-
0.5
-
438
7.3
15.3
1.6
127
155
111
44.4
24.8
-
22.9
1.9
0.4
22.5
<25
<25
0.4
-
0.4
59.7
-
59.2
365
0.6
4.0
3.9
-
290
-
57.9
-
0.2
-
484
7.4
15.0
2.1
126
154
109
44.8
19.4
-
18.7
0.7
0.4
18.3
<25
<25
0.4
-
0.4
0.6
-
0.5
363
0.7
10.0
3.9
-
388
-
57.4
-
0.3
-
484
7.4
15.1
1.9
120
154
109
45.4
27.7
-
24.7
3.0
0.4
24.3
<25
<25
0.5
-
0.4
0.7
-
0.7
358
0.8
9.0
4.1
-
370
-
55.7
-
0.4
-
472
7.4
15.1
2.0
118
146
101
45.5
26.1
-
24.2
1.9
0.4
23.7
<25
<25
0.4
-
0.4
0.6
-
0.7
09/25/06
IN
TA
TB
NA
305
67.0
3.8
-
240
-
57.7
-
0.2
-
460
NA
NA
NA
NA
-
-
-
18.7
-
-
<25
0.7
-
-
-
-
-
227
<1
0.5
-
<10
-
57.0
-
0.1
-
448
NA
NA
NA
NA
-
-
-
5.7
-
-
<25
2.3
-
-
-
-
-
204
<1
0.5
-
<10
-
56.2
-
0.2
-
462
NA
NA
NA
NA
-
-
-
5.9
-
-
<25
1.4
-
-
-
-
-
10/02/06
IN
TA
TB
14,150
254
259
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
VIg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
VIn (soluble)
V (total)
V (soluble)
Unit
gal
mg/L
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
Hg/L
Hg/L
ug/L
ug/L
ug/L
ug/L
ug/L
Hg/L
Hg/L
Hg/L
10/31/06W
IN
TA
TB
NA
331
-
-
78.0
-
4.8
-
320
55.3
0.9
486
-
7.3
15.0
2.1
260
-
23.6
-
-
<25
-
-
0.4
-
398
-
-
<1
-
2.1
-
16.6
56.8
0.7
470
-
7.3
15.2
2.6
229
-
1.8
-
-
<25
-
-
0.6
-
303
-
-
<1
-
0.1
-
<10
54.7
0.8
468
-
7.4
15.0
2.6
231
-
0.4
-
-
<25
-
-
0.6
-
n/oe/oe*1
IN
TA
TB
443,420
311
-
-
76.0
-
4.8
-
253
57.0
0.5
462
-
7.5
16.3
3.1
278
-
24.6
-
-
<25
-
-
2.1
-
376
-
-
2.0
-
3.8
-
97.4
56.4
0.6
438
-
7.6
16.1
3.5
235
-
9.2
-
-
<25
-
-
0.6
-
370
-
-
1.0
-
4.5
-
197
55.6
0.8
432
-
7.6
16.1
3.4
206
-
17.9
-
-
<25
-
-
0.4
-
11/14/06
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Mg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
Unit
gal
mg/L
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
ug/L
Hg/L
Hg/L
Hg/L
Hg/L
12/18/06
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Mg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
Unit
gal
rng/L
rng/L
rng/L
rng/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
02/06/07
IN
TA
TB
278,676
353
-
-
84.0
-
7.2
272
53.6
0.3
536
-
-
NA
NA
NA
NA
19.4
-
-
-
<25
-
-
0.3
395
-
-
<1
-
0.9
<10
53.6
0.4
498
-
-
NA
NA
NA
NA
0.9
-
-
-
<25
-
-
0.3
381
-
-
<1
-
0.9
<10
53.6
0.4
504
-
-
NA
NA
NA
NA
1.0
-
-
-
<25
-
-
0.3
02/12/07
IN
TA
TB
TT
475,337
339
-
0.6
81.0
-
6.4
285
59.2
0.3
514
-
-
NA
NA
NA
NA
170
120
49.8
19.9
20.9
<0.1
0.9
20.0
<25
-
<25
0.5
0.5
50.5
50.4
406
-
1.1
9.0
-
5.6
329
60.0
0.4
480
-
-
NA
NA
NA
NA
182
128
53.7
22 2
21.5
0.7
0.4
21.1
<25
-
<25
0.5
0.5
2.1
1.8
401
-
0.6
18.0
-
7.2
402
59.8
0.5
488
-
-
NA
NA
NA
NA
189
134
55.2
27.3
27.2
0.1
0.3
26.9
<25
-
<25
0.5
0.5
2.4
2.3
399
-
0.5
13.0
-
6.0
394
59.9
0.4
430
-
-
NA
NA
NA
NA
192
136
56.4
26.6
25.4
1.2
0.3
25.1
<25
-
<25
0.5
0.5
2.4
7 9
02/19/07
IN
TA
TB
251,951
344
-
-
93.0
-
6.4
337
55.4
0.6
540
-
-
NA
NA
NA
NA
31.8
-
-
-
<25
-
-
1.1
368
-
-
<1
-
1.2
43.1
56.0
0.7
508
-
-
NA
NA
NA
NA
8.4
-
-
-
<25
-
-
1.2
352
-
-
<1
-
1.2
43.0
55.8
1.6
506
-
-
NA
NA
NA
NA
9.1
-
-
-
<25
-
-
1.3
02/27/07
IN
TA
TB
287,695
343
340
-
92.0
93.0
7.4
7.6
290
296
55.4
55.2
0.4
0.4
526
520
-
NA
NA
NA
NA
20.4
20.8
-
-
-
<25
<25
-
0.2
0.2
401
404
-
<1
<1
1.0
0.9
<10
<10
55.4
55.1
0.3
0.3
472
492
-
NA
NA
NA
NA
1.4
1.3
-
-
-
<25
<25
-
0.2
0.1
392
394
-
<1
<1
1.0
1.1
<10
<10
54.8
55.5
0.1
0.1
480
470
-
NA
NA
NA
NA
1.1
1.1
-
-
-
<25
<25
-
0.2
0.2
03/05/07
IN
TA
TB
NA
346
-
-
79.0
-
6.5
281
55.1
0.3
542
-
-
NA
NA
NA
NA
18.4
-
-
-
<25
-
-
0.3
378
-
-
36.0
-
9.9
664
55.2
0.7
528
-
-
NA
NA
NA
NA
39.4
-
-
-
<25
-
-
0.3
380
-
-
35.0
-
8.9
454
55.1
0.6
526
-
-
NA
NA
NA
NA
27.6
-
-
-
<25
-
-
0.3
03/12/07("'b)
IN
TA
TB
TT
543,862
346
-
1.1
86.1
-
1.4
305
55.5
0.4
554
-
-
7.2
14.8
3.3
226
251
187
63.9
22.9
20.1
2.8
2 3
17.8
<25
-
<25
<0.1
<0.1
50.1
49.9
374
-
1.1
38.0
-
1.4
659
55.2
0.3
532
-
-
7.4
14.7
2.8
217
240
178
61.8
45.8
42.1
3.6
2.5
39.6
<25
-
<25
0.3
0.2
3.0
2.9
381
-
1.0
38.0
-
1.4
458
54.1
0.3
550
-
-
7.4
14.7
2.9
212
241
179
61.6
32.3
29.8
2.5
2.8
27.0
<25
-
<25
<0.1
<0.1
2.6
2.4
384
-
1.3
40.0
-
1.6
559
55.2
0.4
532
-
-
7.4
14.9
2.8
252
229
169
59.8
39.3
35.9
3.4
2.7
33.1
<25
-
<25
<0.1
<0.1
2.9
2.9
(a) Water quality parameters taken on 03/14/07. (b) Process samples taken in counter-current mode.
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
IDS
TOG
pH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Vlg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Vln (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
mg/L
ug/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
ug/L
ug/L
03/19/07
IN
TA
TB
415,021
350
81.0
6.1
294
56.3
0.4
570
NA
NA
NA
NA
-
28.8
-
-
<25
0.6
-
-
409
11.0
5.3
344
56.9
0.6
606
NA
NA
NA
NA
-
30.4
-
-
<25
0.6
-
-
416
7.0
5.1
249
57.2
0.7
544
NA
NA
NA
NA
-
20.0
-
-
<25
0.5
-
-
03/26/07
IN
TA
TB
346,850
342
79.0
6.7
263
55.9
0.5
564
7.2
14.7
3.3
225
-
19.5
-
-
<25
<0.1
-
-
412
<1
2.5
46.1
55.3
0.3
496
7.4
14.8
2.8
216
-
3.6
-
-
<25
<0.1
-
-
412
<1
1.7
<10
55.2
0.8
478
7.4
14.8
2.9
212
-
0.8
-
-
<25
<0.1
-
-
04/02/07
IN
TA
TB
376,943
358
73.1
4.0
285
55.0
0.5
586
7.3
14.8
3.9
253
-
24.1
-
-
<25
0.2
-
-
427
5.0
5.9
249
55.1
1.2
560
7.5
14.8
5.4
224
-
18.3
-
-
<25
0.2
-
-
423
2.0
5 5
154
56.4
0.7
540
7.6
14.8
4.3
222
-
11.1
-
-
<25
0.3
-
-
04/1 0/07°°
IN
TA
TB
TT
114,230
357
0.5
83.0
7.6
279
53.8
0.9
572
7.3
14.8
3.9
294
158
110
48.3
24.2
20.5
3.7
0.8
19.7
<25
<25
0.2
0.3
46.5
48.5
286
0.5
<1
1.9
10.7
54.5
0.8
542
7.1
14.4
3.5
261
165
115
50.4
1.7
1.7
<0.1
0.8
0.9
<25
<25
0.3
0.3
3.6
3.5
251
0.5
<1
2.3
<10
54.6
1.5
550
7.0
14.3
3 2
248
164
115
48.9
1.8
1.8
<0.1
0.7
1.0
<25
<25
0.3
0.3
4.5
4.5
282
0.5
<1
2.1
<10
55.3
1.1
554
7.1
14.0
3.5
242
169
122
47.4
1.6
1.6
<0.1
0.7
0.9
<25
<25
0.3
0.3
3.9
3.5
04/16/07
IN
TA
TB
TT
371,129
-
-
-
-
2.0
8.0
16.3
6.3
258
-
-
-
-
-
-
-
-
-
-
8.3
16.0
6.4
237
-
-
-
-
-
-
-
-
-
-
8.2
16.1
6.5
234
-
-
-
-
-
-
-
-
-
-
8.2
16.0
6.5
233
-
-
-
-
-
-
07/16/07
TT
242,110
-
0.4
-
-
-
NA
NA
NA
NA
-
-
-
-
-
-
07/25/07
TT
50,201
-
0.4
-
-
-
NA
NA
NA
NA
-
3.6
-
-
-
-
-
08/01/07
TT
300,162
-
-
-
-
NA
NA
NA
NA
-
0.9
-
-
-
-
-
(a) Weekly sampling temporarily stopped after 04/10/07.
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Mg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
rng/L
mg/L
rng/L
rng/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
C
mg/L
mV
mg/L
mg/L
mg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
ug/L
ug/L
Hg/L
ug/L
Hg/L
Hg/L
08/08/07
TT
21,930
-
-
-
1.0
-
-
NA
NA
NA
NA
-
-
-
2.0
-
-
-
-
08/14/07
TT
243,014
-
-
-
0.8
-
-
NA
NA
NA
NA
-
-
-
2.1
-
-
-
-
08/21/07
TT
26,825
-
-
-
1.9
-
-
NA
NA
NA
NA
-
-
-
4.3
-
-
-
-
08/28/07
TT
359,292
-
-
-
0.7
-
-
NA
NA
NA
NA
-
-
-
1.4
-
-
-
-
09/1 1/07
TT
94,079
-
-
-
1.4
-
-
NA
NA
NA
NA
-
-
-
1.5
-
-
-
-
09/17/07
TT
163,149
-
-
-
1.1
-
-
8.2
16.3
6.5
233
-
-
-
2.8
-
-
-
-
09/24/07
TT
346,796
-
-
-
0.7
-
-
NA
NA
NA
NA
-
-
-
0.8
-
-
-
-
10/01/07
TT
167,558
-
-
-
1.1
-
-
NA
NA
NA
NA
-
-
-
1.5
-
-
-
-
10/08/07
TT
243,918
-
-
-
0.8
-
-
NA
NA
NA
NA
-
-
-
1.2
-
-
-
-
10/16/07
TT
NA
-
-
-
1.0
-
-
NA
NA
NA
NA
-
-
-
0.7
-
-
-
-
10/22/07
TT
377,889
-
-
-
0.7
-
-
NA
NA
NA
NA
-
-
-
2.1
-
-
-
-
10/29/07
TT
595,337
-
-
-
6.1
-
-
NA
NA
NA
NA
-
-
-
33.5
-
-
-
1.1
11/14/07
TT
131,979
-
-
-
3.7<"
-
-
NA
NA
NA
NA
-
-
-
11. 8<"
-
-
-
-
11/19/07
TT
50,196
-
-
-
35(.)
-
-
NA
NA
NA
NA
-
-
-
10.2
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period I)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Fluoride
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
Total Hardness
(as CaCO3)
Ca Hardness
Mg Hardness
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
C
mg/L
mV
mg/L
mg/L
mg/L
ug/L
Hg/L
Hg/L
ug/L
ug/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
11/27/07
TT
533,870
-
-
-
6.5
-
-
NA
NA
NA
NA
-
-
-
33.8
-
-
-
-
12/03/07
TT
51,996
-
-
-
3 3<«)
-
-
NA
NA
NA
NA
-
-
-
11.9°°
-
-
-
-
12/10/07
TT
530,622
-
-
-
7.1
-
-
NA
NA
NA
NA
-
-
-
48.7
-
-
-
-
12/17/07
TT
200,373
-
-
-
1.1
-
-
NA
NA
NA
NA
-
-
-
1.3
-
-
-
-
01/07/08
TT
195,150
-
-
-
0.7
-
-
NA
NA
NA
NA
-
-
-
2.2
-
-
-
-
01/14/08
TT
418,136
-
-
-
4.0
-
-
NA
NA
NA
NA
-
-
-
20.6
-
-
-
-
(a) Concentrations elevated due to glitches in PLC when reused brine time was set to zero
, causing TA regen to be bypassed. Problem fixed on 12/10/07.
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
Hg/L
ug/L
ug/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
ug/L
03/25/09
IN
TA
TB
TT
59,084
310
74.5
5.7
266
56.5
0.2
496
1.6
NA
NA
NA
NA
21.7
-
-
-
<25
0.2
49.2
-
76.0
0.2
2.1
<10
57.0
1.3
596
<1.0
NA
NA
NA
NA
2.9
-
-
-
<25
0.4
7.3
-
26.4
0.2
2.7
<10
57.4
0.3
622
<1.0
NA
NA
NA
NA
4.5
-
-
-
<25
0.5
14.5
-
52.8
0.2
2.9
<10
56.7
0.4
596
<1.0
NA
NA
NA
NA
3.9
-
-
-
<25
0.5
11.5
-
04/02/09
IN
TA
TB
TT
551,090
320
74.5
5.5
262
54.5
0.3
496
1.8
NA
NA
NA
NA
18.4
-
-
-
<25
0.2
52.6
-
368
21.2
6.3
332
54.9
0.4
474
<1.0
NA
NA
NA
NA
21.9
-
-
-
<25
0.1
7.1
-
372
10.4
4.9
296
54.4
0.4
456
<1.0
NA
NA
NA
NA
19.3
-
-
-
<25
0.2
1.2
-
372
15.1
5.7
303
53.6
0.2
452
<1.0
NA
NA
NA
NA
20.4
-
-
-
<25
0.6
6.0
-
04/08/09
IN
TA
TB
TT
424,882
321
72.6
4.4
345
57.9
<0.1
502
1.7
NA
NA
NA
NA
19.4
-
-
-
<25
0.3
49.8
-
326
<0.1
0.8
<10
57.9
0.3
478
<1.0
NA
NA
NA
NA
1.3
-
-
-
<25
0.3
1.3
-
296
<0.1
0.9
<10
58.2
<0.1
476
<1.0
NA
NA
NA
NA
1.5
-
-
-
<25
0.3
1.7
-
310
0.1
0.9
<10
58.6
0.5
480
<1.0
NA
NA
NA
NA
1.4
-
-
-
<25
0.3
1.7
-
04/22/09
IN
TA
TB
TT
162,061
313
74.4
6.8
308
56.0
0.3
520
2.0
NA
NA
NA
NA
23.3
-
-
-
<25
0.5
59.4
-
241
0.3
1.3
14.5
59.4
0.2
480
<1.0
NA
NA
NA
NA
2.4
-
-
-
<25
0.4
3.4
-
236
0.2
1.3
14.3
59.2
0.2
488
<1.0
NA
NA
NA
NA
2.8
-
-
-
<25
0.8
3.6
-
246
0.3
1.3
13.7
59.1
0.3
488
<1.0
NA
NA
NA
NA
2.6
-
-
-
<25
0.4
3.5
-
04/28/09
IN
TA
TB
TT
145,268
311
71.1
5.2
293
66.2
0.1
508
1.6
NA
NA
NA
NA
22.3
-
-
-
<25
0.4
57.8
-
228
0.4
1.3
20.2
62.8
<0.1
468
<1.0
NA
NA
NA
NA
2.9
-
-
-
<25
0.5
3.3
-
180
0.6
1.2
17.2
67.2
0.2
488
<1.0
NA
NA
NA
NA
3.2
-
-
-
<25
0.7
4.9
-
204
0.6
1.4
19.4
63.2
0.1
502
<1.0
NA
NA
NA
NA
3.0
-
-
-
<25
1.2
4.2
-
o
oo
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
ug/L
Hg/L
ug/L
ug/L
Hg/L
ug/L
Hg/L
Hg/L
ug/L
05/06/09
IN
TA
TB
TT
353,486
316
77.6
6.1
300
63.6
0.4
498
2.1
NA
NA
NA
NA
18.1
-
-
-
-
<25
0.3
50.2
-
360
<0.1
1.1
<10
61.4
0.2
422
<1.0
NA
NA
NA
NA
0.6
-
-
-
-
<25
0.3
0.8
-
374
0.2
0.7
<10
63.7
0.5
460
<1.0
NA
NA
NA
NA
0.6
-
-
-
-
<25
0.3
0.9
-
356
0.1
0.9
<10
63.9
0.3
448
<1.0
NA
NA
NA
NA
0.6
-
-
-
-
<25
0.3
0.9
-
05/19/09
IN
TA
TB
TT
434,234
323
83.2
6.3
258
62.4
<0.1
510
1.7
NA
NA
NA
NA
20.3
-
-
-
-
<25
0.9
49.2
-
381
1.6
4.4
172
62.6
0.3
482
<1.0
NA
NA
NA
NA
11.2
-
-
-
-
<25
0.4
0.8
-
384
0.1
2.3
<10
62.5
0.1
486
<1.0
NA
NA
NA
NA
1.1
-
-
-
-
<25
0.3
0.8
-
396
0.9
3.6
89.2
63.0
0.1
464
<1.0
NA
NA
NA
NA
6.0
-
-
-
-
<25
0.3
0.8
-
05/28/09
IN
TA
TB
TT
172,559
310
81.2
5.8
251
58.5
<0.1
496
2.0
NA
NA
NA
NA
16.0
-
-
-
-
<25
0.3
47.0
-
281
0.1
1.2
<10
59.4
0.1
482
<1.0
NA
NA
NA
NA
0.6
-
-
-
-
<25
0.3
1.7
-
229
0.2
1.2
<10
59.7
0.3
472
<1.0
NA
NA
NA
NA
1.0
-
-
-
-
<25
0.3
2.9
-
246
0.2
1.5
<10
59.7
0.3
486
<1.0
NA
NA
NA
NA
1.0
-
-
-
-
<25
0.3
2.7
-
06/03/09
IN
TA
TB
TT
587,423
322
76.6
5.9
279
61.7
0.2
528
2.0
NA
NA
NA
NA
20.7
-
-
-
-
<25
0.3
54.7
-
354
21.2
9.9
452
61.4
0.2
512
<1.0
NA
NA
NA
NA
30.8
-
-
-
-
<25
0.3
4.8
-
377
11.5
9.9
447
62.0
0.1
496
<1.0
NA
NA
NA
NA
31.1
-
-
-
-
<25
0.3
3.1
-
360
15.4
9.3
457
62.0
0.3
508
<1.0
NA
NA
NA
NA
31.4
-
-
-
-
<25
0.3
4.1
-
06/09/09
IN
TA
TB
TT
417,977
305
74.4
5.2
285
60.3
0.4
506
2.0
NA
NA
NA
NA
20.2
-
-
-
-
<25
0.3
55.2
-
372
0.4
3.3
75.3
60.5
0.9
466
<1.0
NA
NA
NA
NA
4.9
-
-
-
-
<25
0.3
0.8
-
376
0.2
1.1
<10
61.4
0.5
460
<1.0
NA
NA
NA
NA
0.5
-
-
-
-
<25
0.3
0.9
-
368
0.3
1.8
29.4
60.6
0.3
468
<1.0
NA
NA
NA
NA
2.4
-
-
-
-
<25
0.3
0.9
-
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
ug/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
Hg/L
Hg/L
Hg/L
Hg/L
ug/L
Hg/L
Hg/L
ug/L
Hg/L
ug/L
06/17/09
IN
TA
TB
TT
339,974
306
71.6
5.1
279
59.6
0.5
450
1.9
NA
NA
NA
NA
19.0
-
-
<25
0.3
54.3
-
368
0.1
0.7
<10
59.9
1.2
416
<1.0
NA
NA
NA
NA
0.5
-
-
<25
0.2
1.0
-
355
0.1
0.6
<10
60.3
0.8
420
<1.0
NA
NA
NA
NA
0.6
-
-
<25
0.3
1.1
-
364
0.2
0.7
<10
60.2
0.6
438
<1.0
NA
NA
NA
NA
0.6
-
-
<25
0.2
1.1
-
06/30/09
IN
TT
528,358
315
74.6
5.1
304
57.9
0.1
470
1.8
NA
NA
NA
NA
22.8
-
-
<25
0.3
49.7
-
358
6.8
5.3
291
58.7
0.1
440
<1.0
NA
NA
NA
NA
19.9
-
-
<25
0.3
0.9
-
07/08/09
IN
TA
TB
TT
357,543
312
71.7
5.4
262
58.0
0.3
498
1.8
NA
NA
NA
NA
19.8
-
-
<25
0.3
51.5
-
376
61.7
2.8
<10
58.5
0.2
462
<1.0
NA
NA
NA
NA
0.7
-
-
<25
0.3
0.3
-
372
0.2
0.7
<10
58.7
0.4
464
<1.0
NA
NA
NA
NA
0.6
-
-
<25
0.3
0.3
-
369
0.3
0.8
<10
59.1
0.4
368
<1.0
NA
NA
NA
NA
0.7
-
-
<25
0.3
0.3
-
07/13/09
IN
TA
TB
TT
539,420
304
75.2
5.6
263
57.9
0.2
460
1.7
NA
NA
NA
NA
18.9
-
-
<25
0.3
50.4
-
345
20.5
6.6
355
59.1
0.3
460
NA
NA
NA
NA
25.3
-
-
<25
0.3
2.1
-
352
9.2
5.8
325
58.9
0.2
468
<1.0
NA
NA
NA
NA
22.6
-
-
<25
0.3
1.0
-
349
13.7
5.7
326
58.8
<0.1
466
<1.0
NA
NA
NA
NA
23.0
-
-
<25
0.3
1.3
-
07/20/09
IN
TA
TB
TT
444,177
312
71.1
5.3
263
62.2
1.0
456
1.7
NA
NA
NA
NA
18.6
-
-
<25
4.0
50.2
-
386
0.5
3.9
85.3
62.4
1.0
452
<1.0
NA
NA
NA
NA
5.3
-
-
<25
3.2
<0.1
-
390
<0.1
1.4
<10
62.7
0.9
434
<1.0
NA
NA
NA
NA
0.6
-
-
<25
3.3
<0.1
-
383
0.4
3.0
44.1
62.5
1.5
428
<1.0
NA
NA
NA
NA
3.2
-
-
<25
3.0
<0.1
-
08/04/09
IN
TA
TB
TT
236,355
297
72.8
5.8
279
60.2
0.2
532
2 2
NA
NA
NA
NA
21.0
-
-
<25
0.2
51.3
-
322
0.2
0.8
<10
60.3
0.1
502
<1.0
NA
NA
NA
NA
1.6
-
-
<25
0.3
1.4
-
288
0.3
1.1
<10
60.5
0.8
500
<1.0
NA
NA
NA
NA
1.5
-
-
<25
0.4
2.0
-
302
0.3
1.0
<10
60.6
0.2
506
<1.0
NA
NA
NA
NA
1.4
-
-
<25
0.3
1.8
-
o
H-*
O
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
ug/L
08/12/09
IN
TA
TB
TT
568,210
302
63.6
4.7
275
58.7
0.2
588
7 9
NA
NA
NA
NA
18.0
-
-
<25
0.3
0.3
-
336
19.5
5.8
376
58.5
0.3
484
<1.0
NA
NA
NA
NA
23.0
-
-
<25
0.3
0.3
-
345
10.1
5.5
362
58.3
0.4
474
<1.0
NA
NA
NA
NA
21.7
-
-
0.3
0.3
-
343
14.8
5.7
375
58.7
0.3
494
<1.0
NA
NA
NA
NA
22.3
-
-
<25
0.3
0.3
-
08/19/09
IN
TA
TB
TT
229,445
298
71.8
5.3
269
57.9
0.2
500
2.1
NA
NA
NA
NA
20.5
-
-
<25
2.6
2.6
-
317
<0.1
0.7
<10
58.4
0.2
448
<1.0
NA
NA
NA
NA
1.7
-
-
2 2
2 2
-
287
0.2
1.1
<10
58.7
0.5
478
<1.0
NA
NA
NA
NA
1.9
-
-
2.3
2.3
-
303
0.1
0.9
<10
58.4
0.3
480
<1.0
NA
NA
NA
NA
2.0
-
-
<25
2.6
2.6
-
08/26/09
IN
TA
TB
TT
104,715
296
70.6
5.3
265
59.5
0.2
468
1.9
NA
NA
NA
NA
19.7
-
-
0.3
0.3
-
187
0.1
1.2
<10
59.0
0.8
466
<1.0
NA
NA
NA
NA
1.9
-
-
<25
0.5
0.5
-
117
0.2
1.7
<10
60.0
0.6
512
<1.0
NA
NA
NA
NA
2.8
-
-
<25
0.4
0.4
-
161
0.1
1.2
<10
60.1
<0.1
456
<1.0
NA
NA
NA
NA
2.6
-
-
<25
0.2
0.2
-
09/02/09
IN
TA
TB
TT
487,940
293
79.2
5.3
272
60.0
0.4
474
2.0
NA
NA
NA
NA
18.5
-
-
<25
0.3
49.1
-
337
7.5
5.2
386
61.2
0.9
448
<1.0
NA
NA
NA
NA
23.4
-
-
<25
0.2
1.6
-
353
0.2
3.7
70
60.4
4.2
450
<1.0
NA
NA
NA
NA
3.3
-
-
<25
0.3
0.8
-
347
3.6
4.3
239
59.6
0.4
444
<1.0
NA
NA
NA
NA
13.7
-
-
<25
0.2
1.2
-
09/10/09
IN
TA
TB
TT
112,792
282
72.4
5.7
281
59.8
0.1
474
1.8
NA
NA
NA
NA
19.0
-
-
<25
0.3
48.6
-
180
<0.1
0.1
<10
60.8
0.2
440
<1.0
NA
NA
NA
NA
0.8
-
-
<25
0.2
3.1
-
118
0.2
1.6
<10
61.0
0.3
504
<1.0
NA
NA
NA
NA
1.4
-
-
<25
0.3
4.8
-
143
0.1
0.1
<10
60.5
0.2
474
<1.0
NA
NA
NA
NA
1.2
-
-
<25
0.3
4.2
-
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
pH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
ug/L
09/15/09
IN
TA
TB
TT
522,690
279
66.4
4.5
290
59.7
2.6
434
1.9
NA
NA
NA
NA
21.1
-
-
<25
5.3
49.4
-
343
11.0
5.5
348
59.4
0.3
462
<1.0
NA
NA
NA
NA
25.1
-
-
<25
1.1
<0.1
-
345
3.1
4.4
253
58.4
0.5
454
<1.0
NA
NA
NA
NA
17.7
-
-
0.3
<0.1
-
337
6.8
5.1
291
59.3
2.1
446
<1.0
NA
NA
NA
NA
19.2
-
-
<25
0.2
<0.1
-
09/23/09
IN
TA
TB
TT
570,142
293
69.2
4.0
253
56.0
0.1
466
1.8
NA
NA
NA
NA
19.5
-
-
<25
0.3
48.7
-
322
19.0
6.2
346
56.2
0.1
438
<1.0
NA
NA
NA
NA
25.8
-
-
26
0.8
3.5
-
337
11.5
5.3
283
56.1
0.1
426
<1.0
NA
NA
NA
NA
21.4
-
-
<25
0.3
2.2
-
333
14.8
5.7
313
55.2
0.1
430
<1.0
NA
NA
NA
NA
23.2
-
-
<25
0.2
2.4
-
09/30/09
IN
TA
TB
TT
56,986
298
74.0
5.7
272
59.9
0.4
540
1.6
NA
NA
NA
NA
21.7
-
-
0.2
49.1
-
107
<0.1
1.5
<10
60.8
0.2
606
<1.0
NA
NA
NA
NA
1.7
-
-
<25
0.4
3.9
-
29.0
0.1
1.9
14
60.6
0.3
724
<1.0
NA
NA
NA
NA
3.3
-
-
<25
0.3
9.7
-
63.5
0.1
1.8
<10
60.4
0.1
650
<1.0
NA
NA
NA
NA
2.9
-
-
<25
0.3
7.4
-
10/07/09
IN
TA
TB
TT
559,404
300
67.3
6.7
276
58.2
0.4
502
1.5
NA
NA
NA
NA
97 9
-
-
<25
0.2
52.5
-
336
24.8
8.0
449
58.4
1.0
468
<1.0
NA
NA
NA
NA
34.7
-
-
<25
0.2
3 2
-
356
16.0
8.8
340
58.3
0.2
454
<1.0
NA
NA
NA
NA
26.3
-
-
<25
0.2
2.2
-
358
21.3
9.0
397
58.4
0.3
466
<1.0
NA
NA
NA
NA
30.4
-
-
<25
0.2
2.7
-
10/14/09
IN
TA
TB
TT
359,668
312
72.8
5.7
272
55.3
0.2
486
1.4
NA
NA
NA
NA
18.4
-
-
<25
0.3
46.9
-
370
<0.1
2.9
<10
55.7
0.1
442
<1.0
NA
NA
NA
NA
0.1
-
-
<25
0.3
<0.1
-
370
0.1
0.9
<10
54.8
0.1
454
<1.0
NA
NA
NA
NA
<0.1
-
-
<25
0.5
<0.1
-
375
<0.1
1.6
<10
54.5
0.1
460
<1.0
NA
NA
NA
NA
<0.1
-
-
<25
0.2
<0.1
-
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
ug/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
Hg/L
Hg/L
ug/L
Hg/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
10/27/09
IN
TA
TB
TT
540,850
293
72.8
5.7
267
62.5
0.8
480
1.6
NA
NA
NA
NA
18.4
-
-
<25
0.4
49.5
327
19.9
7.8
420
62.9
0.8
462
<1.0
NA
NA
NA
NA
26.9
-
-
<25
0.5
1.6
331
14.1
7.2
343
62.6
0.9
444
<1.0
NA
NA
NA
NA
22.0
-
-
<25
0.6
1.5
327
17.0
7.1
380
62.0
0.6
460
<1.0
NA
NA
NA
NA
24.6
-
-
<25
0.5
1.5
1 1/04/09
IN
TA
TB
TT
339,549
305
75.3
6.2
257
58.7
0.2
484
1.6
NA
NA
NA
NA
16.4
-
-
<25
0.3
50.7
370
<0.1
1.2
<10
58.8
0.3
456
<1.0
NA
NA
NA
NA
0.3
-
-
<25
0.5
0.9
366
<0.1
0.8
<10
58.3
0.2
420
<1.0
NA
NA
NA
NA
0.2
-
-
<25
0.5
0.9
370
<0.1
1.0
<10
58.0
0.4
466
<1.0
NA
NA
NA
NA
0.2
-
-
<25
0.4
0.7
12/10/09
IN
TA
TB
TT
27,963
346
80.6
6.8
249
58.6
0.2
550
1.8
NA
NA
NA
NA
18.1
-
-
<25
0.6
51.7
169
0.5
2.1
12.5
59.3
0.2
534
<1.0
NA
NA
NA
NA
2 3
-
-
<25
0.9
6.5
45.6
0.1
2.7
16.8
59.3
0.2
608
<1.0
NA
NA
NA
NA
4.0
-
-
<25
0.4
12.9
123
0.3
2.6
13.4
60.2
0.3
580
<1.0
NA
NA
NA
NA
3.3
-
-
<25
0.3
9.8
12/16/09
IN
TA
TB
TT
319,637
329
81.1
7.5
277
58.2
0.3
538
1.8
NA
NA
NA
NA
20.5
-
-
<25
0.4
57.8
402
0.2
4.5
22 3
62.3
0.5
506
<1
NA
NA
NA
NA
2.2
-
-
<25
0.3
1.9
387
0.1
1.0
<10
62.4
0.4
488
<1
NA
NA
NA
NA
1.6
-
-
<25
0.4
2.8
400
0.4
3.0
12.8
62.0
0.6
504
<1
NA
NA
NA
NA
1.9
-
-
<25
0.3
2.0
02/02/10
IN
TA
TB
TT
316,110
332
76.4
5.6
271
64.1
0.2
502
1.9
NA
NA
NA
NA
17.7
-
-
<25
0.3
53.7
386
0.2
1.5
<10
65.2
0.3
470
<1
NA
NA
NA
NA
0.7
-
-
<25
0.2
1.3
366
0.2
1.0
<10
65.2
0.2
462
<1
NA
NA
NA
NA
0.6
-
-
<25
0.3
1.4
381
0.2
1.2
<10
64.6
0.4
470
<1
NA
NA
NA
NA
0.6
-
-
<25
0.2
1.5
-------
Analytical Results from Long-Term Sampling at Vale, OR (Study Period II) (Continued)
Sampling Date
Sampling Location
Parameter Unit
Throughput
Alkalinity
(as CaCO3)
Sulfate
Nitrate (as N)
Total P (as P)
Silica (as SiO2)
Turbidity
TDS
TOG
PH
Temperature
DO
ORP
As (total)
As (soluble)
As (particulate)
As (III)
As(V)
Fe (total)
Fe (soluble)
Mn (total)
Mn (soluble)
V (total)
V (soluble)
gal
mg/L
mg/L
mg/L
Hg/L
mg/L
NTU
mg/L
mg/L
S.U.
°C
mg/L
mV
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
Hg/L
ug/L
ug/L
Hg/L
ug/L
02/08/10
IN
TA
TB
TT
246,140
338
77.6
5.9
260
60.0
0.2
526
1.9
NA
NA
NA
NA
18.3
-
-
<25
0.2
-
53.6
-
395
0.2
0.8
127
60.9
0.1
474
<1
NA
NA
NA
NA
0.8
-
-
<25
0.5
-
1.7
-
357
0.3
1.1
<10
60.9
0.6
476
<1
NA
NA
NA
NA
1.1
-
-
<25
0.5
-
2.5
-
386
0.2
0.9
<10
60.0
0.2
484
<1
NA
NA
NA
NA
1.0
-
-
<25
0.2
-
2.0
-
------- |