May 2010
NSF10/33/EPADWCTR
EPA/600/R-10/099
Environmental Technology
Verification Report
Removal of Uranium in Drinking Water
Brimac Environmental Services, Inc.
Brimac HA 216 Adsorptive Media
Prepared by
NSF International
Under a Cooperative Agreement with
U.S. Environmental Protection Agency
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THE ENVIRONMENTAL TECHNOLOGY VERIFICATION
PROGRAM ^
f f
EIV
U.S. Environmental Protection Agency
NSF International
ETV Joint Verification Statement
TECHNOLOGY TYPE: ADSORBTIVE MEDIA
APPLICATION: REMOVAL OF URANIUM IN DRINKING WATER
PRODUCT NAME: BRIMAC HA 216 ADSORPTIVE MEDIA
VENDOR: BRIMAC ENVIRONMENTAL SERVICES, INC.
ADDRESS: 318 GRALAKE AVE.
ANN ARBOR, MI 48103
PHONE: 734-998-0763
WEBSITE: HTTP://WWW.BRIMACSERVICES.COM
EMAIL: INFO@BRIMACSERVICES.COM
NSF International (NSF) manages the Drinking Water systems (DWS) Center under the U.S.
Environmental Protection Agency's (EPA) Environmental Technology Verification (ETV) Program. The
DWS Center recently evaluated the performance of the Brimac Environmental Services, Inc. (Brimac)
HA 216 Adsorptive Media. The New Hampshire Department of Environmental Services (NHDES)
monitored the operation of the pilot unit containing the media, collected water samples, and provided
some laboratory services. NSF also analyzed samples and authored the verification report and this
verification statement. The verification report contains a comprehensive description of the test.
EPA created the ETV Program to facilitate the deployment of innovative or improved environmental
technologies through performance verification and dissemination of information. The ETV Program's
goal is to further environmental protection by accelerating the acceptance and use of improved and more
cost-effective technologies. ETV seeks to achieve this goal by providing high quality, peer-reviewed data
on technology performance to those involved in the design, distribution, permitting, purchase, and use of
environmental technologies.
ETV works in partnership with recognized standards and testing organizations, stakeholder groups
(consisting of buyers, vendor organizations, and permitters), and with the full participation of individual
technology developers. The program evaluates the performance of innovative technologies by developing
test plans that are responsive to the needs of stakeholders, conducting field or laboratory tests (as
appropriate), collecting and analyzing data, and preparing peer-reviewed reports. All evaluations are
conducted in accordance with rigorous quality assurance protocols to ensure that data of known and
adequate quality are generated and that the results are defensible.
NSF 10/33/EPADWCTR The accompanying notice is an integral part of this verification statement. September 2010
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ABSTRACT
The Brimac HA 216 Adsorptive Media was tested for uranium (U) removal from a drinking water source
(well water) at Grappone Toyota located in Bow, New Hampshire. The HA 216 media is a
hydroxyapatite-based material. A pilot unit, consisting of a TIGG Corporation Cansorb® C-5 steel drum
with 50 pounds (Ib) (23 kilograms, 1.3 ft3) of media, was used for this verification test. The pilot unit was
operated at a flow rate of approximately two gallons per minute (gpm), resulting in a hydraulic loading
rate of 1.04 gpm/ft2, and an empty bed contact time (EBCT) of 4 minutes and 54 seconds. The integrity
test phase included observation of the operation of the pilot unit. The pilot test unit was simple and easy
to operate, particularly since there were no pumps required for this installation and no need for automated
controls or backwash systems.
The source water contained a mean uranium concentration of 190 |o,g/L. The pilot unit produced treated
water with uranium concentrations of <1 ng/L at the start of the test. The uranium concentration in the
treated water began to increase after two days of operation and exceeded the EPA National Primary
Drinking Water Regulation (NPDWR) maximum contaminant level (MCL) of 30 |og/L after
approximately 21,400 gallons (gal) of water had been treated, representing 2,200 bed volumes (BV). The
uranium concentration in the treated water exceeded the stop-test concentration of 60 (ig/L at 33,700 gal
(3,500 BV). The test was stopped two days later at 40,500 gal after the uranium results had been received
showing that 60 (ig/L had been passed. While the treated water uranium concentration increased more
quickly than anticipated, the mean concentration for the 15-day monitoring period was 29.7 |o,g/L, which
is below the MCL. Based on the mean source and treated water uranium concentrations (171 |og/L and
12.6 |o,g/L respectively) for the first ten days of operation before the treated water exceeded 30 (ig/L of
uranium, the 23 kilograms (kg) of media absorbed 13.1 g of uranium (5.7xlO~4 g U/g media). For the
entire test period, the media adsorbed approximately 24.8 g of uranium (0.001 g U/g media).
TECHNOLOGY DESCRIPTION
The following technology description was provided by the manufacturer and has not been verified.
Brimac HA 216 Adsorptive Media is a hydroxyapatite-based media. The molecular formula for
hydroxyapatite is Ca5(PO4)3(OH). Hydroxyapatite sequesters uranium by three processes: 1)
incorporation within the hydroxyapatite lattice through ion-exchange with calcium, 2) physisorption and
chemisorption with reactive phosphate and calcium oxide groups at the mineral surface, and 3) reaction
with free phosphate to form solids that precipitate out of solution. The particles are highly porous and
capable of adsorbing heavy metals, color forming compounds, trihalomethane (THM) precursor
compounds, taste and odor producing compounds as well as other organic and inorganic compounds. The
media performs over a wide range of pH and temperature. HA 216 has a Langmuir isotherm capacity of
just over 1 g of uranium per g of media.
Uranium adsorption by hydroxyapatite occurs more slowly than contaminant adsorption by activated
carbon. The rate-determining step is adsorption, not the rate of diffusion, as with activated carbon. For
this reason, Brimac considers uranium adsorption by hydroxyapatite to be more like an ion exchange
process. The bed of hydroxyapatite media has a mass transfer zone that moves through the bed in a plug
flow manner until the media is exhausted.
HA 216 is certified by NSF to NSF/ANSI Standard 61 for water treatment plant applications and received
European Pharmacopeoia and UK Drinking Water Inspectorate approvals. Hydroxyapatite is also listed
'Generally Recognized as Safe' by the U.S. Food and Drug Administration.
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VERIFICATION TESTING DESCRIPTION
Test Site and Equipment
The verification test was conducted using a pilot unit installed at Grappone Toyota at 514 Route 3A in
Bow, New Hampshire. Groundwater was drawn from an 11 gpm capacity well, serving 82 employees.
Brimac provided a pilot unit containing HA 216 media installed in a TIGG Corporation Cansorb® C-5
steel drum. The drum contains internal schedule 40 PVC plumbing to ensure proper distribution of the
feed water onto the media bed. The C-5 is 30 inches (in) high, with a diameter of 19 in. For the
verification test, the pilot unit contained 50 Ib (23 kg) of media, which equals approximately 1.3 ft3 of
media at a depth of 8.2 in. in the C-5 drum. The unit was set up to operate at approximately 2.0 gpm.
The inlet water line was connected to the pressure (bladder) tank that was used to maintain water pressure
in the building water supply system. This provided sufficient water pressure to operate the pilot unit, and
no additional pumping was required to maintain flow to the test system. Treated water was discharged to
the sanitary sewer.
The verification test included two main tasks: system integrity verification and adsorptive capacity
verification. System integrity verification was a two-week test of the pilot unit with daily monitoring to
ensure the media and pilot unit were functioning properly and to identify any major systemic problems
such as channeling, insufficient media, excessive headless buildup, etc. Adsorption capacity verification
evaluated the capability of the media at a set contact time to remove uranium to below the EPA NPDWR
MCL of 30 |og/L. As requested by Brimac, the test was continued until at least 60 |o,g/L of uranium was
detected in the treated water.
Methods and Procedures
The testing methods and procedures are detailed in the Product-Specific Test Plan Removal of Uranium in
Drinking Water Brimac HA 216 Adsorptive Media. The EPA/NSF ETV Protocol for Equipment
Verification Testing for Removal of Radioactive Chemical Contaminants (April 2002, Chapter 1) and the
EPA/NSF ETV Equipment Verification Testing Plan for Adsorptive Media Processes for the Removal of
Arsenic (September 2003, Chapter 6) provided the basis for the procedures used to develop the test plan
and to ensure the accurate documentation of pilot unit performance and treated water quality. NSF and
NHDES co-managed verification responsibilities and analytical laboratory efforts. The pilot unit was
operated 24 hours a day, seven days a week during the testing period.
For the first 14 days of the integrity test, operational data were collected once per day, Monday through
Saturday. These data included cumulative feed water volume, feed water flow rate, treated water pressure,
and time on site. Grab samples for on-site and laboratory water quality analyses were collected daily for
temperature, pH, turbidity, and uranium. Grab samples were collected weekly for TSS, TOC, TDS,
calcium magnesium, sodium, iron, hardness, chloride, sulfate, fluoride alkalinity, phosphorus, nitrate,
arsenic aluminum silica, radon 222, alpha radioactivity, and UV254. Prior to collecting samples, the
sample tap was flushed for at least five seconds. All samples were collected into clean containers.
The analytical laboratories performed the water quality analyses using EPA or Standard Methods
procedures. Samples for off-site laboratory analysis were collected and preserved according to Standard
MethodslQIQB.
VERIFICATION OF PERFORMANCE
System Operation
Brimac coordinated with NHDES and NSF to install the equipment and ready the system for operation.
Once ready for operation, Brimac ran initial startup and shakedown tests to determine operating
conditions for water treatment. The system started up quickly and without any difficulties. Verification
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testing was started on July 10. The two-week integrity test was completed on July 24 and the capacity test
phase ended on July 25 after 15 days of operation. The capacity test was stopped because the uranium
data showed that the concentration in the treated water had exceeded the stop-test level of 60 |o,g/L on the
13th day. The pilot unit continued in operation until July 30, while the analyses were being completed.
The average daily flow rate reported for the 19 total days of operation (Days 0-20) was 1.97 gpm and the
average flow rate calculated using the total volume treated was 2.03 gpm (54,728 gal over 19 days, as
recorded from the flow meter totalizer). The flow rate to the unit cycled between a high to low flow rate,
as the pressure in the well system cycled from high to low. The field technician observed several flow
rates over several minutes and recorded a range of flow rates on the bench sheet. These flow rate ranges
were then used to report an average flow rate for the unit. While the flow rate did change over a range of
readings, the average flow rate was close to the target of 2.0 gpm and was consistent during the test.
Overall, the frequent change in flow rate did not impact the volume of water treated each day, as shown
by comparing the data for the average flow rate and daily volume treated.
The hydraulic loading rate during the test, based on a mean flow rate of 1.97 gpm and a pilot unit surface
area of 1.90 ft2, averaged 1.04 gpm/ft2. The EBCT during the verification test was approximately 4.9
minutes (4 minutes, 54 seconds).
Test Results
The source water had a mean uranium concentration of 190 |og/L. All turbidity measurements were <1
NTU and all TSS concentrations were <2 mg/L. A sediment/particulate pre-filter was not used ahead of
the test unit. There was no indication during the test of any problems with particulate accumulation in the
media bed. The pH of the source water and treated water was steady throughout the test, with a range of
6.52-6.93 SU and 6.63-7.29 SU, respectively.
Figure VS-1 presents the uranium removal results plotted as a function of the bed volumes treated during
the integrity and capacity tests. At the beginning of the verification, the uranium concentration observed
in the treated water was near or below 1 ng/L. The uranium concentration observed in the treated water
began to increase as the cumulative bed volumes of treated water increased. The concentration exceeded
the water quality standard of 30 |o,g/L after approximately 21,400 gal of water were treated, or 2,200 BV.
The capacity test was stopped two days later at 40,500 gal after the uranium results had been received
showing that the treated water concentration had exceeded 60 (ig/L. While the treated water uranium
concentration increased more quickly than anticipated, the mean concentration for the 15-day monitoring
period was 29.7 |og/L, which is below the MCL. However, the treated water was below the water quality
standard for only the first 10 days of the test.
Considering the mean source and treated water uranium concentrations (171 |o,g/L and 12.6 |o,g/L) for the
first ten days of data (until breakthrough had occurred at 30 |og/L), the 50 Ibs (23 kg) of media adsorbed
13.1 g of uranium (5.7xlO~4 g U/g media). Over the entire test period, the 23 kg of media adsorbed
approximately 24.8 g of uranium (0.001 g U/g media). These data indicate that while the HA 216 media
had capacity to adsorb uranium beyond the first 10 days, movement of the mass transfer zone thru the
media and the adsorption kinetics were not well predicted for the contactor configuration used in the test,
and the media would need to be changed frequently using the current contactor configuration.
Uranium adsorption kinetics of HA 216 media are slow compared to activated carbon, and design EBCT
has a significant impact on the final treated water concentration, as the media is loaded with uranium. The
size of the mass transfer zone moving through the bed and the equilibrium between the media and the
treated water concentrations will vary as a function of EBCT. Particle size can also affect the kinetics of
NSF 10/33/EPADWCTR The accompanying notice is an integral part of this verification statement. September 2010
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the adsorption process with smaller particle sizes providing more surface area for adsorption in a given
media volume.
250 -
200 -
3 150 -
U 100 -
E
1
50 -
Bed Volumes Treated
Figure VS-1. Uranium Concentration versus Bed Volumes Treated
Supplemental data provided by Brimac is presented in the report concerning adsorption rates and capacity
of the HA 216 media. Their documentation indicates that reducing the particle size of the media increases
the adsorption rate. Brimac is currently developing an approach to manufacture a smaller particle size
media. Brimac has indicated the need for additional verification testing in the future with a redesigned
treatment contactor and media.
Feed and treated water concentrations of cations and anions (calcium, magnesium, sodium, iron, silica,
chloride, sulfate, alkalinity, fluoride, nitrate, phosphorus) were about the same, with the exception of
phosphorus. The phosphorus levels increased from <0.05 mg/L in the source water to a concentration
range of 0.08 to 0.19 mg/L in the treated water. The F£A 216 adsorptive media contains calcium,
phosphorus, and hydroxide. The slight increase in phosphorus could be due to a small amount of
dissolution of the phosphorus from the media. The contribution appears small. There was minimal or no
increase in calcium or hydroxide (alkalinity) concentrations in the treated water.
System Operation
The test unit was simple and easy to operate, particularly since there were no pumps required for this
installation and no need for automated controls or backwash systems. Flow control was maintained by
one manual control valve and the source water was fed to the unit using well system pressure. In this
application with the treated water discharging by gravity to the sewer system, there was no concern with
operating the unit in-line with the water supply system. Time to operate and monitor the system was
NSF 10/33/EPADWCTR
The accompanying notice is an integral part of this verification statement. September 2010
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minimal with most time being spent for sample collection. Over the testing period, the average time on
site was about 40 minutes each day (90 minutes, the first two days).
The feed water contained low turbidity and low TSS concentrations, and pressure buildup due to solids
entering the media bed was not observed. Other source waters may require pre-filtration and continuous
monitoring of inlet and outlet pressures to address possible media fouling conditions.
QUALITY ASSURANCE/QUALITY CONTROL
NSF provided technical and QA oversight of the verification testing, including an on-site audit of
operating and sampling procedures. The NSF QA Department performed a QA review of the analytical
data. A complete description of the QA/QC procedures is provided in the verification report.
Original signed by Sally Gutierrez 10/06/10 Original signed by Robert Ferguson 09/17/10
Sally Gutierrez Date Robert Ferguson Date
Director Vice President
National Risk Management Research Water Systems
Laboratory NSF International
Office of Research and Development
United States Environmental Protection
Agency
NOTICE: Verifications are based on an evaluation of technology performance under specific,
predetermined criteria and the appropriate quality assurance procedures. EPA and NSF make no
expressed or implied warranties as to the performance of the technology and do not certify that a
technology will always operate as verified. The end-user is solely responsible for complying with
any and all applicable federal, state, and local requirements. Mention of corporate names, trade
names, or commercial products does not constitute endorsement or recommendation for use of
specific products. This report is not an NSF Certification of the specific product mentioned
herein.
Availability of Supporting Documents
Copies of the test protocol, the verification statement, and the verification report (NSF
report # NSF 10/33/EPADWCTR) are available from the following sources:
1. ETV Drinking Water Systems Center Manager (order hard copy)
NSF International
P.O. Box 130140
Ann Arbor, Michigan 48113-0140
2. Electronic PDF copy
NSF web site: http://www.nsf.org/info/etv
EPA web site: http://www.epa.gov/etv
NSF 10/33/EPADWCTR The accompanying notice is an integral part of this verification statement. September 2010
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May 2010
Environmental Technology Verification Report
Removal of Uranium in Drinking Water
Brimac Environmental Services, Inc.
Brimac HA 216 Adsorptive Media
Prepared by:
NSF International and Scherger and Associates
Ann Arbor, Michigan 48105
Under a cooperative agreement with the U.S. Environmental Protection Agency
Jeffrey Q. Adams, Project Officer
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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Notice
The U.S. Environmental Protection Agency, through its Office of Research and Development,
funded and managed, or partially funded and collaborated in, the research described herein. It
has been subjected to the Agency's peer and administrative review and has been approved for
publication. Any opinions expressed in this report are those of the author (s) and do not
necessarily reflect the views of the Agency, therefore, no official endorsement should be inferred.
Any mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
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Foreword
The EPA is charged by Congress with protecting the nation's air, water, and land 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, the EPA's Office of Research and
Development provides data and science support that can be used to solve environmental
problems and to build the scientific knowledge base needed to manage our ecological resources
wisely, to understand how pollutants affect our health, and to prevent or reduce environmental
risks.
The Environmental Technology Verification (ETV) Program has been established by the EPA to
verify the performance characteristics of innovative environmental technology across all media
and to report this objective information to permitters, buyers, and users of the technology, thus
substantially accelerating the entrance of new environmental technologies into the marketplace.
Verification organizations oversee and report verification activities based on testing and quality
assurance protocols developed with input from major stakeholders and customer groups
associated with the technology area. ETV consists of six environmental technology centers.
Information about each of these centers can be found on the internet at http://www.epa.gov/etv.
Under a cooperative agreement, NSF International has received EPA funding to plan, coordinate,
and conduct technology verification studies for the ETV "Drinking Water Systems Center"
(DSWC) and report the results to the community at large. The DWSC has targeted drinking
water concerns such as arsenic reduction, microbiological contaminants, particulate removal,
disinfection by-products, radionuclides, and numerous chemical contaminants. Information
concerning specific environmental technology areas can be found on the internet at
http ://www. epa.gov/nrmrl/std/etv/verifications.html.
in
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Table of Contents
Verification Statement VS-i
Title Page i
Notice ii
Foreword iii
Table of Contents iv
List of Tables vi
List of Figures vi
Abbreviations and Acronyms vii
Acknowlegements viii
Chapter 1 Introduction 1
1.1 Environmental Technology Verification (ETV) Program Purpose and Operation 1
1.2 Purpose of Verification 1
1.3 Testing Participants and Responsibilities 2
1.3.1 Field Testing Organizations 2
1.3.1.1 NSF International 2
1.3.1.2 New Hampshire Department of Environmental Services 3
1.3.2 Brimac Environmental Services, Inc 4
1.3.3 U.S. Environmental Protection Agency 4
1.4 Verification Test Site Location 5
1.5 Raw Water Characterization 5
Chapter 2 Equipment Description 7
2.1 Statement of Performance Capabilities 7
2.2 Equipment Description 7
2.2.1 Basic Scientific and Engineering Concepts of Treatment 7
2.2.2 Brimac HA 216 Media 8
2.2.3 Pilot Unit Containing HA 216 Media 8
2.3 Operator Requirements 12
2.4 Required Consumables 12
2.5 Waste Production 12
2.6 Licensing Requirements Associated with Equipment Operation 12
2.7 Known Limitations of HA 216 12
Chapters Methods and Procedures 13
3.1 Objectives 13
3.2 Quantitative and Qualitative Evaluation Criteria 13
3.3 Operational Data and water quality analyses 13
3.4 Field Operations Procedures 14
3.5 Recording Statistical Uncertainty for Water Quality Parameters 15
3.6 Verification Testing Schedule 15
3.7 Product Specific Test Plan 16
3.8 TASK A: Raw Water Characterization 16
3.9 TASKB: Initial TestRuns 16
3.9.1 Objectives 16
3.9.2 Work Plan 16
3.10 TASK C: Verification test 17
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3.10.1 Introduction 17
3.10.2 Experimental Objectives 17
3.10.3 Task 1: System Integrity Verification 17
3.10.3.1 Experimental Objectives 17
3.10.3.2 Operating Conditions 17
3.10.3.3 Operational Measurements and Analytical Schedule 17
3.10.4 Task 2: Adsorptive Capacity Verification 19
3.10.4.1 Experimental Objective 19
3.10.4.2 Operating Conditions 19
3.10.4.3 Operational and Analytical Schedule 19
3.10.5 Task 3: Documentation of Operating Conditions and Treatment Equipment
Performance 21
3.10.5.1 Task3 Objective 21
3.10.5.2 Work Plan and Analytical Schedule 21
3.10.6 Task 4: Data Management 22
3.10.6.1 Task 4 Experimental Objectives 22
3.10.6.2 Work Plan 22
3.10.7 Task 5: Quality Assurance/Quality Control (QA/QC) 23
3.10.7.1 Experimental Objectives 23
3.10.7.2 Work Plan 23
3.10.7.3 Analytical Methods 23
3.10.7.4 Samples Shipped Offsite for Analysis 24
Chapter 4 Results and Discussion 25
4.1 Introduction 25
4.2 System Integrity Verification Testing 25
4.2.1 Integrity Test Flow and Treated Water Volume 26
4.2.2 Integrity Test Uranium Results 27
4.2.3 Integrity Test Water Quality Results 28
4.2.4 Integrity Test Operational Observations and Findings 31
4.3 Capacity Verification Test 32
4.3.1 Flow, Volumetric Loading, and Bed Volumes 32
4.3.2 Capacity Test Uranium Results 33
4.3.3 Capacity Test Uranium Removal Discussion 35
Chapter 5 QA/QC 36
5.1 Introduction 36
5.2 Test Procedure QA/QC 36
5.3 Sample Handling 36
5.4 Chemistry Analytical Methods QA/QC 36
5.5 Documentation 37
5.6 Data Quality Indicators 37
5.6.1 Representativeness 37
5.6.2 Accuracy 37
5.6.2.1 Field Equipment Accuracy and Calibration 39
5.6.3 Precision 39
5.6.4 Completeness 41
5.7 Sampling, sample handling, and preservation 41
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5.7.1 Sampling Locations 41
5.7.2 Sample Collection 41
5.7.3 Sample Storage and Transport 42
Chapter 6 References 43
APPENDIX A: Additional Data on HA 216 Media Adsorption Rates and Capacity, Provided by
Brimac
List of Tables
Table 1-1. Grappone Toyota Well Monitoring Data 6
Table 2-1. Brimac HA 216 Media specifications 8
Table 3-1. Quantitative and Qualitative Evaluation Criteria 13
Table 3-2. Operational and Water Quality Data Recorded 14
Table 3-3. System Integrity Test Monitoring and Operation Data Collection Schedule 18
Table 3-4. System Integrity Test Water Quality Sampling Schedule 18
Table 3-5. Adsorptive Capacity Test Monitoring and Operation Data Collection Schedule 20
Table 3-6. Adsorptive Capacity Test Water Quality Sampling Schedule 21
Table 3-7. Water Quality Analytical Methods 24
Table 4-1. Verification Test Operational Data 26
Table 4-2. Verification Test Uranium Results 28
Table 4-3. Verification Test Temperature, pH, and Turbidity Results 29
Table 4-4. Verification Test Feed and Treated water General Water Quality Results 30
Table 4-5. Capacity Test Flow Rate, Treated Bed Volumes and Uranium Results 32
Table 5-1. Laboratory Analyses - Accuracy and Precision 38
Table 5-2. Field Instrument Calibration Check Schedule 39
Table 5-3. Precision Results - Field Duplicates -Relative Percent Deviation 40
Table 5-4. Completeness Requirements 41
Table 5-5. Sample Collection and Preservation Details 42
List of Figures
Figure 1-1. ETVtest organization chart 2
Figure 2-1. Photo #1 of the Brimac pilot unit 10
Figure 2-2. Photo #2 of the Brimac pilot unit 11
Figure 2-3. Photo #3 of the Brimac pilot unit 11
Figure 4-1. Uranium concentration versus time 34
Figure 4-2. Uranium concentration versus bed volume treated 34
VI
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Abbreviations and Acronyms
ANSI
BV
Brimac
cm
°C
DWSC
EBCT
EPA
ETV
FNPT
FTO
ft
g
gpm
kg
L
Ib
LCS
LFM
MB
MCL
N/A
NA
ND
NHDES
NIST
NRC
NRMRL
NSF
NTU
pCi
psi
PSTP
PVC
QA
QC
QAPP
RPD
SM
SOP
TDS
TOC
TSS
U
MS
jamhos
American National Standards Institute
bed volume
Brimac Environmental Services, Inc.
centimeter
degrees Celsius
Drinking Water Systems Center
empty bed contact time
U. S. Environmental Protection Agency
Environmental Technology Verification
Female National Pipe Thread
Field Testing Organization
foot
gram
gallons per minute
kilogram
liter
pound
laboratory control sample
laboratory fortified matrix
method blank
maximum contaminant level
not applicable
not analyzed
not detected
New Hampshire Department of Environmental Services
National Institute of Standards and Technology
United States Nuclear Regulatory Agency
National Risk Management Research Laboratory
NSF International (formerly known as National Sanitation Foundation)
Nephelometric Turbidity Units
picocuries
pounds per square inch
product-specific test plan
polyvinyl chloride
quality assurance
quality control
Quality Assurance Project Plan
relative percent difference
Standard Methods for the Examination of Water and Wastewater
Standard Operating Procedure
total dissolved solids
total organic carbon
total suspended solids
uranium
microgram
micromhos
vn
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Acknowledgments
NSF International (NSF) and the New Hampshire Department of Environmental Services
(NHDES) co-managed the Field Testing Organization (FTO) responsibilities. NHDES staff
provided on site services including sample collection, observation and recording of the
equipment operating conditions, measurement of pH, temperature, radon, and alpha
radioactivity. NHDES also participated in review of the Test Plan and Final Report. NSF
provided logistical and communications support for the verification test, and was responsible for
data management, data interpretation, and the preparation of this report. The NSF laboratory
provided analytical services for uranium testing and related water quality parameters. Brimac
Environmental Services (Brimac) personnel installed the equipment and provided technical
assistance during the testing.
Field Testing Organizations
State of New Hampshire Department of Environmental Services
Drinking Water and Groundwater Bureau
Bernie Lucey
29 Hazen Drive
P.O. Box 95
Concord, NH 03301
Phone: (603)271-2513
NSF International
Mike Blumenstein, Project Manager
789 North Dixboro Road
Ann Arbor, MI 48105
Phone: (734) 913-5752
E-mail: blumenstein@nsf.org
Analytical Laboratories
NSF International Chemistry Laboratory
Kurt Kneen
789 N. Dixboro Road
Ann Arbor, MI 48105
Phone: 734-769-8010, ext. 2338
State of New Hampshire Department of Environmental Services Laboratory
Ms. Pat Bickford
29 Hazen Drive
P.O. Box 95
Concord, NH 03301
Vlll
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Manufacturer
Brimac Environmental Services, Inc.
Symon Thomas
318Gralake Ave
Ann Arbor, Michigan 48103
Phone: (734) 998-0763
E-mail: symonthomas@brimacservices.com
NSF also wishes to acknowledge Bruce Bartley for providing guidance and program
management support, and Dale Scherger of Scherger and Associates for help with report
preparation.
IX
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Chapter 1
Introduction
1.1 Environmental Technology Verification (ETV) Program Purpose and Operation
The U.S. Environmental Protection Agency (USEPA) has created the ETV Program to facilitate
the deployment of innovative or improved environmental technologies through performance
verification and dissemination of information. The goal of the ETV Program is to further
environmental protection by accelerating the acceptance and use of improved and more cost-
effective technologies. ETV seeks to achieve this goal by providing high-quality, peer-reviewed
data on technology performance to those involved in the design, distribution, permitting,
purchase, and use of environmental technologies.
ETV works in partnership with recognized standards and testing organizations; with stakeholder
groups consisting of buyers, vendor organizations, and permitters; and with the full participation
of individual technology developers. The program evaluates the performance of innovative
technologies by developing test plans that are responsive to the needs of stakeholders; by
conducting field or laboratory testing, collecting and analyzing data; and by preparing peer-
reviewed reports. All evaluations are conducted in accordance with rigorous quality assurance
protocols to ensure that data of known and adequate quality are generated and that the results are
defensible.
The USEPA has partnered with NSF International (NSF) under the ETV Drinking Water
Systems Center (DWSC) to verify performance of drinking water treatment systems that benefit
the public and small communities. It is important to note that verification of the equipment does
not mean the equipment is "certified" by NSF or "accepted" by USEPA. Rather, it recognizes
that the performance of the equipment has been determined and verified by these organizations
under conditions specified in ETV protocols and test plans.
1.2 Purpose of Verification
The DWSC evaluated the performance of the Brimac Environmental Services, Inc. (Brimac) HA
216 adsorptive media for removal of uranium (U)from drinking water. The verification was
initially split into two phases. The initial test (the test reported herein) was designed to evaluate
the ability of the adsorptive media to remove uranium from a drinking water source to a level at
or below the EPA National Primary Drinking Water Regulations (NPDWR) maximum
contaminant level (MCL) of 30 |ig/L, and to determine the adsorptive capacity of the media. This
report presents the verification test results for the initial test of the Brimac HA 216 adsorptive
media. The second test was planned to verify the media capacity and adsorptive performance at a
second drinking water location. The second test was designed to be performed with changes to
the media and test conditions (quantity of media used, residence time, loading and flow rates,
media particle size, etc.) based on the findings from this initial verification. Based on these
initial findings, the second test has been postponed until Brimac can make changes to the media
particle size to address media capacity and the short run times encountered during this test.
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1.3 Testing Participants and Responsibilities
The ETV testing of the Brimac HA 216 adsorptive media was a cooperative effort between the
following participants:
NSF
New Hampshire Department of Environmental Services (NHDES)
Brimac
USEPA
Figure 1-1 presents the primary participants in the ETV and their organizational relationships.
Bruce Bartley
NSF
Center Manager
QA/QC
1
1 1
Mike Blumenstein
NSF
Project Manager
Primary Contact
Kurt Kneen
NSF Chemistry Laboratory
Primary Contact
1
1 1 1
Symon Thomas
Brimac
Project Manager
Bernie Lucey
NHDES
FTO Project Manager
Jeff Adams
EPA
Project Officer
ETV DWS Center
Figure 1-1. ETV test organization chart.
The following is a brief description of each of the ETV participants and their roles and
responsibilities.
1.3.1 Field Testing Organizations
NSF and NHDES co-managed the field-testing organization (FTO) responsibilities for this ETV
test. The FTO was responsible for conducting verification testing of the pilot unit. Specific
responsibilities of the FTO were as follows:
• Provide needed logistical support, establish a communications network, and schedule and
coordinate the activities of all verification testing participants (NSF);
• Verify that the locations selected as the test sites have feed water quality consistent with
the objectives of the verification testing (NSF); and
• Oversee and conduct the daily testing activities, collecting test samples and delivering
those samples to the laboratories for analysis (NSF and NHDES).
1.3.1.1 NSF International
NSF is a not-for-profit organization dedicated to public health and safety, and to protection of the
environment. Founded in 1946 and located in Ann Arbor, Michigan, NSF has been instrumental
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in the development of consensus standards for the protection of public health and the
environment. The USEPA partnered with NSF to verify the performance of drinking water
treatment systems through the USEPA's ETV Program. NSF entered into an agreement on
October 1, 2000 with the EPA to create a DWSC dedicated to technology verifications. NSF
manages an ETV Program within the DWSC for the purpose of providing independent
performance evaluations of drinking water technologies. Verified results of product evaluations
presented in reports from ETV tests may accelerate a technology's entrance into the commercial
marketplace.
For the Brimac HA 216 adsorptive media verification test, NSF prepared the test/QA plan,
provided laboratory testing services, managed, evaluated, interpreted, and reported on the data
generated by the testing, and reported on the performance of the technology.
The following were specific NSF roles and responsibilities:
• Prepare the Product Specific Test Plan (PSTP) for the verification testing;
• Review the PSTP to insure compliance with the general requirements of the appropriate
EPA/NSF ETV Protocols;
• The NSF QA/QC Department conducted an audit at the test site to confirm testing
followed the PSTP;
• Manage, evaluate, interpret and report on the test data;
• Coordinate the report reviews; and
• The NSF Chemistry Laboratory analyzed samples throughout the test for uranium and
various other water quality parameters.
Contact Information:
NSF International
789 N. Dixboro Road
Ann Arbor, MI 48105
Phone: 734-769-8010
Fax: 734-769-0109
Contact: Bruce Bartley, Project Manager
Email: bartley@nsf.org
1.3.1.2 New Hampshire Department of Environmental Services
NHDES was responsible for the field support for the verification test. NHDES personnel
conducted the daily testing and observation activities at the test site in New Hampshire. NHDES
staff observed the equipment operation, recorded field measurements for flow, treated water
volume, pressure, temperature, etc. NHDES staff was responsible for collecting all water
samples and packaging the samples for transport to the NHDES laboratory and for shipment to
NSF.
In addition to FTO responsibilities, NHDES was responsible for reviewing the test plan and final
report since this testing may also serve as a pilot study component of a water supply permit
application for the installation of a full-scale version of this type of process at this site. Also,
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since the site was already a permitted public water supply, NHDES needed to be involved with
any modifications that may occur.
The NHDES Laboratory was responsible for analyzing samples throughout the test for various
water quality parameters, including pH, turbidity, radon, and alpha radioactivity,
Contact Information:
State of New Hampshire Department of Environmental Services
Drinking Water and Groundwater Bureau
29 Hazen Drive
P.O. Box 95
Concord, NH 03301
Phone: (603)271-2513
Fax: (603)271-2513
Contact: Bernie Lucey, Project Administrator
1.3.2 Brimac Environmental Services, Inc.
As the equipment manufacturer, Brimac was responsible for installing and removing the pilot
unit at the test site. Brimac was also responsible for providing written and verbal instructions for
equipment operation. Brimac provided technical assistance to the FTO during testing and during
the development of the PSTP. Brimac also reviewed this Verification Report.
Contact Information:
Brimac Environmental Services, Inc.
318Gralake Ave
Ann Arbor, Michigan 48103
Phone: (734) 998-0763
Contact: Symon Thomas
E-mail: symonthomas@brimacservices.com
1.3.3 U.S. Environmental Protection Agency
EPA provides leadership in the nation's environmental science, research, education and
assessment efforts. EPA works closely with other federal agencies, state and local governments,
and Indian tribes to develop and enforce regulations under existing environmental laws. EPA is
responsible for researching and setting national standards for a variety of environmental
programs and delegates to states and tribes responsible for issuing permits, and monitoring and
enforcing compliance. Where national standards are not met, EPA can issue sanctions and take
other steps to assist the states and tribes in reaching the desired levels of environmental quality.
The Agency also works with industries and all levels of government in a wide variety of
voluntary pollution prevention programs and energy conservation efforts.
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The following are specific EPA roles and responsibilities for this ETV:
• Technical review and QA oversight of the PSTP;
• Final approval of lab methods; and
• Technical review of the final report.
Contact Information:
United States Environmental Protection Agency
National Risk Management Research Laboratory
Water Supply and Water Resources Division
26 W. M.L. King Drive
Cincinnati, OH 45268
Phone: (513)569-7835
Fax: (513)569-7185
Contact: Jeffrey Q. Adams, Project Officer
E-mail: adams.jeff@epamail.epa.gov
1.4 Verification Test Site Location
This initial test was performed using a pilot unit containing HA 216 media installed at a business
served by groundwater drawn from a well deriving water from the fractured bedrock. The site
was at Grappone Toyota at 514 Route 3A in Bow, New Hampshire. This well serves 82
employees. The well can draw up to 11 gpm. The treated water was discharged to the sanitary
sewer system, which discharges to a municipal treatment plant.
1.5 Raw Water Characterization
The first task (Task A) of the verification test was to obtain a chemical and physical
characterization of the raw water. Historical data were needed to confirm that the source water
selected for the verification test had chemical constituents that would challenge the treatment
system and were also within the specifications required by the treatment system to be tested.
Historical water quality data supplied by NHDES for the test site are presented in Table 1-1.
Note that Table 1-1 gives uranium in picocuries per liter (pCi/L). Uranium reported as pCi/L can
be estimated in |j,g/L by multiplying the pCi/L number by 1.5, as specified by USEPA in the Safe
Drinking Water Act. This conversion applies to naturally occurring uranium, where the most
abundant isotope is U238.
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Table 1-1. Grappone Toyota Well Monitoring Data
Parameter
Uranium (pCi/L)(1)
Gross Alpha Radiation (pCi/L)
Radon (pCi/L)
Radium 226 (pCi/L)
pH
Specific Conductance (|amhos/cm)
Alkalinity (mg/L)
Hardness (mg/L)
Chloride (mg/L)
Cyanide (M-g/L)
Nitrate (mg/L N)
Nitrite (mg/L N)
Sulfate (mg/L)
Antimony (|J.g/L)
Arsenic (M-g/L)
Barium (|J.g/L)
Beryllium (|J.g/L)
Cadmium (M-g/L)
Chromium (|J.g/L)
Fluoride (mg/L)
Iron (mg/L)
Manganese (M-g/L)
Mercury (ng/L)
Nickel (|o,g/L)
Selenium (M-g/L)
Silver (|ag/L)
Sodium (mg/L)
Thallium (|J.g/L)
Zinc (M-g/L)
Sample Date
11/09/99 10/15/01
187
183
70,000
ND(O.l)
6.8
1093
90.2
273
267
ND(50)
1.76
ND (0.05)
11
ND(2)
9.5
ND(5)
ND(2)
ND(1)
ND(5)
1.19
ND (0.05)
19.3
ND(1)
ND(5)
ND(5)
ND(5)
93.8
ND(1)
12
177
192
57,000
0.6
NA
NA
NA
NA
340
NA
1.81
ND (0.05)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
(1) Note that uranium here is presented in pCi/L.
NA = Not analyzed
ND(X) = Not detected; (X) is the laboratory reporting limit for the analysis.
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Chapter 2
Equipment Description
2.1 Statement of Performance Capabilities
Brimac provided the following statement of performance capability:
"The Brimac Environmental Services, Inc. pilot treatment unit containing Brimac HA 216
adsorptive media is capable of reducing uranium up to 150 (ig/L to less than one (1) ug/L when
the feed water is treated at a hydraulic loading rate of 1.05 gpm/ft2 of media cross-sectional
surface area. Under these treatment conditions, approximately 83,000 gallons (gal) of feed water
can be treated per ft3 of media before uranium is detected in the treated water."
Brimac's statement of performance capabilities was used to establish the data quality objectives
for this verification test.
2.2 Equipment Description
2.2.1 Basic Scientific and Engineering Concepts of Treatment
The conceptual treatment process for uranium adsorption is based on passing uranium-
contaminated feed water through a bed of adsorptive media that has a strong affinity for uranium.
Uranium occurs in water predominantly as U234 (0.0057% abundance), U235 (0.7198%) and U238
(99.276%). These isotopes are radioactive alpha particle emitters. The isotopes have long half
C O Q
lives (2.33x10 years, 7.04x10 and 4.5x10 years, respectively), so uranium is stable for
treatment and disposal.
Brimac HA 216 is a hydroxyapatite-based media. The molecular formula for hydroxyapatite is
Cas(PO4)3(OH). Hydroxyapatite sequesters uranium by three processes: 1) incorporation within
the hydroxyapatite lattice through ion-exchange with calcium, 2) physisorption and
chemisorption with reactive phosphate and calcium oxide groups at the mineral surface, and 3)
reaction with free phosphate to form solids that precipitate out of solution.
According to Sorg (1988), uranium is a very reactive element that can form a variety of
complexes. Near pH 7, the common uranyl ion (UC>2+2) forms stable complexes with phosphate
and carbonate. In waters ranging from pH 7 to 10, and in the presence of carbonate, the
predominant soluble uranium complexes are UO2(CO3)2~2 and UO2(CO3)3~4. Millard and Hedges
(1996) found that the presence of carbonate increases uranyl sorption to hydroxyapatite.
Adsorptive media is normally in a packed bed contained in a pressure vessel. As the water flows
through the bed the uranium concentration decreases until it is no longer detectable. As the feed
water continues to flow through the treatment bed, the media, which comes in first contact with
the feed water, becomes saturated with uranium. A treatment band then progresses through the
treatment bed until breakthrough occurs. At that point, traces of uranium appear in the treated
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water. As flow continues the treatment band progresses through the media until the bed is
saturated. The uranium concentration in the treated water is then the same as that in the feed
water
Uranium adsorption by hydroxyapatite occurs slower than contaminant adsorption by activated
carbon, such that the rate-determining step is the chemical reaction resulting in adsorption, not
the rate of diffusion, as with activated carbon. For this reason, Brimac considers uranium
adsorption by hydroxyapatite to be more like an ion exchange process. The bed of
hydroxyapatite media has a mass transfer zone that moves through the bed in a plug flow manner
until the media is exhausted. Mass transfer zone length can be controlled by controlling the
hydraulic loading rate of the media.
2.2.2 Brimac HA 216 Media
As described in Section 2.2.1, Brimac HA 216 is a hydroxyapatite media. The particles are
highly porous and capable of adsorbing heavy metals, color forming compounds, trihalomethane
(THM) precursor compounds, taste and odor producing compounds as well as other organic and
inorganic compounds. The media can perform over a wide range of pH and temperature. HA
216 has a Langmuir isotherm capacity of just over one gram (g) of uranium per g of media. HA
216 specifications are given below in Table 2-1.
HA 216 is certified by NSF to NSF/ANSI Standard 61 for water treatment plant applications.
HA 216 also has European Pharmacopeoia and UK Drinking Water Inspectorate approvals.
Furthermore, hydroxyapatite is listed as 'Generally Recognized as Safe' by the U.S. Food and
Drug Administration.
Table 2-1. Brimac HA
Chemical Constituents:
216 Media Specifications
70-76% hydroxyapatite
7-9% CaCOs
9-ll%caibon
Physical Properties:
Total surface area
Bulk density
Pore size
Pore volume
100 m2/g
560 - 720 kg/m3
7.5 - 60,000 nm
0.225 cnrVg
Moisture < 5%
2.2.3 Pilot Unit Containing HA 216 Media
Brimac provides custom-designed treatment systems containing HA 216 media, or can also
supply the media alone. For verification testing, Brimac provided a pilot unit containing HA
216. The pilot unit consisted of the media in a TIGG Corporation Cansorb® C-5 steel drum. The
drum contains internal schedule 40 PVC plumbing to ensure proper distribution of the feed water
onto the bed of media. The C-5 is 30 inches (in) high, with a diameter of 19 in. The inner
diameter of the vessel was assumed to be 18.7 in. The vessel has an internal volume of
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approximately 4.8 ft3. The inlet and outlet openings are 3/4" female national pipe thread
(FNPT). The recommended maximum pressure to the vessel is 10 psig.
For this test, the pilot unit contained 50 pounds (Ib) (23 kilograms (kg)) of media. Table 2-1 lists
a bulk density range of 560-720 kg/m3 (35-45 Ib/ft3) for the media. Using the median density of
40 Ib/ft3, the volume of 50 Ib of media is approximately 1.3 ft3. With an internal diameter of
18.7 in, the media depth in the C-5 drum was approximately 8.2 in. The 18.7 in diameter gives a
media surface area of 1.9 ft . The unit was setup to be operated at 2.0 gpm, for a hydraulic
loading rate of 1.05 gpm/ft2. This flow would yield an empty bed contact time (EBCT) of
approximately 4.9 minutes (4 minutes and 54 seconds).
The feed and treated water lines were fitted with sample taps by installing 3/4 inch tees that
provided locations for sample collection. A totalizing water flow meter was installed in the inlet
line, downstream of the inlet sample tap and upstream of a gate valve. The gate valve was used
to control flow to the unit. A pressure gauge was installed on the inlet line downstream of the
gate valve to monitor inlet water pressure to the unit. The pressure gage was installed by placing
a 3/4 tee in the inlet line and connecting the pressure gauge to the tee. All fittings and meters
were easy to install using standard 3/4 inch pipe and fittings. These meters and gauges were
supplied by NSF and installed in the field. The feed line was connected to the pressure (bladder)
tank that is used to maintain water pressure in the building water supply system. The pressure
from the water system, as maintained by the well pump and bladder system was used to feed the
pilot unit. No additional pumping was required or used to maintain flow to the test system.
Figures 2-1 through 2-3 show pictures of the pilot unit and the installation.
Treated water was discharged to the sanitary sewer. This was accomplished by placing the
discharge hose into a toilet tank that flowed into the building sewer system. The potential for
cross contamination of the water and wastewater systems with this configuration was recognized,
but was considered acceptable for this temporary installation for the verification test. In a
permanent installation the treated water line would be piped directly into the water supply
system.
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Figure 2-1. Photo #1 of the Brimac pilot unit.
10
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Figure 2-2. Photo #2 of the Brimac pilot unit.
Figure 2-3. Photo #3 of the Brimac pilot unit.
11
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2.3 Operator Requirements
Operator attention during the verification test consisted of monitoring the equipment, conducting
on-site process water quality analyses, collecting samples for laboratory water quality analyses,
and to confirm operation in accordance with the PSTP. The pilot unit did not require daily
attention. However, an operator was on site six days per week to collect water samples and
record flows and pressures during the first two weeks (14 days) for the system integrity test. The
initial plan was to take daily readings and samples for the first 14 days (system integrity test
task) and then change to three site visits per week for the continuing capacity test. However, the
capacity test was completed shortly after the 14-day integrity test. Therefore, during the
verification test, an operator was present to collect samples, take readings, and observe the unit
operation on a daily basis, except Sundays.
2.4 Required Consumables
The following consumables were used in the ETV test:
• Brimac HA 216 media: one 50 Ib bag.
• No chemicals were added to the water and no electricity was used to pump influent water
to the unit for this verification. Therefore, there were no other consumables used for this
test.
2.5 Waste Production
The media does not require backwashing, so the only waste produced is spent media. The media
needs to be disposed of following United States Nuclear Regulatory Commission (NRC)
guidelines. Spent media that has accumulated uranium above 0.05 percent by weight is
classified as a source material under The Atomic Energy Act of 1954. Brimac has assumed
ultimate responsibility for disposal of the spent media. Brimac has an agreement with a uranium
recovery and reprocessing company to recover the adsorbed uranium from the spent media.
2.6 Licensing Requirements Associated with Equipment Operation
States generally require a specific grade of waterworks operator permit in order to operate a filter
process on a public water supply. However, this requirement did not apply for the ETV since all
of the treated water was discharged to the sewer system.
2.7 Known Limitations of HA 216
Divalent metals, calcium, and lead present at concentrations higher than 1 mg/L may reduce
uranium adsorption capacity by competing for reactive sites. General water quality parameters,
such as Ca, Mg, Mn, Fe, Alkalinity, SO4, Cl, Fl, and silica were monitored to determine if any
significant adsorption of these common constituents was occurring in the media.
12
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Chapter 3
Methods and Procedures
3.1 Objectives
The objectives of the verification test were to evaluate the pilot unit in the following areas:
• Evaluate the ability of Brimac HA 216 adsorptive media to remove uranium from a
drinking water source;
• Determine the adsorptive capacity of the HA 216 media for uranium;
• Determine impacts of any variations in feed water quality or process variation on media
performance;
• Report the logistical, human and other resources necessary to operate the equipment; and
• Determine ease of operation of the equipment.
3.2 Quantitative and Qualitative Evaluation Criteria
In order to address the above objectives, the verification test employed the quantitative and
qualitative factors listed in Table 3-1 for evaluation of the Brimac pilot unit.
Table 3-1. Quantitative and Qualitative Evaluation Criteria
Quantitative Criteria
Feed water flow
Feed and treated water quality
Hours of operator attention
Quantity of spent media
Length of operation until uranium exceeds 30 ug/L
Qualitative Criteria
Ease of operation
Safety
Maintenance requirements
Impact of operator experience on successful operation
3.3 Operational Data and water quality analyses
Table 3-2 gives operational and water quality parameters monitored during the verification test.
Turbidity and pH were measured at the NHDES Laboratory instead of in the field. The NHDES
Laboratory is only a few miles from the test sites, so grab samples for these parameters were
collected and immediately transported to the lab for analysis within the allowable holding times.
The radiological analyses (radon and alpha radioactivity) performed by the NHDES were only
for informational purposes, because the media is not designed to remove radioactive
contaminants as a group, only uranium. As such, the data for these parameters were not included
as primary verification parameters during development of the test plan.
13
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Table 3-2. Operational and Water Quality Data Recorded
On-Site Parameters
Operational Data
Feed water flow
Feed water pressure
Cumulative volume of water treated
Hours operators) spent on site
Water Quality Data
Temperature
Water Quality Laboratory Analyses
NHDES
pH
Turbidity
Alpha Radioactivity
Radon 222
NSF
Alkalinity
Arsenic (total)
Aluminum
Calcium
Chloride
Total Dissolved Solids (TDS)
Fluoride
Hardness (total)
Iron (total)
Magnesium
Manganese
Nitrate
Total Organic Carbon (TOC)
Phosphate (total)
Silica (total)
Sodium
Sulfate
Total Suspended Solids (TSS)
UV254
Uranium
3.4 Field Operations Procedures
The EPA/NSF ETV Protocol for Equipment Verification Testing for Removal of Radioactive
Chemical Contaminants (April 2002, Chapter 1) and the EPA/NSF ETV Equipment Verification
Testing Plan for Adsorptive Media Processes for the Removal of Arsenic (September 2003,
Chapter 6) specify the procedures to be used to ensure the accurate documentation of pilot unit
performance and treated water quality.
NSF and NHDES co-managed the verifications test, sharing the responsibilities of FTO and
analytical laboratory. Testing activities were conducted following the procedures described in
the PSTP. The pilot unit was operated 24 hours a day, seven days a week throughout the testing
period.
The verification test plan included two main tasks: System Integrity Verification and Adsorptive
Capacity Verification. System Integrity Verification was a two-week operation of the pilot unit
with daily monitoring to ensure the media and pilot unit were functioning properly, and to
identify any major systemic problems such as channeling, insufficient media, excessive headloss
buildup, etc. Adsorption Capacity Verification was intended to evaluate the capability of the
media at a set contact time to remove uranium to below the EPA NPDWR MCL of 30 |J,g/L.
14
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3.5 Recording Statistical Uncertainty for Water Quality Parameters
For the analytical data obtained during verification testing, 95% confidence intervals were
calculated for uranium data and for all other water quality data where the sample set contained
eight or more values.
The following formula was employed for confidence interval calculation:
Confidence interval = X + tn-i, i.- \S/*Jnj
Where: X is the sample mean;
S is the sample standard deviation;
n is the number of independent measures included in the data set;
t is the Student's t distribution value with n-1 degrees of freedom; and
a is the significance level, defined for 95% confidence as: 1 - 0.95 = 0.05.
According to the 95% confidence interval approach, the a term is defined to have the value of
0.05, thus simplifying the equation for the 95% confidence interval in the following manner:
95% confidence interval = X + tn-1,0.9
Results of these calculations are expressed as the sample mean plus or minus the width of the
confidence interval.
pH statistics were calculated on a log basis. It should be noted that using mean data and
confidence intervals for treated water (effluent) samples for a parameter that is removed in an
adsorptive process has only limited application when the test run is short (1-2 months). The
concentration of uranium in the treated water was expected to start at a low concentration and
then rise as the media was exhausted. Therefore, the mean concentration represented the average
of very low and much higher values.
3.6 Verification Testing Schedule
Verification testing activities include equipment set up and shakedown, equipment integrity,
adsorptive capacity verification tests, and water quality sampling and analysis. The test schedule
was developed to encompass all of these activities.
Testing began in July of 2007. The system integrity and adsorptive capacity verification tests
were initiated simultaneously. The system integrity test ran for a two-week (13 full days plus 8
hours) period. The adsorptive capacity test was designed to run until at least 60 ng/L of uranium
was detected in the treated water. Initially, it was expected that the capacity test would run for
three weeks after the end of the integrity test. However, the capacity ended after 15 days of
operation as the effluent concentration of uranium had exceeded the 60 (ig/L level.
15
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3.7 Product Specific Test Plan
The ETV protocol and PSTP prepared for this verification test divided the work into three main
tasks (A, B, C) with Task C, the verification test itself, divided into five sub-tasks. These tasks
were:
Task A: Raw Water Characterization
Task B: Initial Test Runs
Task C: Verification Test
Task 1: System Integrity Verification
Task 2: Adsorptive Capacity Verification
Task 3: Documentation of Operating Conditions and Treatment Equipment Performance
Task 4: Data Management
Task 5: Quality Assurance/Quality Control
Shakedown testing was conducted during Task B to assure the equipment was functioning as
intended. There were no changes made to the PSTP after the shakedown period as the media and
pilot equipment was found to be working properly.
3.8 TASK A: Raw Water Characterization
The objective of this task was to obtain a chemical and physical characterization of the raw
water. Historical water quality data was supplied by NHDES for the test site. These data
provided sufficient information to determine that the water source were compatible with the HA
216 adsorptive media and present a fair challenge to the media. The data for the test site is
presented in Table 1-1 in Section 1.5.
The first feed water samples from the system integrity test were compared to the historical data
to ensure there were no significant changes in the source water quality.
3.9 TASK B: Initial Test Runs
3.9.1 Objectives
The primary objective of this task was to install and operate the test unit to check system
integrity and ensure the unit was functioning properly for the verification test. A Brimac
representative and an NSF testing technician performed all startup and shakedown testing
activities.
3.9.2 Work Plan
Brimac staff coordinated with the FTO to install the equipment and ready the test system for
operation. A Brimac representative was on-site to direct final connections and the startup of the
equipment. Once ready for operation, Brimac ran the initial startup and shakedown tests to
determine the proper operating conditions for water treatment. The system started without any
difficulties and no sampling and analysis was performed during the one-day startup period.
16
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3.10 TASK C: Verification test
3.10.1 Introduction
There are five sub-tasks to be performed to achieve a successful verification test. Each of these
tasks is described in this section.
3.10.2 Experimental Objectives
The objective of this task is to assess the ability of the Brimac HA 216 media to remove uranium
from the feed water, and to assess the media's capacity for uranium adsorption. The tasks
described herein are designed to assess uranium removal, monitor equipment operation, and also
monitor other water quality parameters. Statistical analysis (standard deviation and confidence
intervals) was performed on all analytes with eight or more discrete samples collected over the
verification period.
3.10.3 Task 1: System Integrity Verification
3.10.3.1 Experimental Objectives
The objectives of Task 1 were as follows:
• Establish equipment operational reliability under field conditions; and
• Collect operational and water quality data under field conditions that can be related to the
operating time, throughput and water quality objectives stated by the manufacturer.
The System Integrity Verification testing was designed to demonstrate the initial ability of the
adsorptive media to remove the feed water uranium concentration to below the EPA MCL of 30
Hg/L in the treated water. During Task 1, the FTO also evaluated the reliability of pilot unit
operation under the environmental and hydraulic conditions at the test site, and determined
whether performance objectives stated in 2.1 could be achieved for uranium removal at the set
operating parameters for the pilot unit.
3.10.3.2 Operating Conditions
The pilot unit was operated for 320 hours (13 full days plus eight hours) during Task 1 to collect
data on equipment performance and water quality for pilot unit and media performance
verification. The pilot unit was operated continuously, within the target flow of 2.0 + 0.5 gpm.
Note that the wide tolerance for the flow was necessary due to the water pressure fluctuations at
the test site.
3.10.3.3 Operational Measurements and Analytical Schedule
Operational Measurements
Operational data was collected once per day, Monday through Saturday. The dealership was
closed on Sundays, so the pilot unit could not be accessed, but the flow was maintained on a
continuous basis at approximately 2 gpm. The data collection schedule is summarized in Table
3-3.
17
-------
Table 3-3. System Integrity Test Monitoring and Operation Data Collection Schedule
Parameter
Feed water cumulative volume
Feed water flow
Treated water pressure
Operating hours
Labor Hours
Monitoring Frequency
Record once per day
Check & record once per day (adjust if 3
minute running average flow is below
1.5 gpm, or above 2.5 gpm.)
Check & record once per day
Record once per day in log the total
hours of operation since last site visit.
Determine labor hours required.
Monitoring Method
Feed water totalizer meter
Feed water flow meter
Treated water pressure gauge
Note operation/downtime in
logbook.
Record time on-site daily in
logbooks.
Water Quality Measurements
Grab samples for on-site and laboratory water quality analyses were collected based on the
sampling schedule presented in Table 3-4.
Table 3-4. System Integrity Test Water Quality Sampling Schedule
Parameter
On-Site Analysis
Temperature
Laboratory Analyses
pH
Turbidity
Uranium
Arsenic (total)
Radon 222
Alpha Radioactivity
Alkalinity
Aluminum
Calcium
Chloride
TDS
Fluoride
Total Hardness (as CaCO3)
Iron (total)
Magnesium
Manganese
Nitrate
TOC
Phosphate (total)
Silica (total)
Sodium
Sulfate
TSS
UV254
Sampling Frequency
Daily, Mon.-Sat.
Daily, Mon.-Fri.
Daily, Mon.-Fri.
Daily, Mon.-Sat.
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Streams to be Sampled
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
Feed and Treated
18
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3.10.4 Task 2: Adsorptive Capacity Verification
3.10.4.1 Experimental Objective
The objective of this task was to determine the media's capacity to remove uranium from the
feed waters to concentrations less than 30 |ig/L. The performance of the media is a function of
the feed water quality and contact time. Uranium breakthrough is highly dependent on the
source water's uranium concentration, and the adsorptive characteristics of the media. While the
water quality standard for uranium is 30 |J,g/L, Brimac requested that the pilot units be operated
until the treated water uranium concentration reached 60
The adsorptive capacity test was designed to provide quality operating and water quality data
relative to Brimac' s statement of performance capabilities, which was as follows:
"The Brimac Environmental Services, Inc. pilot treatment unit containing Brimac HA 216
adsorptive media is capable of reducing uranium up to 150 |J,g/L to less than one ug/L when the
feed water is treated at a hydraulic loading rate of 1.05 gpm/ft2 of media cross-sectional surface
area. Under these treatment conditions, approximately 83,000 gal of feed water can be treated
per ft3 of media before uranium is detected in the treated water."
3.10.4.2 Operating Conditions
The Task 2 Adsorption Capacity Verification began simultaneously with Task 1: System
Integrity Verification Testing. Based on the performance statement above, Brimac estimated that
the pilot unit would need to operate for approximately 36 days until uranium was detected in the
treated water.
During the verification test, the unit was operated at the target flow of 2.0 ±0.5 gpm, as for Task
1. The unit was operated until the treated water uranium concentration rose to 60 ug/L. This
occurred sooner than anticipated and the Adsorptive Capacity test ended on July 25 after 15 days
of operation.
Test unit operation was monitored, and operational data was collected as described below.
3.10.4.3 Operational and Analytical Schedule
Operational Measurements
The original planned data collection schedule for Task 2 is summarized in Table 3-5. System
operation monitoring was similar to that for Task 1, the main difference being the monitoring
frequency.
19
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Table 3-5. Adsorptive Capacity Test Monitoring and Operation Data Collection Schedule
Parameter
Feed cumulative volume
Feed flow
Feed pressure
Operating hours
Labor Hours
Monitoring Frequency
Record at each site visit
Check & record at each site visit (adjust
when 5% above or below target; record
before and after adjustment)
Check & record at each site visit
Record once each site visit the total
hours of operation since last site visit.
Note any operation downtime in the log
book
Record number of hours on site at each
visit
Monitoring Method
Feed totalizer meter
Feed flow meter
Feed pressure gauge
Note any operation downtime in
the log book
Record time in logbooks
The original test schedule assumed that the integrity test would end before the adsorptive
capacity of the media was reached. The plan at that time was to reduce the monitoring frequency
and continue the capacity test. However, since the uranium concentration reached the 60 [ig/L
level within two days of completion of the integrity test, the monitoring frequency for the
capacity test was the same as for the integrity test.
Water Quality Measurements
As discussed above in 3.10.4.2, Task 2 began simultaneously with Task 1. For the duration of
Task 1, the Task 1 analytical schedule in Table 3-4 was followed. Once Task 1 was completed,
the Task 2 sampling schedule presented in Table 3-6 was going to be followed for the duration of
Task 2. The uranium sampling frequencies were intended to provide sufficient water quality
data to effectively characterize the breakthrough profile of uranium.
However, as discussed above, the uranium concentration in the treated water had reached 60
Hg/L at the end of the integrity test. Therefore the capacity test was stopped after 15 operating
days (Days 0-15) and the original plan to reduce sampling frequency was not implemented. The
test unit continued to operate for 20 days (Days 0-20). Flow data and operational data were
collected on Days 17 and 20, but uranium analyses were not performed.
20
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Table 3.6. Adsorptive Capacity Test Water Quality Sampling Schedule
Parameter
On-Site Analyses
Temperature
Laboratory Analyses
pH
Turbidity
Uranium
Arsenic (total)
Radon 222
Alpha Radioactivity
Alkalinity
Aluminum
Calcium
Chloride
TDS
Fluoride
Total Hardness (as CaCO3)
Iron (total)
Magnesium
Manganese
Nitrate
TOC
Phosphate (total)
Silica (total)
Sodium
Sulfate
TSS
UV254
Sampling Frequency
M, W, F
M, W, F
M, W, F
M, W, F
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Streams to be Sampled
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
Feed and Treated water
3.10.5 Task 3: Documentation of Operating Conditions and Treatment Equipment
Performance
3.10.5.1 Task 3 Objective
The objective of this task was to accurately and fully document the operating conditions and
performance of the equipment. The task was performed in conjunction with both Task 1: System
Integrity Verification and Task 2: Adsorptive Capacity Verification.
During each site visit (daily except Sunday), system operating conditions were documented. The
volumetric flow through adsorptive media is a critical parameter, and was monitored and
documented. Adsorptive media performance is affected by the EBCT, which varies directly with
the volumetric flow through the vessel.
3.10.5.2 Work Plan and Analytical Schedule
During each site visit for both Tasks 1 and 2, the treatment equipment operating parameters were
monitored and recorded as described in 3.10.3.3 and 3.10.4.3.
21
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3.10.6 Task 4: Data Management
3.10.6.1 Task 4 Experimental Objectives
The objective of this task was to establish an effective protocol for data management at the field
operations site, and for data transmission and sample shipment between NHDES and NSF
DWSC staff. Development of a viable structure for the recording and transmission of field-
testing data by the NHDES was important to ensure NSF received sufficient and reliable data for
verification purposes.
The data management system used for this verification involved the use of computer spreadsheet
software and manual recording of system operating parameters.
3.10.6.2 Work Plan
The following outline was used for data handling and data verification by the FTO:
• The field technicians recorded operating and water quality data and calculations by hand
on custom-designed data sheets bound in a three-ring binder.
• All logbook pages were numbered.
• The logbook indicated the starting and ending dates that apply to entries in the logbook.
• All logbook entries were made in blue or black water-insoluble ink.
• All corrections in the logbook were made by placing one line through the erroneous
information and initialed by the field-testing operator.
• Pilot operating logs included a description of the adsorptive media equipment, description
of test run(s), names of visitor(s), description of any problems or issues, etc; such
descriptions were provided in addition to experimental calculations and other items.
The original logbook was stored on site. The original logbook pages were periodically faxed to
the NSF Project Manager.
The database for this verification-testing program was set up in the form of custom-designed
spreadsheets. The spreadsheets were capable of storing and manipulating each monitored water
quality and operational parameter from each task, each sampling location, and each sampling
time. All data from the laboratory notebooks and data log sheets were entered into the
appropriate spreadsheets. NSF DWSC staff conducted the data entry offsite. All recorded
calculations were checked at this time. Following data entry, the spreadsheet was printed out
and another individual checked the printout against the handwritten data sheet. Any corrections
were noted on the hard copies and corrected on the screen, and then a corrected version of the
spreadsheet was printed out.
22
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3.10.7 Task 5: Quality Assurance/Quality Control (QA/QC)
3.10.7.1 Experimental Objectives
The objective of this task was to maintain strict QA/QC methods and procedures during
verification testing. Maintenance of strict QA/QC procedures is important so that if a question
arises when analyzing or interpreting data collected, it is possible to verify exact conditions at the
time of testing.
3.10.7.2 Work Plan
Equipment flow was verified and recorded during each site visit. The items listed below are in
addition to any specified checks outlined in the analytical methods.
It is extremely important that system flow is maintained at a set value, and monitored frequently.
Doing so allows a constant and known EBCT to be maintained in the pilot units. Therefore, an
important QA/QC objective was the maintenance of a constant volumetric flow rate through the
adsorptive media by frequent monitoring and documentation. Documentation included an
average and standard deviation of recorded flows through the adsorptive media.
The flow meter and pressure gauges used for verification testing are subject to periodic
calibrations as part of the NSF testing laboratory's QA/QC program. The flow meter and
pressure gauges used for this test were calibrated within the six months previous to the start of
testing.
Weekly QA/QC Verifications:
• In-line flow meter (clean any fouling buildup as needed, and verify flow volumetrically);
• In-line totalizer meter (clean any foulant buildup as needed and verify production rate
volumetrically); and
• Tubing/piping (verify good condition of all tubing and connections, replace as
necessary).
3.10.7.3 Analytical Methods
The analytical methods used for on-site and laboratory analyses are listed in Table 3-7. The
analytical laboratories performed the water quality analyses using EPA or Standard Methods
procedures. All of the required QA/QC procedures were performed in accordance with the
published methods, and as described in the Quality Assurance Project Plan (QAPP) in Chapter 6
ofthePSTP.
23
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Table 3-7. Water Quality Analytical Methods
Parameter
pH
Temperature
Turbidity
Uranium
Arsenic (total)
Radon 222
Gross Alpha Radioactivity
Alkalinity
Aluminum
Calcium
Chloride
TDS
Fluoride
Total Hardness (as CaCO3)
Iron (total)
Magnesium
Manganese
Nitrate
TOC
Phosphorous (total)
Silica (total)
Sodium
Sulfate
TSS
UV254
Analytical Method
EPA 150.1
SM(2) 2550
EPA 180.1
EPA 200.8
EPA 200.8
EPA 913
EPA 900
EPA 3 10.2
EPA 200.7
EPA 200.7
EPA 300.0
SM 2540 C
SM 4500-F C
SM 2340 B
EPA 200.7
EPA 200.7
EPA 200.8
EPA 300.0
SM5310C
SM 4500-P E
EPA 200.7
EPA 200.7
EPA 300.0
SM 2540 D
SM5910B
Method Detection Limit
N/A(1)
N/A
1.0 MTU
lUg/L
2ug/L
200 pCi/L
4pCi/L
5mg/L
lOug/L
20ug/L
0.5 mg/L
5mg/L
0.1 mg/L
2 mg/L
20ug/L
20ug/L
lug/L
50ug/L
0.1 mg/L
0.1 mg/L
0.2 mg/L
0.5 mg/L
0.5 mg/L
2 mg/L
0.000 Absorbance/cm (A/cm)
(1) Not applicable
(2) SM = Standard Methods for the Examination of Water and Wastewater
3.10.7.4 Samples Shipped Offsite for Analysis
Samples for off-site laboratory analysis were collected and preserved in accordance with
Standard Methods 3010 B, paying particular attention to the sources of contamination as outlined
in Standard Methods 3010 C. The samples were kept cool, in the range of 2°C to 8°C
immediately upon collection, shipped in a cooler, and maintained at a temperature of 2°C to 8°C.
Any samples collected Friday through Sunday were kept at 2°C to 8°C until they could be
shipped on Monday. Temperature blanks accompanied all samples shipped to NSF. The
temperature of each blank was measured and recorded for each sample set.
24
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Chapter 4
Results and Discussion
4.1 Introduction
The ETV test of the Brimac HA 216 adsorptive media was designed with two primary tasks, the
Integrity Verification Test and the Adsorption Capacity Test. The pilot unit, which contained the
media, was installed at the Grappone Toyota location in Bow New Hampshire in early July 2007.
A totalizing flow meter and feed pressure gauge, calibrated and supplied by NSF, were installed
when the equipment was setup. The well system pump and bladder tank provided sufficient
pressure to easily achieve the target flow. The pressure in the bladder tank did vary with water
use at the business and cycled based on the minimum and maximum pressure set by the well
control system. While the changing pressure did cause some flow fluctuation during a well pump
cycle, the flow to the test unit remained within the test specifications of 2.0 gpm + 0.5 gpm.
Overall the system startup went smoothly and quickly with the unit being ready for the start of
verification testing within a two days. No samples were collected during the startup/shakedown
period.
The Integrity Test began on July 10 and ran continuously through July 24. This met the target of
operating the unit for two weeks (13 days plus 8 hours). The Adsorption Capacity Test began
simultaneously with the Integrity Test and continued until July 25. By this date, the
concentration of uranium in the treated water had risen to 68 ng/L, which exceeded the target for
the capacity test. Therefore the capacity test was stopped after only 15 days of operation.
This section of the ETV report presents the results of the Integrity Verification Test and
Adsorption Capacity Verification Test, and a discussion of these results. The results and
discussion include the concentration of uranium in the feed and treated water, the operational and
other water quality data collected during the tests, and an assessment of the equipment operation.
4.2 System Integrity Verification Testing
The Integrity Test was started on July 10 and ran without interruption through the scheduled test
period. Monitoring and on site data collection were performed as scheduled to verify equipment
performance. There were no significant difficulties encountered during the test. Table 4-1
summarizes the operational data collected during the test. Table 4-1 also includes the additional
operating data collected as part of the Adsorption Capacity Test. These data were combined into
one table for ease of presentation.
25
-------
Table 4-1. Verification Test Operational Data
Day
0
1
2
o
J
4
5
6
7
8
9
10
11
12
13
14
15
17
20
Date
10-Jul
11-Jul
12-Jul
13-Jul
14-Jul
15-Jul
16-Jul
17-Jul
18-Jul
19-Jul
20-Jul
21-Jul
22-Jul
23-Jul
24-Jul
25-Jul
27-Jul
30-Jul
Number
Mean
Max.
Min.
Std. Dev.
95% Conf. Interval
Flow(1)
(gpm)
1.89
2.00
1.58
1.65
1.90
n/m
1.85
1.90
1.98
1.90
2.17
2.16
n/m
2.15
2.16
n/m
2.10
2.10
15
1.97
2.17
1.58
0.18
1.88-2.06
Cumulative Volume
from Flow Totalizer
(gal)
0
2,101
4,307
6,638
9,489
n/m
15,243
17,330
18,694
21,402
24,503
28,231
n/m
33,729
36,731
n/m
45,726
54,728
—
—
—
—
—
—
Feed Pressure
(psi)
0
0.7
8.5^
1
1
n/m
1
1
1
1
1
1
n/m
1
1
n/m
1
n/m
14
1.4
8.5
<0.5
2.1
0.4-2.5
Time On Site
(hrs)
n/r
1.50
0.50
0.75
0.42
n/s
0.50
1.25
0.33
0.75
0.50
0.50
n/s
0.33
0.75
n/s
0.33
0.67
14
0.65
1.50
0.33
0.35
0.47-0.83
(1) The reported flows are the averages of several flows recorded over several minutes.
(2) The field notes indicate the outlet line was kinked, which most likely caused this high pressure reading.
Pressure dropped to more normal range after the kink was removed
n/m - not measured
n/s - not on site
n/r - not recorded
4.2.1 Integrity Test Flow and Treated Water Volume
Flow and volume of water treated were identified as critical parameters, because residence time
(EBCT) and total volume of water treated directly relate to the performance of adsorptive media.
The goal for flow control was to maintain the flow at 2.0 gpm + 0.5 gpm during the verification
test. As shown by the data in Table 4-1, the flow was steady during the test with a mean value of
1.97 gpm, and a range of 1.58 to 2.17 gpm.
The flow to the unit cycled as the pressure in the well system cycled from high to low, varying
by up to 0.4 gpm. The well pump would activate every few minutes when the pressure in the
bladder tank reached the low-pressure set point and then the pump would shut off when the
system reached the high-pressure set point. Therefore, the field technician observed several flow
rates over several minutes and recorded a range of flows on the bench sheet. These flow ranges
were then used to report an average flow for the unit. While the flow did change over a range of
readings, the average flow was close to the target of 2.0 gpm and was consistent during the test.
26
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Overall, the frequent change in flow rate did not impact the volume of water treated on a daily
basis, as shown by comparing the data for the average flow and daily volume treated. The mean
flow reported for the 20 days of operation (Days 0-20) was 1.97 gpm, while the mean flow
calculated using the total volume treated was 2.03 gpm (54,728 gal over 20 days as measured by
the totalizer on the flow meter (449.6 hours of operation)).
The hydraulic loading rate during the test, based on a mean flow of 1.97 gpm and a pilot unit
surface area of 1.90 ft2, averaged 1.04 gpm/ft2. This was very close to the Brimac recommended
test condition hydraulic loading rate of 1.05 gpm/ft2. The Pilot Unit contained 50 Ib of media
with an approximate volume of 1.3 ft3. The EBCT during the verification test was approximately
4 minutes and 54 seconds.
4.2.2 Integrity Test Uranium Results
The primary objectives of the System Integrity Test were to demonstrate that the source water
contained uranium at levels needed for the capacity test and that the test unit could achieve the
targeted concentration for uranium (30 |J,g/L) in the treated water. Table 4-2 shows the uranium
results for the entire duration of the verification test (Integrity and Capacity Tests). The uranium
concentration in the source water had a mean concentration of 190 |J,g/L, which was within the
target range for the verification test. The pilot unit produced treated water with uranium
concentrations of <1 |j,g/L at the start of the test. Thus, the goals of the Integrity Test were met
and the verification test proceeded for the duration of the Integrity Test period (minimum of 13
days, 8 hours). The uranium concentration in the treated water began to increase after two days
of operation and exceeded the water quality standard of 30 |j,g/L on Day 10. As will be discussed
further in the Capacity Test Section 4.3, this indicated that the capacity of the media was less
than expected. From an Integrity Test perspective, the objectives to demonstrate that the unit
could remove uranium to levels below the water quality standard and that the source water
concentrations were sufficient to challenge the unit were achieved.
The mean source water uranium concentration was 190 |J,g/L, which was somewhat lower than
the historical concentrations of 260 to 280 ng/L. Note these historical concentrations were
estimated based on the concentrations of 177 and 187 pCi/L, as shown in Table 1-1. The
conversion factor used for this estimate was 1.5. The somewhat lower concentrations of uranium
in the source water were sufficient to provide a challenge to the test unit, as Brimac' s
performance claim was based on a source water concentration of 150
While the treated water uranium concentration increased more quickly than anticipated, the mean
concentration for the 15 day monitoring period was 29.7 ng/L. However, the treated water was
only below the water quality standard for the first 10 days of the test.
Figure 4-1 in Section 4.3 presents the uranium results in a time series graph.
27
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Table 4-2. Verification Test Uranium Results
Day
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Date
10-Jul
11-Jul
12-Jul
13-Jul
14-Jul
15-Jul
16-Jul
17-Jul
18-Jul
19-Jul
20-M
21-Jul
22-M
23-M
24-M
25-M
Number
Mean
Max.
Min.
Std. Dev.
95% Conf. Interval
Uranium Concentration
Feed (ng/L) Treated (ng/L)
230
140
140
140
160
n/m
170
210
170
180
220
190
n/m
200
230
250
14
190
250
140
36.6
170 -210
1
<1
2
4
8
n/m
30
26
16
25
45
49
n/m
67
45
68
13
29.7
68
<1
23.5
16.9-42.5
n/m - not measured
4.2.3 Integrity Test Water Quality Results
Several water quality parameters were monitored on a weekly basis during the test. Tables 4-3
and 4-4 show the results for these parameters.
The source water did not contain any noticeable suspended sediment as shown by the turbidity
data presented in Table 4-3 and the total suspended solids (TSS) data presented in Table 4-4. All
turbidity measurements were <1 NTU and all TSS concentrations were <2 mg/L. A
sediment/particulate pre-filter was not used in front of the test unit. There was no indication
during the test of any problems with particulate accumulation in the media bed. However, in
applications where the source water contains particulate matter, it may be necessary to use a pre-
filter to protect the media from accumulating solids, which could result in plugging the media
bed.
28
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Table 4-3. Verification Test Temperature, pH and Turbidity Results
Day
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
17
20
Date
10-Jul
11-Jul
12-Jul
13-Jul
14-Jul
15-Jul
16-Jul
17-Jul
18-Jul
19-Jul
20-Jul
21-Jul
22-Jul
23-Jul
24-Jul
25-Jul
27-Jul
30-Jul
Number
Mean
Max.
Min.
Std. Dev.
95% Conf. Interval
pH (SU)
Feed Treated
6.68
6.69
6.68
6.63
6.93
n/m
6.60
6.68
6.52
6.67
6.66
6.74
n/m
6.69
6.73
6.56
6.64
6.72
16
6.68
6.93
6.52
0.09
6.64-6.72
7.29
6.79
6.88
6.68
6.74
n/m
6.64
6.63
6.69
6.68
6.63
6.63
n/m
6.64
6.67
6.65
6.65
6.71
16
6.72
7.29
6.63
0.17
6.64-6.80
Temperature (°C)
Feed Treated
13.7
14.5
14.5
14.5
14.5
n/m
14.5
14.5
15.0
15.0
14.5
14.5
n/m
14.5
14.5
n/m
14.5
15.0
15
14.5
15.0
13.7
0.31
14.3-14.7
14.5
14.5
14.5
14.5
14.5
n/m
14.5
14.5
15.0
15.0
14.5
15.0
n/m
14.5
14.5
n/m
15.0
15.0
15
14.7
15.0
14.5
0.24
14.6-14.8
Turbidity (NTU)
Feed Treated
<1
<1
<1
<1
<1
n/m
<1
<1
<1
<1
<1
<1
n/m
<1
<1
<1
<1
<1
16
<1
<1
<1
N/A
N/A
<1
<1
<1
<1
<1
n/m
<1
<1
<1
<1
<1
<1
n/m
<1
<1
<1
<1
<1
16
<1
<1
<1
N/A
N/A
n/m - not measured
The temperature and pH of the source water were steady over the entire test. This was expected,
as groundwater sources generally do not vary over short periods of time. The source water pH
had mean value of 6.68, and the temperature averaged 14.6 °C. No treatment chemicals were
added to the system and the media did not impact the pH or temperature of the water. The treated
water pH had a mean value of 6.72, and the outlet temperature averaged 14.7 °C.
The water quality data for normal cations and anions (calcium, magnesium, sodium, iron, silica,
chloride, sulfate, alkalinity, fluoride, nitrate, phosphorus), as shown in Table 4-4, indicate that
the source water and treated water concentrations are basically the same, with the exception of
phosphorus. The phosphorus levels increased from <0.05 mg/L in the source water to a
concentration range of 0.08 to 0.19 mg/L in the treated water. The HA 216 adsorptive media is a
material that contains calcium, phosphorus, and hydroxide. The slight increase in phosphorus is
most likely due to a small amount of dissolution of the phosphorus in the media. The
contribution appears small. There was minimal or no discernable increase in calcium or
hydroxide (alkalinity) concentrations in the treated water. Calcium and hydroxide are the other
two components of the media (Cas(PO4)3(OH)).
29
-------
Table 4-4. Verification Test Feed and Treated water
Date
10-Jul
17-Jul
25-M
Max
Min
Date
10-Jul
17-Jul
25-Jul
Max
Min
Date
10-Jul
17-Jul
25-Jul
Max
Min
Date
10-Jul
17-Jul
25-Jul
Max
Min
Date
10-Jul
17-Jul
25-Jul
Max
Min
Date
10-Jul
11-Jul
17-Jul
19-Jul
25-Jul
Max
Min
Calcium (mg/L)
Feed Treated
130 120
360 390
130 130
360 390
130 120
Chloride (mg/L)
Feed Treated
430 440
480 460
400 400
480 460
400 400
Fluoride (mg/L)
Feed Treated
0.90 <0.1
0.90 0.5
0.98 0.8
0.98 0.8
0.90 <0.1
Aluminum (mg/L)
Feed Treated
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
TOC (mg/L)
Feed Treated
0.6 0.3
0.6 0.4
0.6 0.5
0.6 0.5
0.6 0.3
Radon 222 (pCi/L)
Feed Treated
n/m n/m
60,000 65,000
57,000 64,000
n/m n/m
64,000 71,000
64,000 71,000
57,000 64,000
Magnesium (mg/L)
Feed Treated
20 30
97 100
160 170
160 170
20 30
Sulfate (mg/L)
Feed Treated
13 9.4
14 13
12 13
14 13
12 9.4
Nitrate (mg/L N)
Feed Feed
1.7 0.007
1.9 0.007
1.6 0.007
1.9 0.007
1.6 0.007
Manganese (mg/L)
Feed Treated
0.074 <0.01
0.190 0.01
0.053 <0.01
0.190 <0.01
0.053 <0.01
TSS (mg/L)
Feed Treated
<2 <2
<2 <2
<2 <2
<2 <2
<2 <2
General Water Quality Results
Sodium (mg/L)
Feed Treated
170
230
170
230
170
170
200
170
200
170
Alkalinity
(mg/L CaCO3)
Feed Treated
82
81
91
91
81
120
82
85
120
82
Phosphorus (mg/L P)
Feed Treated
0.007
0.007
0.007
0.007
0.007
Silica
Feed
<0.01
<0.01
<0.01
<0.01
<0.01
Alpha Radioactivity (pCi/L)
Feed Treated
n/m n/m
170 10
n/m n/m
n/m 36
230 73
230 73
170 10
0.08
0.19
0.12
0.19
0.08
(mg/L SiO2)
Treated
0.074
0.19
0.053
0.19
0.053
Iron (mg/L)
Feed Treated
<0.02
O.02
<0.02
O.02
O.02
O.02
O.02
O.02
O.02
O.02
Hardness
(mg/L CaCO3)
Feed Treated
420
450
960
960
420
430
490
1,000
1,000
430
Arsenic (mg/L)
Feed Treated
0.007 O.002
0.007 0.006
0.007 0.007
0.007 0.007
0.007 0.006
TDS (mg/L)
Feed Treated
1,000
1,000
1,100
1,100
1,000
UV254 (absorbance)
Feed Treated
0.0109 0.9981
n/m n/m
0.0113 0.0033
n/m n/m
0.0139 0.0048
0.0139 0.9981
0.0109 0.0033
1,000
1,100
1,100
1,100
1,000
n/m - not measured
30
-------
There was no indication that the adsorption of metals, arsenic, manganese, or aluminum
impacted the media or its capacity. Aluminum was not detected in the source water. Arsenic was
present at 0.007 mg/L in the source water. On the first sampling day, the treated water arsenic
concentrations was <0.002 mg/L indicating that some adsorption of arsenic may have occurred.
However, the next two sample results (Day 7 and 15) showed that the treated water had similar
concentrations to the source water. If some arsenic adsorption did occurred it was only for the
first few days. Manganese concentrations on Day 1 and 7 were lower in the treated water
indicating some adsorption may be occurring. However, the concentration in the treated water
was higher on Day 15. Any adsorption that may have occurred did not appear to be at levels high
enough to impact the media.
NHDES monitored radon and alpha radioactivity for informational purposes. Verification testing
did not include radon and alpha radioactivity as key or primary parameters. The radon results
shown in Table 4-4 indicate that the media had no effect on radon levels in the water. These
results were expected, as there is no indication that the HA 216 media provides any treatment for
radon in groundwater. The alpha radioactivity was lower in the treated water. The source water
ranged from 170 to 230 pCi/L and the treated water ranged from 10 to 73 pCi/L. These data
would seem to suggest that the HA 216 media removes some of the materials contributing to the
alpha radioactivity.
4.2.4 Integrity Test Operational Observations and Findings
The objectives of the Integrity Test included establishing the equipment reliability and observing
factors related to ease of operation.
The pilot test unit was simple and easy to operate, particularly since there were no pumps
required for this installation and no need for automated controls or backwash type systems. As
described earlier, flow control was maintained by one manual control valve and the source water
was fed to the unit using well system pressure. In this application with the treated water
discharging by gravity to the sewer system there was no concern with operating the unit in -line
with the water supply system.
Time to operate and monitor the system was minimal with most time being spent for sample
collection. Table 4-1 shows the time that was spent on site to monitor the system and collect
samples. The average time on site was about 40 minutes. Time on site was longer the first two
days of the test, 90 minutes, and then decreased for the remainder of the test period.
As noted in the water quality discussion (Section 4.2.3), this source water had very low turbidity
and suspended solids levels. Therefore, concerns about plugging the media due to solids
accumulation and possible pressure buildup on the inlet side of the unit were not real issues in
this application. One of the initial measurements in the PSTP was to monitor the pressure
differential across the media by monitoring the inlet and outlet pressure. Measurement of the
inlet pressure was not performed, as it was not possible to maintain a steady inlet pressure to
compare with the outlet pressure. The inlet pressures varied as the well pump cycled between the
high and low set points on the bladder tank. Manual measurements once per day would not
account for the variation and could yield biased pressure differential data. Further, based on the
-------
low turbidity and low TSS concentrations, it was not expected that any pressure buildup would
occur due to solids entering the bed. While solids accumulation and the need for pre-filtration
was not a concern for this source water, other source waters may present a need for pre-filtration
and continuous monitoring of inlet and outlet pressure.
4.3 Capacity Verification Test
The Capacity test was started on July 10 and ran until July 25, a total of 15 days. The capacity
test was stopped early when it was discovered that the uranium concentration in the treated water
had exceeded the stop-test level of 60 ng/L. As discussed below, the test ended sooner than the
expected 36 days. Monitoring and on site data collection were performed as scheduled in the test
plan or at a greater frequency. There were no significant difficulties encountered during the test,
other than unit reached capacity sooner than predicted. Table 4-1 summarized the operational
data collected during the test.
4.3.1 Flow, Volumetric Loading, and Bed Volumes
As described in Section 4.2.1, the pilot unit operated on steady basis around the targeted flow of
2.0 gpm during the verification test. The mean flow of 2.0 gpm yielded a hydraulic loading rate
of 1.05 gpm/ft2. The media volume was estimated to be 1.3 ft3, which gives an EBCT of 4
minutes and 54 seconds.
Table 4-5 shows the flow data for the capacity test and also shows the bed volumes (BV) treated
during the capacity test. The test was stopped on July 25*, after 40,941 gal had been treated or
approximately 4,400 BV.
Table 4-5. Capacity Test Flow, Treated Bed Volumes, and Uranium Results
Date
10-Jul
11-Jul
12-Jul
13-Jul
14-Jul
16-Jul
17-Jul
18-Jul
19-Jul
20-Jul
21-Jul
23-Jul
24-Jul
25-Jul
27-Jul
Flow
(gpm)
1.89
2.00
.58
.65
.90
.85
.90
.98
.90
2.17
2.16
2.15
2.16
n/m
2.10
Cumulative Volume from
Flow Totalizer (gal)
0
2,101
4,307
6,638
9,489
15,243
17,330
18,694
21,402
24,503
28,231
33,729
36,731
40,511(1)
45,726
Bed Volumes
0
220
440
680
980
1,600
1,800
1,900
2,200
2,500
2,900
3,500
3,800
44,200
4,700
Uranium (jig/L)
Feed Treated
230
140
140
140
160
170
210
170
180
220
190
200
230
250
n/m
1
<1
2
4
8
30
26
16
25
45
49
67
45
68
n/m
n/m - not measured - (Note:
(1) Estimated based on flow
test stopped)
for period July 24-27.
32
-------
4.3.2 Capacity Test Uranium Results
The objective of the capacity test was to determine the media capacity to remove uranium to
meet the EPA MCL of 30 ng/L. Brimac requested that the capacity test be planned to continue
until the uranium concentration in the treated water reached 60
The Brimac performance claim based on their evaluation of the HA 216 adsorptive media was as
follows:
"The Brimac Environmental Services, Inc. pilot treatment unit containing Brimac HA 216
adsorptive media is capable of reducing uranium up to 150 |j,g/L to less than 1 ug/L when the
feed water is treated at a hydraulic loading rate of 1.05 gpm/ft2 of media cross-sectional surface
area. Under these treatment conditions, approximately 83,000 gal of feed water can be treated
per ft3 of media before uranium is detected in the treated water."
Based on the Brimac performance claim, Brimac estimated that the pilot unit, operated at 2.0
gpm with 1.3 ft3 of media (50 Ib) and an EBCT of 4.9 minutes, would treat approximately
108,000 gal of source water before any uranium is detected in the treated water. This equates to
approximately 36 days of operation and 1 1,000 BV.
As shown in Table 4-5, the uranium concentration in the treated water consistently was above the
water quality standard after 21,402 gal of water was treated, or approximately 2,200 BV. These
data indicate that at the loading rate used in the capacity test and a mean source water
concentration of 190 ug/L, the media had a lower capacity than expected. Using the mean source
and treated water uranium concentrations (171 [ig/L and 12.6 |J,g/L) for the first ten days of data
(until breakthrough had occurred at 30 ug/L), the 50 Ibs (23 kg) of media had absorbed 13.1 g of
uranium (0.00057 g U/g media). For the entire test period, the average the uranium concentration
in the treated water was 29.7 ug/L, just under the MCL. Using the entire test period, the 23 kg of
media had adsorbed approximately 24.8 grams of uranium (0.001 1 g U/g media).
Figures 4-1 and 4-2 show the uranium concentration plotted as a time series and as a function of
bed volumes treated. While the media capacity to adsorb uranium and meet the water quality
standard was lower than expected, the media was able to remove uranium to levels below the
MCL for a period of time. Under the conditions of the verification test, namely a source
concentration of 190 |J,g/L and an EBCT of 4 minutes and 54 seconds, the media would need to
be changed frequently or a larger amount of media used per volume being treated. However,
with sufficient media in a treatment unit, and frequent media change out, these data show that the
water quality standard can be achieved.
33
-------
300
250 -
§? 200 H
t 150 H
u
g
1 100
50 -
0
10-M
12-Jiil 14-Jul 16-M 18-M 20-JtU
Days
22-M
24-Jill
26-M
Figure 4-1. Uranium concentration versus time.
250 -
200 -
3 150
a
|
5 100 -
Bed Volumes Treated
Figure 4-2. Uranium concentration versus bed volumes treated.
34
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4.3.3 Capacity Test Uranium Removal Discussion
The performance of the media is a function of feed water quality and contact time. Uranium
breakthrough is highly dependent on the source water concentration and the adsorption
characteristics of the media. Thus, there are several factors that can impact the performance and
the capacity of the media to adsorb uranium.
The source water quality as described in section 4.2.3 indicates the source water quality did not
change significantly through the treatment unit. Adsorption of "other" chemicals can reduce the
capacity of an adsorptive media, but the water quality data collected during the verification
would seem to indicate that is was not the case for this source water. The concentration of
uranium in the source water was close to the expected concentrations and within a reasonable
range based on the Brimac specification (150 ng/L). Therefore source water quality does not
appear to have had a major impact on the capacity of the media.
The adsorption process for uranium is a slow process and the EBCT will have an impact on the
final treated water concentration, as the media is loaded with uranium. The size of the mass
transfer zone moving through the bed and the equilibrium between the media and the treated
water concentrations will change as bed contact time changes. Particle size can also effect the
kinetics of the adsorption process with smaller particle sizes providing more surface and pore
area for adsorption, thus increasing overall capacity at a given EBCT.
It would appear that the conditions (media size and EBCT) during this verification test resulted
in the treated water reaching the breakthrough target (30 ng/L) long before the actual full
capacity of the media was utilized. This was probably due to slow kinetics of the uranium
adsorption process.
Initially, a second test was designed to use the same media particle size, flow rates, and hydraulic
loading rates as this first test. The depth of the bed was to be increased, which would provide a
longer EBCT (11.7 minutes versus 4.9 minutes). The second test, under the planned conditions,
was expected to run for approximately 90 days. Brimac estimated that pilot unit #2, if operated at
2.0 gpm would treat approximately 259,000 gal of source water. However, based on this
verification data, the planned second test would be projected to run for only 25 to 30 days. It is
possible depending on the length and shape of the mass transfer wave, the deeper bed would
actually run longer, but it is not expected that it would approach the desired 90 days.
Brimac has provided additional information and data on the adsorption rates and capacity of the
HA 216 media. This information, presented in Appendix A, shows that reducing the particle size
of the media increases the adsorption rate. Brimac is currently developing the best approach to
working with a smaller particle size media that can be used in an additional test. Once this work
is complete, a new set of flow rates, EBCT, hydraulic loading will be developed for the
additional test.
35
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Chapter 5
QA/QC
5.1 Introduction
An important aspect of the verification testing was the QA/QC procedures and requirements.
Careful adherence to the procedures ensured that the data presented in this report were of sound
quality, defensible, and representative of the equipment performance. The primary areas of
evaluation were representativeness, accuracy, precision, and completeness.
A Quality Assurance Project Plan (QAPP) was developed as part of the PSTP. The full details of
the QAPP can be found in the Chapter 6 of the approved PSTP. All of the NSF laboratory
activities were conducted in accordance with the provisions of the NSF International
Laboratories Quality Assurance Manual (NSF 2004).
Both the NSF and NHDES Laboratories are NELAP accredited drinking water laboratories.
Furthermore, the NHDES Laboratory is the NELAP accrediting authority for the State of New
Hampshire.
5.2 Test Procedure QA/QC
All of the analytical tests performed by the NSF testing laboratory followed the USEPA-
approved test/QA plan created specifically for this verification. The NSF QA Department staff
reviewed the test procedures and results as part of the normal audit procedure to ensure the
proper procedures were followed.
The NHDES Laboratory provided to NSF the daily calibration logs for the pH meter and
turbidimeter used for the pH and turbidity measurements. The NSF QA Department reviewed
these records and the results to ensure proper procedures were followed. The audit of the data
showed that it was acceptable. As specified in the PSTP, the NHDES Laboratory did not provide
copies of the raw data logs or QA/QC summaries for the radiological analyses, radon and alpha
radioactivity. These data were provided only for informational purposes, since the HA 216
media was not designed to remove these contaminants.
5.3 Sample Handling
All samples analyzed by the NSF and NHDES Chemistry Laboratories were labeled with unique
ID numbers. These ID numbers appear in the laboratory reports for the tests. All samples were
analyzed within allowable holding times.
5.4 Chemistry Analytical Methods QA/QC
The calibrations of all analytical instruments and the analyses of all parameters complied with
the QA/QC provisions of the NSF International Laboratories Quality Assurance Manual. The
36
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NSF QA/QC requirements are all compliant with those given in the USEPA method or Standard
Method for the parameter. Also, each analytical instrument has an NSF Standard Operating
Procedure governing its use.
The field parameters analyzed by the NHDES laboratory (pH, turbidity) were analyzed in
accordance with the methods and procedures established in the QAPP. These data were reviewed
by the NSF QA Department and found to be acceptable.
5.5 Documentation
All laboratory activities were documented using specially prepared laboratory bench sheets or
NSF laboratory reports. Data from the bench sheets and laboratory reports were entered into
Excel spreadsheets. These spreadsheets were used to calculate average, maximum, minimum
values and other statistics. One hundred percent of the data entered into the spreadsheets was
checked by a reviewer to confirm all data and calculations were correct.
5.6 Data Quality Indicators
The quality of data generated for this ETV was established through four indicators of data
quality: representativeness, accuracy, precision, and completeness.
5.6.1 Representativeness
Representativeness refers to the degree to which the data accurately and precisely represent the
expected performance of the equipment tested. Representativeness was ensured by consistent
execution of the test protocol, including timing of sample collection, sampling procedures, and
sample preservation. Representativeness was also ensured by using each analytical method at its
optimum capability to provide results that represent the most accurate and precise measurement
it is capable of achieving.
5.6.2 Accuracy
Accuracy was quantified as the percent recovery of the parameter in a sample of known quantity.
Accuracy was measured through use of both matrix spikes of a known quantity, and certified
standards during calibration of an instrument. The following equation was used to calculate
percent recovery:
Percent Recovery = 100 X [(X^owa - XmeasurecD/Xknown]
where: XknOWn = known concentration of the measured parameter
Xmeasured = measured concentration of parameter
Table 5-1 shows the accuracy limits and checks that were established for all analytical
parameters. The percent recoveries of all matrix spikes and standards were within the allowable
limits for all analytical methods.
37
-------
Table 5-1. Laboratory Analyses- Accuracy and Precision
Parameter
pH
Turbidity
Uranium
Alkalinity
Alpha
Radioactivity
Aluminum
Arsenic (Total)
Calcium
Chloride
TDS
Fluoride
Total Hardness
Iron (total)
Magnesium
Manganese
Nitrate
TOC
Phosphate
(total)
Radon 222
Silica (total)
Sodium
Sulfate
TSS
UV254
LFM(1)
(spike
sample)
Frequency
N/A
N/A
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
N/A
LFM
Acceptance
Limits
(% Recovery)
N/A
N/A
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
90-110%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
70-130%
N/A
N/A
MB(2)
Frequency
N/A
N/A
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
N/A
MB
Acceptance
Limits
N/A
N/A
-------
5.6.2.1 Field Equipment Accuracy and Calibration
Equipment operating parameters must be accurate and verifiable for use in evaluating system
operating conditions. Routine calibrations and checks of the key operating meters and gauges
ensured accurate readings.
Water flow - the difference between the reported flow indicated by a flow meter and the flow as
actually measured on the basis of known volumes of water and carefully defined times are
standard practices in hydraulics laboratories or water meter calibration shops. The "bucket and
stopwatch" technique was used to determine the accuracy of the accessory flow meter and
totalizer meter. A stainless steel 5-gallon Seraphin® container was used for the "bucket". A
Seraphin® container is a calibrated container that provides high accuracy for volume
measurements. The time to fill the 5-gallon Seraphin® container was measured with a stop watch
and then the flow calculated in gpm.
Pressure measurement - accuracy was determined based on a current (within the last six months)
manufacturer's calibration certification.
Meters and gauges were checked at the frequencies presented in Table 5-2 for accuracy. The
flow/totalizer meter maintained acceptable accuracy through the test period.
Table 5-2. Field Instrument Calibration Check Schedule
Instrument
Pressure Gauge
Flow Meter
Totalizer Meter
Thermometer
Calibration Check Method
manufacturer's certification
volumetric using a calibrated 5-gallon Seraphin®
container
volumetric using a calibrated 5-gallon Seraphin®
container
calibration against NIST traceable reference
thermometer
Frequency
once before
testing
weekly
weekly
monthly
Acceptable
Accuracy
± 10%
± 10%
± 1.5%
±5%
5.6.3 Precision
Precision refers to the degree of mutual agreement among individual measurements and provides
an estimate of random error. Analytical precision can be a measure of how far an individual
measurement may be from the mean of replicate measurements, or it may be measured as the
percent difference between duplicate measurements.
Field duplicate samples were collected to quantify precision. In addition, the samples analyzed
by the NSF laboratory were subject to NSF's laboratory duplicate analysis requirements for
verifying precision of the analytical method. The NSF requirement is that at least one out of
every ten samples, or one out of every batch of samples, be analyzed in duplicate. The precision
of duplicate analyses is calculated using relative percent difference (RPD). The precision control
limits are listed in Table 5-1.
39
-------
RPD is measured using the following equation:
RPD =
S, +S,
x200
where:
Sl = sample analysis result; and
^ = sample duplicate analysis result.
The RPD calculations for the field duplicates are shown in Table 5-3. As can be seen all results
are <20% relative percent deviation, except two treated water uranium sample pairs.
The NSF laboratory duplicate data met NSF's internal RPD limits shown in Table 5-1. The data
is not displayed here because the samples for this project were batched with samples from other
NSF testing activities, therefore, the laboratory duplicate analyses may have been on samples
that were not from this project.
Table 5-3: Precision Results - Field Duplicates - Relative Percent Deviation
Date
7/10/2007
7/20/2007
7/11/2007
7/10/2007
7/10/2007
7/20/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/10/2007
7/16/2007
7/20/2007
7/25/2007
7/10/2007
Source
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Feed
Treated
Feed
Treated
Feed
Parameter
pH (SU)
pH (SU)
Radon 222 (pCi/L)
Temperature (°C)
Turbidity (NTU)
Turbidity (NTU)
Alkalinity (mg/L CaCO3)
Aluminum (mg/L)
Arsenic (mg/L)
Calcium (mg/L)
Chloride (mg/L)
Fluoride (mg/L)
Hardness (mg/L CaCO3)
Iron (mg/L)
Mg (mg/L)
Mn (mg/L)
Nitrate (mg/L N)
Phos. (mg/L P)
Silica (mg/L SiO2)
Sodium (mg/L)
Sulfate (mg/L)
TDS (mg/L)
TOC (mg/L)
TSS (mg/L)
Uranium (ug/L)
Uranium (ug/L)
Uranium (ug/L)
Uranium (ug/L)
UV254 (Abs)
Base Result
6.68
6.66
60,000
13.7
<1
<1
82
<0.01
0.007
130
430
0.9
420
O.02
20
0.074
1.7
O.05
20
170
13
1,000
0.6
<2
230
30
220
68
0.0109
Duplicate Result
6.71
6.6
64,000
13.6
<1
<1
84
<0.01
0.007
130
440
0.9
410
<0.02
18
0.084
1.7
<0.05
20
170
13
1,100
0.6
<2
230
17
190
49
0.009
RPD
0.45
0.90
6.45
0.73
n/c
n/c
2.41
n/c
0.00
0.00
2.30
0.00
2.41
n/c
10.5
12.7
0.00
n/c
0.00
0.00
0.00
9.52
0.00
n/c
0.00
55.3
14.6
32.5
19.1
n/c = not calculated
40
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5.6.4 Completeness
Completeness refers to the amount of data collected from a measurement process compared to
the amount that was expected to be obtained. Completeness is the proportion of valid,
acceptable data generated using each method.
The completeness objective for data generated during verification testing was based on the
number of samples collected and analyzed for each parameter. Table 5-4 illustrates the
completeness objectives for the performance parameters based on the sample frequency.
Table 5-4. Completeness Requirements
Number of Samples per Parameter
0-10
11-50
>50
Percent Completeness
80%
90%
95%
Completeness is defined as follows for all measurements:
%C = (V/T)X100
where:
%C = percent completeness;
V = number of measurements judged valid;
T = total number of measurements.
All completeness objectives were met during the verification test.
5.7 Sampling, sample handling, and preservation
5.7.1 Sampling Locations
Feed and treated water samples were collected from the sample taps outfitted on the feed and
treated water lines. The sample taps were installed as close as possible to the feed and treated
water ports on the pilot unit drum.
5.7.2 Sample Collection
Prior to collecting samples, the tap was flushed for at least five seconds. All samples were
collected into clean containers. Samples requiring 1 liter of volume were collected directly into
the 1-liter container. For samples requiring less than 1-liter of volume, a 1-liter container was
filled from the tap and then aliquots of the sample were immediately poured into the required
containers for laboratory or on-site analysis. Sample times were recorded for all samples
collected. Samples for parameters requiring immediate analysis, such as pH and turbidity, were
collected separately and transported to the NHDES laboratory as quickly as possible.
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The sample bottles for laboratory analysis were prepared ahead of time with the appropriate
preservative.
5.7.3 Sample Storage and Transport
Samples for off-site laboratory analysis were collected and preserved in accordance with
Standard Method?, 3010 B, paying particular attention to the sources of contamination as outlined
in Standard Methods 3010 C. The samples were kept cool, in the range of 2°C to 8°C
immediately upon collection, shipped in a cooler, and maintained at a temperature of 2°C to 8°C.
Any samples collected Friday through Sunday were kept at 2°C to 8°C until they could be
shipped on Monday. Temperature blanks accompanied all samples shipped to NSF. The
temperature of each blank was measured and recorded for each sample set.
All samples were analyzed within the Standard Methods or EPA method recommended holding
times. The sample collection and preservation details for each parameter are presented in Table
5-5.
Table 5-5. Sample Collection and Preservation Details
Parameter
pH
Temperature
Turbidity
Uranium
Alkalinity
Gross Alpha
Radioactivity
Aluminum
Arsenic (Total)
Calcium
Chloride
TDS
Fluoride
Total Hardness
Iron (total)
Magnesium
Manganese
Nitrate
TOC
Phosphate (total)
Radon 222
Silica (total)
Sodium
Sulfate
TSS
UV254
Bottle Type
1 L polyethylene
N/A
1 L polyethylene
125 mL polyethylene
1 L polyethylene
1 L polyethylene
125 mL polyethylene
125 mL polyethylene
125 mL polyethylene
40 ml glass vial
1 L polyethylene
1 L polyethylene
N/A
125 mL polyethylene
125 mL polyethylene
125 mL polyethylene
40 mL glass vial
40 mL glass vial
250 mL amber glass
4 40 mL glass vials
125 mL polyethylene
125 mL polyethylene
40 mL glass vial
2 1L polyethylene
125 mL amber glass
Preservation
none
none
none
nitric acid
none
nitric acid
nitric acid
nitric acid
nitric acid
none
none
none
N/A
nitric acid
nitric acid
nitric acid
none
phosphoric acid
sulfuric acid
none
nitric acid
nitric acid
none
none
none
Holding
Time
48 hours
N/A
48 hours
180 days
14 days
180 days
180 days
180 days
180 days
28 days
7 days
28 days
N/A
180 days
180 days
180 days
48 hours
28 days
28 days
4 days
180 days
180 days
28 days
7 days
48 hours
Notes
Immediate analysis in the field
no headspace
no sample, calculated from
calcium and magnesium results
42
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Chapter 6
References
NSF International (2004). NSF International Laboratories Quality Assurance Manual. Ann
Arbor, NSF International.
APHA, AWWA, and WEF (1999). Standard Methods for the Examination of Water and
Wastewater, 20th edition. Washington D.C., APHA, AWWA, and WEF.
EPA and NSF (2000). EPA/NSFETVProtocolfor Equipment Verification Testing for Removal
of Radioactive Chemical Contaminants.
EPA and NSF (2003). EPA/NSFETVProtocolfor Equipment Verification Testing for the
Removal of Arsenic (Chapter 6).
Millard, A. R. and R. E. M. Hedges (1996). A diffusion-adsorption model of uranium uptake by
archeological bone. Geochimica Et Cosmochimica Acta 60(12): 2139-2152.
Sorg, T. J. (1988). Methods for removing uranium from drinking water. Journal of the
American Waterworks Association. July: 105-111.
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APPENDIX A
Additional Data on HA 216 Media Adsorption Rates and Capacity
Provided by Brimac
(Note that this information is provided for informational purposes and was not verified as
part of the ETV test)
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Adsorption of Uranium onto Adsorbent from Brimac
Brimac has been manufacturing the adsorbent media Hydroxyapatite (HA) for over 180 years.
Originally this media was exclusively used in the sugar industry for its ability to adsorb very
large molecular weight organic compounds (color) and adsorb / exchange / retain 'ash' or
inorganic salts such as sulfates, the two combined together being the first process for the
manufacture of white sugar. Over the past 50 years, Brimac has expanded the application of HA
into the areas of heavy metals removal (with a specifically tailored media) as well as broad
drinking water treatment, under the NSF 61 standard.
With the ever increasing need for drinking water, the reducing availability of fresh water sources
and the increasing awareness of the need to remove harmful contaminates, the opportunity for
novel adsorption solutions to low level contamination issues is gaining momentum. Along with
the removal of arsenic and other heavy metals, Brimac sees a market in the remediation of radio
nucleotides, especially Uranium and in particular from residential scale borehole sources.
Early work on the adsorption of Uranium onto HA media showed a capacity of 1 g/Uranium per
g/HA (potentially dangerous, in that fission conditions might be possible if this capacity was
realized in real world conditions and scale).
Due to the difficulty surrounding laboratory uranium availability and testing above batch
isotherm scale, the ETV process has been the vehicle for the next stage of this project. The
evaluation of a small scale filter was not designed or intended to be a rigorous evaluation of a
'finished product', but a real word development project in progress.
Brimac is a company with an extensive background in design and utilization of media adsorption
systems, we knew that while total theoretical capacity is important, the achievable kinetics of
adsorption is by far the most important criteria when judging if a system is economically
feasible. Hydroxyapatite is not an activated carbon and a number of application errors have been
made by third parties in trying to fit this media into the accepted Empty Bed Contact time 'rules
of thumb' used for GAC applications. In this case, we knew from experience that the adsorption
of metals by HA can have very long 'effective' contact time requirements and this study was to
be that first rough cut evaluation of 'column based' Uranium removal.
It is evident from this first test that capacity is present and adsorption is possible, but a
systematic work up of the bed depth requirements based on these results indicated a system scale
that is not economically practical. Again from previous experience, we understood the
relationship between particle size and effective utilization of readily available surface area and it
was with this knowledge we approached Arizona State University and the Rapid Small Scale
Column Test (RSSCT) team to evaluate the dynamic relationship between the available
capacities to the available surface area.
Without a doubt, the conclusions of this test indicate that a granular system would never meet the
real world requirements of contact time and only a powder based technology would realize the
potential of the media.
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In the continuation of our ETV project, the goal of our Stage two study will be the application of
the media using block filter technology. Brimac is currently in a development program with KX
Technologies to manufacture a nominal 10 micron block filter, comprising of 100% drinking
water grade Hydroxyapatite. It is hoped that the enormous increase in readily available surface
area provided by the block filter technology will provide the means to utilize the capacity
demonstrated in the RSSCT results.
Stage one of our ETV project has been an informative journey, even if our initial expectations
may not have been met. I hope you will agree that the conclusions reached point in a logical
manner to a new product in a developing field of application. The distribution of this report and
the media's potential will hopefully lead to more opportunities to partner with other organization,
local and State authorities etc. in the real word application of solving problems and providing
cleaner drink water for us all.
1 Adsorption experiment
Faster mass transfers can be obtained by reducing the size of the adsorbents. The adsorbent
were grinded and sieved. Adsorbent with the particle size from 75 um to 90 um were collected.
Adsorption capacities of uranium onto the adsorbent both at the original size and 75 um to 90 um
were accessed.
Adsorption kinetics and isotherm were determined using duplicate batch experiments. In
each experiment, certain amounts of adsorbent were added to a series of 50 ml PTEE tubes.
Uranium contaminated water was added into the tube. The tubes were put in a shaker and kept at
25 °C.
Kinetic data were collected by adding 0.045, 0.225, 0.450, 1.35, 2.250 g adsorbent to 45 mL
uranium contaminated water. Residual aqueous uranium concentrations at 0, 10, 30, 60, 180 and
360 min were analyzed using ICP-MS after the suspensions were centrifuged for 5 min at 6,000
rpm using centrifuge.
Isotherm tests were conducted for 180 min by changing the concentration of adsorbent at a
fixed uranium concentration. The adsorbed amount of uranium onto the adsorbent was calculated
from the initial and final concentrations of uranium. Blank experiments were also conducted
demonstrated that uranium adsorption onto the walls of the flasks was negligible.
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2 Experimental results
2.1 Adsorption kinetics (adsorbent in original size, 250-1000 um )
50 100 150 200 250 300 350 400
Adsorption time (mm)
Fig 1 Adsorption kinetics of uranium onto adsorbent with original size
Adsorption kinetics was observed for 360 min, and the results are shown in Fig. 1. Uranium
was adsorbed onto adsorbent quickly, and equilibrium was reached within 180 min. Increasing
adsorption rate was observed with the increasing of adsorbent concentration. Only 10% of the
initial uranium was adsorbed at the adsorbent concentration of 1 g/L, However, 100% adsorption
was reached when the adsorbent concentration increased to 50 g/L.
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2.2 Adsorption kinetics (grinded adsorbent, 75-90 um )
cj
O
50 100 150 200 250 300 350 400
Adsorption time (min)
Fig 2 Adsorption kinetics of uranium onto adsorbent within75 um to 90 um
Due to the higher surface area, the adsorption ability of the adsorbent with smaller particle
size was much higher than that of at the original particle size. 90% of the initial uranium was
adsorbed at the adsorbent concentration of 1 g/L, and, 100% adsorption was reached when the
adsorbent concentration was higher than to 5 g/L.
2.3 Adsorption isotherms
The adsorption isotherm data were analyzed using Freundlich (eq 1) and Langmuir (eq 2)
adsorption expressions:
ioge=iog^F+-iogce (i)
n
J_
~0
(2)
where Qm (mg g"1) is the maximum adsorption capacity, Q (mg g"1) is the amount of adsorbed
uranium, Ce is the equilibrium uranium concentration in solution (mg/L),^F and n are the
48
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Freundlich constants, and b is the Langmuir constant. The Freundlich and Langmuir parameters
were obtained by nonlinear least-squares regression analysis.
Table 1 The Freundlich and Langmuir parameters of adsorption data
Size (um)
Original size
(250-1000)
Grinded
(75-90)
Langmuir isotherm
Qmax (mg/g) b
0.010 263.6
1.647 24.6
Freundlich isotherm
R2
0.754
0.983
KF (mg/g)
0.030
7.800
n
0.372
0.809
R2
0.890
0.990
As shown in Table 1, the correlation coefficient (R ) values of the Freundlich isotherm for
the adsorbents with original size and at the range of within 75 um to 90 um are 0.890 and 0.990,
while those of the Langmuir isotherm are 0.745 and 0.983, respectively. The Langmuir and
Freundlich plot of the two adsorbents are shown in Fig 3 and Fig 4 respectively. Experimental
data of uranium adsorption onto the adsorbents fit Freundlich isotherm well, indicating that
heterogeneity of the surface due to involvement of both strong and weaker binding sites for
adsorption, thus resulting in a multisite adsorption processes for these adsorbate ions.
300-
250-
200-
150-
100-
50-
0-
• Original size
• Grinded, 75-90 um
0 2000 4000 6000 8000 10000 12000
l/Ce(L/mg)
Fig 3 Langmuir plot of adsorption of uranium onto the two adsorbents
49
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8?
-0.8-
-1.0-
-1.2-
-1.4-
-1.6-
-1.8-
-2.0-
-2.2-
-2.4-
-2.6
Original size
Grinded 75-90 um
-4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5
logCe
Fig 4 Freundlich plot of adsorption of uranium onto the two adsorbents
3 Conclusions
3.1 Adsorption process is fast; equilibriums can be reached in about 3 hours.
3.2 Grinded particles with the smaller particle size have much stronger adsorption capability for
uranium.
3.3 Freundlich isotherm is better to describe the adsorption of uranium onto the adsorbents.
3.4 Faster mass transfers can be obtained by crushing adsorbents to much smaller sizes and using
smaller column, higher loading rate, and thus the pilot scale tests can be scaled in a short period.
50
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