January 2004
04/9208/E PAD WCTR
Environmental Technology
Verification Protocol
Drinking Water Systems Center
PROTOCOL FOR EQUIPMENT
VERIFICATION TESTING FOR
REMOVAL OF SYNTHETIC ORGANIC
CHEMICAL CONTAMINANTS
Prepared by
ฎ
NSF International
Under a Cooperative Agreement with
U.S. Environmental Protection Agency
ETVETYElV
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EPA/NSF ETV
PROTOCOL FOR EQUIPMENT VERIFICATION TESTING
FOR THE REMOVAL OF SYNTHETIC ORGANIC
CHEMICAL CONTAMINANTS
Prepared by:
NSF International
789 Dixboro Road
Ann Arbor, MI 48105
Recommended by
the Steering Committee for the Verification of
Drinking Water Systems
on August 2, 1999
Modified in March 2002 and January 2004
With support from
the U.S. Environmental Protection Agency
Environmental Technology Verification Program
Copyright 2004 NSF International 40CFR35.6450.
Permission is hereby granted to reproduce all or part of this work,
subject to the limitation that users may not sell all or any part of the
work and may not create any derivative work therefrom. Contact ETV
Drinking Water Systems Center Manager at (800) NSF-MARK with
any questions regarding authorized or unauthorized uses of this work.
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U.S. ENVIRONMENTAL PROTECTION AGENCY
Throughout its history, the United States Environmental Protection Agency (EPA) has evaluated
technologies to determine their effectiveness in preventing, controlling, and cleaning up pollution. EPA is
now expanding these efforts by instituting a new program, the Environmental Technology Verification
Programor ETVto verify the performance of a larger universe of innovative technical solutions to
problems that threaten human health or the environment. ETV was created to accelerate the entrance of
new environmental technologies into the domestic and international marketplace. It supplies technology
buyers and developers, consulting engineers, states, and EPA regions with high quality data on the
performance of new technologies. This encourages more rapid availability of approaches to better
protect the environment.
ETV Drinking Water Systems Center
Concern about drinking water safety has accelerated in recent years due to much publicized outbreaks
of waterborne disease and information linking ingestion of arsenic to cancer incidence. The EPA is
authorized through the Safe Drinking Water Act (SDWA) to set numerical contaminant standards and
treatment and monitoring requirements that will ensure the safety of public water supplies. However,
small communities are often poorly equipped to comply with all of the requirements; less costly package
treatment technologies may offer a solution. These package plants can be designed to deal with specific
problems of a particular community; additionally, they may be installed on site more efficiently
requiring less start-up capital and time than traditionally constructed water treatment plants. The
opportunity for the sales of such systems in other countries is also substantial.
The EPA has partnered with NSF International (NSF) to verify performance of small drinking water
systems that serve small communities. It is expected that both the domestic and international markets
for such systems are substantial. The EPA and NSF have formed an oversight stakeholders group
composed of buyers, sellers, and states (issuers of permits), to assist in formulating consensus testing
protocols. A goal of verification testing is to enhance and facilitate the acceptance of small drinking
water treatment equipment by state drinking water regulatory officials and consulting engineers while
reducing the need for testing of equipment at each location where the equipment use is contemplated.
NSF will meet this goal by working with equipment manufacturers and other agencies in planning and
conducting equipment verification testing, evaluating data generated by such testing, and managing and
disseminating information. The manufacturer is expected to secure the appropriate resources to support
its part of the equipment verification process, including provision of equipment and technical support.
The verification process established by the EPA and NSF is intended to serve as a template for
conducting water treatment verification tests that will generate high quality data for verification of
equipment performance. The verification process can help in moving small drinking water equipment
into routine use more quickly. The verification of an equipment's performance involves five sequential
steps:
1. Development of a Product Specific Test Plan (PSTP);
2. Execution of verification testing;
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3. Data reduction, analysis, and reporting;
4. Performance and cost factor (labor, chemicals, energy) verification; and
5. Report preparation and information transfer.
This verification testing program is being conducted by NSF with participation of manufacturers, under
the sponsorship of the EPA Office of Research and Development (ORD), National Risk Management
Research Laboratory (NRMRL), Water Supply and Water Resources Division (WSWRD) -
Cincinnati, Ohio. NSF's role is to provide technical and administrative leadership and support in
conducting the testing. It is important to note that verification of the equipment does not mean that the
equipment is "certified" by NSF or EPA. Rather, it recognizes that the performance of the equipment
has been determined and verified by these organizations.
Partnerships
The EPA and NSF cooperatively organized and developed the ETV Drinking Water Systems (DWS)
Center to meet community and commercial needs. NSF and the Association of State Drinking Water
Administrators (ASDWA) have an understanding to assist each other in promoting and communicating
the benefits and results of the project.
NSF INTERNATIONAL
Mission Statement
NSF, an independent, non-governmental organization, is dedicated to being the leading global provider
of public health and safety-based risk management solutions while representing the interest of all
stakeholders.
NSF Purpose and Organization
NSF is an independent not-for-profit organization. For more than 52 years, NSF has been in the
business of developing consensus standards that promote and protect public health and the environment
and providing testing and certification services to ensure manufacturers and users alike that products
meet those standards. Today, millions of products bear the NSF Name, Logo and/or Mark, symbols
upon which the public can rely for assurance that equipment and products meet strict public health and
performance criteria and standards.
Limitations of use of NSF Documents
This protocol is subject to revision; contact NSF to confirm this revision is current. The testing against
this protocol does not constitute an NSF Certification of the product tested.
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ORGANIZATION AND INTENDED USE OF PROTOCOL AND TEST PLANS
NSF encourages the user of this protocol to also read and understand the policies related to the
verification and testing of drinking water treatment systems and equipment.
The first chapter of this document describes the protocol required in all studies verifying the
performance of equipment or systems removing synthetic organic chemical contaminants (SOCs). The
remaining chapters, or Technology Specific Test Plans (TSTPs), describe the additional requirements
for equipment and systems using specific technologies to attain the goals and objectives of the protocol:
the removal of (SOCs).
Prior to the verification testing of drinking water treatment systems, plants, and/or equipment, the
equipment manufacturer and/or supplier must select an NSF-qualified Field Testing Organization
(FTO). This designated FTO must write a PSTP to define the testing plan specific to the product. The
equipment manufacturer and/or supplier will need this protocol and the TSTP(s) contained herein and
possibly other ETV protocols and TSTPs to develop the PSTP, depending on the treatment
technologies used in the unit processes or treatment train of the equipment or system. More than one
protocol and/or TSTP may be necessary to address the equipment's capabilities in the treatment of
drinking water.
Testing shall be conducted by an NSF-qualified FTO that is selected by the manufacturer. Water
quality analytical work to be completed as a part of a TSTP shall be contracted with a laboratory that is
certified, accredited or approved by a state, a third-party organization (i.e., NSF), or the EPA For
information on a listing of NSF-qualified FTOs, contact NSF.
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ACKNOWLEDGMENTS
The EPA and NSF would like to acknowledge those persons who participated in the preparation,
review and approval of this protocol. Without their hard work and dedication to the project, this
document would not have been approved through the process which has been set forth for this ETV
Program.
Chapter 1: Requirements for All Studies
Writer: Steven J. Duranceau, PhD, PE, Boyle Engineering Corporation
Technical reviewer: Jim Taylor, PhD, University of Central Florida
Chapter 2: Testing Plan Membrane Filtration Processes
Writer: Steven J. Duranceau, PhD, PE, Boyle Engineering Corporation
Technical reviewer: Jim Taylor, PhD, University of Central Florida
Chapter 3: Testing Plan SOC Oxidation by Ozone and Advanced Oxidation Processes
Writer: Holly Shorney, PhD, Black & Veatch
Contributing writer: Gary Logsdon, PhD, Black & Veatch
Technical reviewer: Steven J. Duranceau, PhD, PE, Boyle Engineering Corporation
Chapter 4: Testing Plan for Adsorptive Media Processes
Writers: Scott Summers, PhD and Stuart Hooper, Water Evaluation Laboratory; and Mark
Carlson, PhD, PE, CH2M HILL, Inc.
Technical reviewer: Steven J. Duranceau, PhD, PE, Boyle Engineering Corporation
Steering Committee Members that recommended Chapters 1,2, and 3:
Mr. Jim Bell Mr. Jerry Biberstine, Chairperson
Mr. Stephen W. Clark Mr. John Dyson
Mr. Joseph Harrison Dr. Joseph G. Jacangelo
Mr. Glen Latimer Dr. Gary S. Logsdon
Mr. Robert Mann Mr. David Pearson
Mr. Robert Taylor (for Mr. Allen Hammer) Mr. John Trax
Steering Committee Members that recommended Chapter 4:
Mr. Jerry Biberstine Mr. Kevin Brown, Chairperson
Mr. John Dyson Mr. Buck Henderson
Dr. Gary Logsdon Mr. Robert Mann
Mr. Rick Pistorius (for Mr. Jim Bell)
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TABLE OF CONTENTS
Page
Chapter 1: EPA/NSF ETV Protocol for Equipment Verification Testing for the Removal
of Synthetic Organic Chemical Contaminants: Requirements for All Studies 1-1
Chapter 2: EPA/NSF ETV Equipment Verification Testing Plan for the Removal of Synthetic
Organic Chemical Contaminants by Membrane Filtration Processes 2-1
Chapter 3: EPA/NSF ETV Equipment Verification Testing Plan for SOC Oxidation by
Ozone and Advanced Oxidation Processes 3-1
Chapter 4: EPA/NSF ETV Equipment Verification Testing Plan for the Removal of Synthetic
Organic Chemical Contaminants by Adsorptive Media Processes 4-1
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CHAPTER 1
EPA/NSF ETV
PROTOCOL FOR EQUIPMENT VERIFICATION TESTING
FOR THE REMOVAL OF
SYNTHETIC ORGANIC CHEMICAL CONTAMINANTS
REQUIREMENTS FOR ALL STUDIES
Prepared by:
NSF International
789 Dixboro Road
Ann Arbor, MI 48105
Copyright 2004 NSF International 40CFR35.6450.
Permission is hereby granted to reproduce all or part of this work,
subject to the limitation that users may not sell all or any part of the
work and may not create any derivative work therefrom. Contact ETV
Drinking Water Systems Center Manager at (800) NSF-MARK with
any questions regarding authorized or unauthorized uses of this work.
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TABLE OF CONTENTS
1.0 INTRODUCTION
1.1 Objectives
1.2 Scope
2.0 EQUIPMENT VERIFICATION TESTING RESPONSIBILITIES
2.1 Verification Testing Organization and Participants
2.2 Organization
2.3 Verification Testing Site Name and Location
2.4 Site Characteristics
2.5 Responsibilities 1-9
3.0 EQUIPMENT CAPABILITIES AND DESCRIPTION 1-10
3.1 Equipment Capabilities 1-10
3.2 Equipment Description 1-12
4.0 EXPERIMENTAL DESIGN 1-13
4.1 Objectives 1-13
4.2 Equipment Characteri sties 1-13
4.2.1 Qualitative F actors 1-14
4.2.2 Quantitative F actors 1-14
4.3 Water Quality Considerations 1-15
4.3.1 F eedwater Quality 1-15
4.3.2 Treated Water Quality 1-16
4.4 Synthetic Organic Chemical Contaminants Testing 1-16
4.5 Recording Data 1-16
4.6 Recording Statistical Uncertainty 1-17
4.7 Verification Testing Schedule 1-18
5.0 FIELD OPERATIONS PROCEDURES 1-19
5.1 Equipment Operations and Design 1-19
5.2 Selection of Analytical Laboratory and Field Testing Organization 1-19
5.3 Communications, Documentation, Logistics, and Equipment 1-20
5.4 Initial Operations 1-21
5.5 Equipment Operation and Water Quality Sampling for Verification Testing 1-21
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TABLE OF CONTENTS (continued)
6.0 QUALITY ASSURANCE PROJECT PLAN 1-22
6.1 Purpose and Scope 1-22
6.2 Quality Assurance Responsibilities 1-22
6.3 Data Quality Indictors 1-23
6.3.1 Accuracy 1-23
6.3.2 Precision 1-24
6.3.3 Completeness 1-25
6.3.4 Representativeness 1-26
6.3.5 Statistical Uncertainty 1-26
6.4 Quality Control Checks 1-26
6.4.1 Quality Control for Equipment Operation 1 -27
6.4.2 Water Quality Data 1-27
6.4.2.1 Duplicate Samples 1-27
6.4.2.2 Method Blanks 1-28
6.4.2.3 Spiked Samples 1-28
6.4.2.4 Travel Blanks 1-28
6.4.2.5 Performance Evaluation Samples for On-Site Water Quality Testing 1-28
6.5 Data Reduction, Validation, and Reporting 1 -28
6.5.1 Data Reduction 1-28
6.5.2 Data Validation 1-28
6.5.3 Data Reporting 1 -29
6.6 Calculation of Data Quality Indicators 1-29
6.7 System Inspections 1-29
6.8 Reports 1-29
6.8.1 Status Reports 1-29
6.8.2 Inspection Reports 1-30
6.9 Corrective Action 1-30
7.0 DATA MANAGEMENT, ANALYSIS AND REPORTING 1-31
7.1 Data Management and Analysis 1-31
7.2 Report of Equipment Testing 1-31
8.0 SAFETY AND MAINTENANCE CONSIDERATIONS 1-32
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1.0 INTRODUCTION
This document is the protocol that will be used for verification testing of equipment designed to achieve
removal of synthetic organic chemical contaminants (SOCs). This protocol may be applicable to
various types of water treatment equipment capable of removing SOCs. Equipment testing may be
undertaken to verify performance of drinking water treatment systems employing processes that may
include but are not limited to coagulation/clarification, oxidation or mixed oxidation processes,
adsorption, granular activated carbon biological filtration, encapsulation, and/or membrane processes
for removal of SOCs. The specific SOC to be targeted for removal during verification testing shall be
clearly identified in the Product Specific Test Plan (PSTP) prior to the initiation of testing by the Field
Testing Organization (FTO). The PSTP may include more than one Technology Specific Test Plan
(TSTP); however, the FTO must adhere to the specific minimum requirements of each protocol in
developing a PSTP.
The testing of new technologies and materials that are unfamiliar to NSF International (NSF) and/or the
Environmental Protection Agency (EPA) will not be discouraged. It is recommended that resins or
membranes or any other material or chemical in the equipment conform to NSF /American National
Standards Institute (NSF/ANSI) Standard 60 and 61.
The final submission of the PSTP shall:
Include the information requested in this protocol;
Conform to the format identified herein; and
Conform to the specific Environmental Technology Verification (ETV) TSTP(s) related to the
manufacturer's statements) of performance capabilities that are to be verified.
This protocol document is presented in two fonts. The non-italicized font provides the rationale for the
requirements and background information that the FTO may find useful in preparation of the PSTP.
The italicized text indicates specific protocol deliverables that are required of the FTO or the
manufacturer and that must be incorporated in the PSTP.
The following glossary terms are presented here for subsequent reference in this protocol:
Distribution System - A system of conduits by which a primary water supply is conveyed to
consumers, typically by a network of pipelines.
EPA - The United States Environmental Protection Agency, its staff or authorized
representatives.
Equipment - Testing equipment for use in the verification test, which may be defined as either a
package plant or modular system.
Field Testing Organization (FTO) - An organization qualified to conduct studies and testing of
drinking water treatment systems in accordance with protocols and test plans. The role of the
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FTO is to ensure preparation of an acceptable PSTP; to enter into contracts with NSF, as
discussed herein; arrange for or conduct the skilled operation of a system during the intense
periods of testing during the study, and to perform the tasks required by the protocol.
Manufacturer - A business that assembles and/or sells package plant equipment and/or modular
systems. The role of the manufacturer is to provide the package plant and/or modular system
and technical support during the verification test. The manufacturer is also responsible for
providing assistance to the third party FTO during operation and monitoring of the package
plant or modular system during the verification test.
Modular System - A packaged functional assembly of components for use in a drinking water
treatment system or packaged plant that provides a limited form of treatment of the feedwater(s)
and which is discharged to another packaged plant or the final step of treatment to the
distribution system.
NSF - NSF International, its staff, or other authorized representatives.
Package Plant - A complete water treatment system including all components from the
connection to the raw water(s) intake through discharge to the distribution system.
Plant Operator - The person working for a small water system who is responsible for operating
water treatment equipment to produce treated drinking water. This person may also collect
samples, record data and attend to the daily operations of equipment throughout the testing
periods.
Product Specific Test Plan (PSTP) - A written document of procedures for on-site/in-line
testing, sample collection, preservation, and shipment and other on-site activities described in
the EPA/NSF ETV protocol(s) and TSTP(s) that apply to a specific make and model of a
package plant/modular system.
Protocol - A written document that clearly states the objectives, goals and scope of the study as
well as the TSTP(s) for the conduct of the study. The protocol shall be used for reference
during manufacturer participation in verification testing.
Report - A written document that includes data, test results, findings, and any pertinent
information collected in accordance with a protocol, analytical methods, procedures etc., in the
assessment of a product whether such information is in preliminary, draft or final form.
Technology Specific Test Plan (TSTP) - A written document that describes the procedures for
conducting a test or study for the application of water treatment technology. At a minimum, the
TSTP will include detailed instructions for sample and data collection, sample handling and
sample preservation, precision, accuracy, reproducibility goals, and quality assurance/quality
control (QA/QC) requirements.
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Testing Laboratory - An organization certified by a third- party independent organization,
Federal agency, or a pertinent state regulatory authority to perform the testing of drinking water
samples. The role of the testing laboratory in the verification testing of equipment is to analyze
the water samples in accordance with the methods and meet the pertinent QA/QC requirements
described in the protocol, TSTP, and PSTP.
Verification - To establish the evidence on the range of performance of equipment and/or device
under specific conditions following a predetermined protocol(s) and TSTP(s).
Verification Statement - A written document that summarizes a final report reviewed and
approved by NSF on behalf of the EPA or directly by the EPA.
Water System - The water system that operates water treatment equipment to provide treated
water to its customers.
1.1 Objectives
The specific objectives of verification testing may be different for each system, depending upon the
statement of performance objectives of the specific equipment to be tested. The objectives developed
by each manufacturer will be defined and described in detail in the PSTP developed for each piece of
equipment. The manufacturer's performance objectives are used to establish data quality objectives
(DQOs) to develop the experimental design of the verification test. The broader the performance
objectives, the more comprehensive the PSTP must be to achieve the DQOs. The objectives of
equipment verification testing may include but are not limited to the following:
Generation of field data appropriate for verifying the performance of the equipment;
Generation of operation and maintenance (O&M) information to assist users and potential
operators of equipment; and
Evaluation of new advances in equipment and equipment design.
An important aspect in the development of verification testing is to describe the procedures that will be
used to verify the statement of performance objectives made for water treatment equipment. A PSTP
document shall incorporate the QA/QC elements needed to provide data of appropriate quality
sufficient to reach a defensible position regarding the equipment performance. Although verification
testing conducted at a single site may not represent every environmental situation, which may be
acceptable for the equipment tested, it will provide data of sufficient quality to make a judgment about
the application of the equipment under conditions similar to those encountered in the verification testing.
It is important to note that verification of the equipment does not mean that the equipment is "certified"
by NSF or EPA. Rather, it recognizes that the performance of the equipment has been determined and
verified by these organizations.
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1.2 Scope
This protocol outlines the verification process for equipment designed to remove SOCs. This protocol
can be used in conjunction with a number of different TSTPs for drinking water treatment systems
designed to achieve removal of SOCs. This protocol is not an NSF or third-party consensus standard
and it does not endorse the equipment or technologies described herein.
An overview of the verification process and the elements of the PSTP to be developed by the FTO are
described in this protocol. Specifically, the PSTP shall define the following elements of the verification
test:
Roles and responsibilities of verification testing participants;
Procedures governing verification testing activities such as equipment operation and process
monitoring; sample collection, preservation, and analysis; and data collection and interpretation;
Experimental design of the field operations procedures. The field operations procedures will
identify recommended equipment maintenance and cleaning methods;
QA/QC procedures for conducting the verification test and for assessing the quality of the data
generated from the verification test; and
Health and safety measures relating to biohazard (if present), electrical, mechanical and other
safety codes.
Content of PSTP:
The structure of the PSTP must conform to the outline below: The required components of the
Document will be described in greater detail in the sections below.
TITLE PAGE
FOREWORD
TABLE OF CONTENTS - The Table of Contents for the PSTP should include the
headings provided in this document although they may be modified as appropriate for a
particular type of equipment to be tested.
LIST OF DEFINITIONS - A list of key terms used in the PSTP should be provided
EXECUTIVE SUMMARY - The Executive Summary describes the contents of the PSTP
(not to exceed two pages). A general description of the equipment and the statement of
performance objectives which will be verified during testing as well as the testing
locations, a schedule, and a list of participants.
ABBREVIATIONS AND ACRONYMS - A list of the abbreviations and acronyms used in
the PSTP should be provided.
EQ UIPMENT VERIFICA TION TESTING RESPONSIBILITIES (described in the sections
below)
EQUIPMENT CAPABILITIES AND DESCRIPTION (described in the sections below)
EXPERIMENTAL DESIGN (described in the sections below
FIELD OPERATIONS PROCEDURES (described in the sections below)
QUALITY ASSURANCE PROJECT PLAN (described in the sections below)
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DATA MANAGEMENT AND ANALYSIS (described in the sections below)
SAFETY PLAN (described in the sections below)
2.0 EQUIPMENT VERIFICATION TESTING RESPONSIBILITIES
2.1 Verification Testing Organization and Participants
The required content of the PSTP and the responsibilities of participants are listed at the end of each
section. In the development of a PSTP, a manufacturer and its designated FTO shall provide a table
including:
The name, affiliation, and mailing address of each participant;
A point of contact;
Description of participant's role;
Telephone and fax numbers; and
E-mail address.
2.2 Organization
The organizational structure for the verification testing showing lines of communications shall be
provided by the FTO in its application on behalf of the manufacturer.
2.3 Verification Testing Site Name and Location
This section discusses background information on the verification testing site(s), with emphasis on the
quality of the feedwater, which in some cases may be the source water at the site. The PSTP must
provide the site names and locations at which the equipment will be tested. In most cases, the
equipment will be demonstrated at more than one site. Depending upon the verification testing
requirements stipulated in the TSTP employed, testing of the equipment may be required under different
conditions of feedwater quality (or source water quality) that allow evaluation of system performance
over a range of seasonal climate and weather conditions.
2.4 Site Characteristics
The PSTP shall include an area location map showing access from major streets and highways and a
site layout drawing with equipment footprints and dimensions. The drawing should indicate the location
of existing facilities, the source of the feedwater, and where the treated water will be discharged and the
waste streams disposed. The PSTP shall also indicate if any facilities other than the equipment would
be required to perform the test such as additional trailers or temporary structures for sample collection
and preparation, electrical power, concrete pads, drainage, easements, etc. The location of SOC waste
treatment, disposal and discharge facility or method of removal shall be clearly identified in the site plan.
The PSTP must include a description of the test site. This shall include a description of where the
equipment will be located. If the feedwater to the equipment is the source water for an existing water
treatment plant, describe:
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The raw water intake;
The opportunity to obtain raw water without the addition of any chemicals; and
The operational pattern of raw water pumping at the full-scale facility (is it continuous or
intermittent?).
The source water characteristics shall be described and documented. The PSTP shall also describe
facilities to be used for handling the treated water and wastes (i.e., residuals) produced during the
verification test. The PSTP will state whether the required water flows and waste flows produced are
dealt with in an acceptable way, and whether any water pollution discharge permits are needed.
2.5 Responsibilities
The PSTP shall identify the organizations involved in the testing and describes the primary
responsibilities of each organization. Multiple manufacturers testing for removal of SOCs may be
conducted concurrently. The responsibilities of the manufacturer will vary depending on the type of
verification testing. However, at a minimum, the manufacturer shall be responsible for:
Providing the equipment to be evaluated during verification testing. The equipment must be in
complete working order at delivery to the test site;
Providing logistical and technical support, as required; and
Providing equipment that explicitly meets all requirements of the Occupational Safety and Health
Administration (OSHA), National Electrical Manufacturers Association (NEMA), Underwriters
Laboratory Inc. (UL), NSF, and other appropriate agencies to ensure operator safety during
verification testing.
The FTO shall be responsible for:
Preparation of the PSTP;
Providing needed logistical support, establishing a communication network, and scheduling and
coordinating the activities of all verification testing participants;
Ensuring that locations selected as test sites have feedwater quality consistent with the
objectives of the verification testing (the manufacturer may recommend a site(s) for verification
testing.);
Managing, evaluating, interpreting, and reporting on data generated by the verification testing;
and
Evaluating and reporting on the performance of the technologies applied to achieve removal of
SOCs.
Content of PSTP Regarding Verification Testing Responsibilities:
The FTO shall be responsible for including the following elements in the PSTP:
Definition of the roles and responsibilities of appropriate verification testing participants;
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A table, which includes the name, affiliation, and mailing address of each participant, a
point-of-contact, their role, telephone andfax numbers, and e-mail address;
Organization of operational and analytical support;
List of the site name(s) and location(s); and
Description of the test site(s), the site characteristics and identification of where the
equipment will be located.
The manufacturer shall be responsible for:
Provision of complete, field-ready equipment for verification testing;
Provision of logistical, and technical support, as required;
Provision of assistance to the qualified FTO during operation and monitoring of the
equipment during the verification testing;
Reviewing the PSTP; and
Reviewing the verification report.
3.0 EQUIPMENT CAPABILITIES AND DESCRIPTION
3.1 Equipment Capabilities
The manufacturer and its designated FTO must identify in a statement of performance objectives the
specific performance criteria to be verified and the specific operational conditions under which the
verification testing shall be performed. In conjunction with a statement of performance objectives, the
FTO shall state the pertinent detection limits for the specific analytical method. Statements should be
made regarding the applications of the equipment, the known limitations of he equipment and under
what conditions the equipment is likely to fail or underperform. The statement of performance
objectives must be specified and verifiable by a statistical analysis of the data. Examples of two
different types of statements of performance objectives that may be verified in this testing are:
1. "This system is capable of achieving 98% removal of the SOC chlordane 60-day operation
period at a flux of 15 gpm/sf (75% recovery; temperature between 20 and 25ฐC) in feedwaters
with chlordane concentrations less than 0.1 mg/L and total dissolved solids (IDS)
concentrations less than 500 mg/L."
2. "This system is capable of producing a product water with a chlordane concentration less
than 2 |j,g/L during a 60-day operation period at a flux of 15 gpm/sf (75% recovery;
temperature between 20 and 25ฐC) in feedwaters with chlordane concentrations less than 0.1
mg/L and IDS concentrations less than 500 mg/L."
An example of a statement of performance objectives that would not be acceptable is presented below:
"This system will achieve removal of SOCs in accordance with the Safe Drinking Water Act
(SDWA) on a consistent and dependable basis."
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The statement of performance objectives shall identify the water quality objectives to be achieved by the
equipment and evaluated in the verification testing. For each statement of performance objectives
proposed by the FTO and the manufacturer in the PSTP, the following information shall be provided:
Applications of the equipment;
Known limitations of the equipment;
Advantages it provides over existing equipment;
Percent removal of the targeted SOC;
Rate of treated water production (i.e., flux);
Product water recovery;
Feed stream water quality regarding pertinent water quality parameters;
Temperature;
Concentration of targeted SOC; and
Other pertinent water quality and operational conditions.
During verification testing, the FTO must demonstrate that the equipment is operating at a steady-state
prior to collection of data to be used in verification of the statement of performance objectives. The
following equation shall be used to determine percent removal of the SOC investigated:
Percent SOC Removal =
Finished Water SOC Concentration
1
Feed Water SOC Concentrat ion
*100%
The FTO, on behalf of the manufacturer, shall be responsible for identification of which SOC shall be
monitored and recorded for testing under the statement of performance objectives in the PSTP. The
analysis of SOCs in the feedwater, treated water and wastewater streams shall be performed by a
state-certified, third-party accredited or EPA-accredited laboratory using an approved Standard
Method.
The statement of performance objectives prepared by the FTO (in collaboration with the manufacturer)
shall also indicate the range of water quality under which the equipment can be challenged while
successfully treating the feedwater. Statements of performance objectives that are not too easily met
may not be of interest to the potential user, while performance objectives that are overstated may not be
achievable. If a manufacturer relies on integrated physio-chemical processes for SOC removal, the
statement of performance objectives must include the overall water treatment system SOC lemoval
performance. The statement of performance objectives forms the basis of the entire verification test and
must be chosen appropriately. Therefore, the design of the PSTP should include a sufficient range of
feedwater quality to permit verification of the statement of performance objectives.
It should be noted that many of the drinking water treatment systems participating in verifying SOC
removal might be capable of achieving multiple water treatment objectives. Although this protocol and
the associated TSTPs are oriented towards removal of SOCs from feedwaters, the manufacturer may
want to look at the treatment system's removal capabilities for additional water quality parameters.
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3.2 Equipment Description
Description of the equipment for verification testing shall be included in the PSTP. Data plates shall be
permanent and securely attached to each production unit. The data plate shall be easy to read in English
or the language of the intended user, located on the equipment where it is readily accessible, and contain
at least the following information:
Equipment Name;
Model Number;
Manufacturer's name and address;
Electrical requirements - volts, amps, hertz and phase;
Equipment size and weight;
Shipping requirements and special handling precautions;
Equipment maintenance requirements;
Serial Number;
Warning and Caution statements in legible and easily discernible print size; and
Capacity or output rate (if applicable).
In addition, the manufacturer must provide the equipment with all OSHA required safety devices (if
applicable).
Content of PSTP Regarding Equipment Capabilities and Description:
The PSTP shall include the following elements:
Description of the equipment to be demonstrated including photographs from several
perspectives;
Brief introduction and discussion of the engineering and scientific concepts on which the
SOC removal capabilities of the water treatment equipment are based;
Description of the treatment equipment and each process included as a component in the
modular system including all relevant schematics of treatment andpretreatment systems;
Brief description of the physical construction/components of the equipment, including the
general environment requirements and limitations, required consumables; weight,
transportability, ruggedness, power and other pertinent information needed, etc.;
Statement of typical rates of consumption of chemicals, a description of the physical and
chemical nature of wastes, and the rates of waste generation (concentrates, residues,
waste products, required regeneration frequencies; materials replacement frequencies;
etc.);
Definition of the performance range of the equipment;
Identification of any special licensing requirements associated with the operation of the
equipment;
Description of the applications of the equipment and the removal capabilities of the
treatment system relative to existing equipment. Comparisons shall be provided in such
areas as: treatment capabilities, requirements for chemicals and materials, power, labor
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requirements, suitability for process monitoring and operation from remote locations,
ability to be managed by part-time operators; and
Discussion of the known limitations of the equipment. The following operational details
shall be included: the range of feedwater quality suitable for treatment with the
equipment, the upper limits for concentrations of contaminants that can be removed to
concentrations below a certain level, level of operator skill required to successfully use
the equipment.
4.0 EXPERIMENTAL DESIGN
This section discusses the objectives of the verification testing, factors that must be considered to meet
the performance objectives, and the statistical analysis and other means that the FTO will use to
evaluate the results of the verification testing.
4.1 Objectives
The objectives of verification testing are to evaluate equipment in the following areas:
Performance relative to the manufacturer's stated range of SOC removal objectives and
equipment operation;
The impacts of variations in feedwater quality (such as dissolved organic carbon (DOC),
temperature, turbidity, microbial concentration, pH, alkalinity, etc.) on equipment performance;
The logistical, human, and economic resources necessary to operate the equipment; and
The reliability, ruggedness, cost factors, range of usefulness, and ease of operation
The manufacturer shall be responsible for selection of those treatment challenges listed in the TSTPs that
are most appropriate for their equipment. For example, if equipment were only intended for removal of
SOCs, there would be no need to conduct testing to evaluate the removal of hardness ions or metal ion
species. However, it should be noted that many of the drinking water treatment systems participating in
verifying SOC removal might be capable of achieving multiple water treatment objectives. The
verification test may for example be undertaken to demonstrate equipment removal capabilities for a
wide number of constituents. In addition, the FTO and the manufacturer may wish to construct the
PSTP so that verification testing may also demonstrate the treatment system's removal capabilities and
treatment operations for additional water quality parameters. The incorporation of additional treatment
objectives may also necessitate attention to the other applicable protocol and TSTPs in the development
of the PSTP.
4.2 Equipment Characteristics
This section discusses equipment characteristics or factors that will be considered in the design and
implementation of verification testing These factors include:
Ease of operation;
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Degree of operator attention required;
Response of equipment and treatment process to changes in feedwater quality;
Electrical requirements;
System reliability features including redundancy of components;
Feed flow requirements;
Discharge requirements;
Spatial requirements of the equipment (footprint);
Unit processes included in treatment train;
Chemicals needed;
Chemical hazards associated with equipment operation; and
Response of treatment process to intermittent operation.
Verification testing procedures shall simulate routine conditions as much as possible and in most cases
testing may be done in the field. Under such circumstances, simulation of field conditions would not be
necessary.
4.2.1 Qualitative Factors
Some factors, while important, are difficult or impractical to quantify. These are considered
qualitative factors. Important factors that cannot easily be quantified are the modular nature of
the equipment, ease of operation, the safety of the equipment, the portability of equipment, and
the logistical requirements necessary for using it.
Typical qualitative factors to be discussed are listed below, and others may be added. The
PSTP shall discuss those factors that are appropriate to the test equipment that may include:
Reliability or susceptibility to environmental conditions:
Equipment safety:
Effect of operator experience on results; and
Effect of operator's technical knowledge on system performance and robustness of
operation.
4.2.2 Quantitative Factors
Many factors of the equipment characteristics can be quantified by various means during
verification testing. Some can be measured while others cannot be controlled. Typical
quantitative factors to be discussed are listed below, and others may be added. The PSTP shall
discuss those factors that are appropriate to the test equipment that may include:
Power and consumable supply (such as chemical and materials) requirements;
Productivity and performance of equipment;
Monitoring requirements for pressure, flow, and temperature;
Cost factors of operation, expendables and waste disposal;
Hydrodynamics of system;
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Chemical equivalents of process streams;
Safety features of equipment;
Length of operating cycle; and
Daily labor hours required for O&M.
These quantitative factors will be used as an initial benchmark to assess equipment performance.
4.3 Water Quality Considerations
The primary treatment goal of the equipment employed in verification testing through this protocol is to
achieve removal of SOCs found in feedwaters (or raw waters) such that finished waters are of
acceptable water quality. The objectives of verification testing may also be to assure production of
water with palatable, healthful and consistent water quality. The experimental design and statement of
performance objectives in the PSTPs shall be developed so the relevant questions about water
treatment equipment capabilities can be answered.
Manufacturers should carefully consider the capabilities and limitations of their equipment and have their
statement of performance objectives sufficiently challenge their equipment. The FTO on behalf of the
manufacturer should adopt an experimental approach to verification testing that would provide a broad
market for their products, while recognizing the limitations of the equipment. The FTO should not adopt
a verification experimental approach to removal of SOCs that would be beyond the capabilities of the
equipment. A wide range of contaminants or water quality problems that can be addressed by water
treatment equipment varies, and some treatment equipment can address a broader range of problems
than other types. Manufacturers shall use TSTPs as the basis for the development of the experimental
plan in each specific PSTP.
4.3.1 Feedwater Quality
One of the key aspects related to demonstration of equipment performance in verification testing
is the range of feedwater quality that can be treated successfully, resulting in treated water
quality that meets water quality goals or regulatory requirements. The manufacturer and FTO
should consider the influence of feedwater quality on the quality of treated waters produced by
the equipment, such that product waters meet the designated water quality goals stated in the
PSTP. As the range of feedwater quality that can be treated by the equipment becomes
broader, the potential applications for treatment equipment with verified performance
capabilities might also increase.
The FTO shall provide a list of SOCs in the PSTP that may be pertinent in equipment
performance for removal of SOCs. Characteristics of feedwater quality that may be important
for treatment equipment intended to remove SOCs should be identified in the applicable PSTP.
One of the questions often asked by regulatory officials in approval of water treatment
equipment is: "Has it been shown to work on the water where it is proposed to be used?" By
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covering a large range of water qualities, verification testing is more likely to provide an
affirmative answer to that question.
4.3.2 Treated Water Quality
Production of treated water of a high quality, having no trace of SOC shall be the primary goal
of the water treatment systems included in verification testing If an FTO states that water
treatment equipment can be used to treat water to meet specified regulatory requirements for
removal of SOCs, verification testing must provide data that support such a statement of
performance objectives, as appropriate.
The FTO, on behalf of the manufacturer, shall be responsible for identification of the specific
SOCs that shall be monitored during verification testing. A state-certified, third-party
accredited or EPA accredited laboratory shall perform water quality analysis for the specific
SOCs identified in water samples provided by the FTO. This issue shall be discussed further in
Section 5.2.
In addition, the FTO may wish to make a statement about performance objectives of the
equipment for removal of other contaminants that are not directly related to SOC removal For
example, some water treatment equipment can be used to meet aesthetic goals. Removal goals
for some of these parameters may also be presented in the PSTP as additional statements of
performance objectives.
4.4 Synthetic Organic Chemical Contaminants Testing
Because of the numerous varieties of SOCs, analytical procedures must be approved or proven
techniques. Many methods for SOC analysis are outlined in Standard or EPA Methods and shall be
employed in verification testing and evaluation of SOCs. Should an approved method be non-existent
for an individual SOC, then a proposed method may be allowed after at least three labs have
successfully demonstrated the method to achieve a standard degree of uncertainty in analysis. The
manufacturer would be required to document and submit details of analytical procedures used to
measure the specific SOC.
Frequency of sampling and SOC analysis shall be specified by the individual TSTPs used for the
verification test and shall also be stipulated in the PSTP.
4.5 Recording Data
For all SOC experiments targeted towards removal of SOCs, water quality data on feedwater, finished
water, and wastewater should be maintained at a minimum on the identified SOCs and other water
quality parameters identified by the FTO. The specific water quality parameters to be monitored and
with what frequency shall be stipulated in the TSTP(s) employed for development of the PSTP prior to
initiation of the verification test. At a minimum, the following conditions shall also be maintained for each
experiment:
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Water type (raw water, pretreated feedwater, product water, waste water);
Experimental run (e.g., 1st run, 2nd run, 3rd run, etc.);
Type of chemical addition, dose and chemical combination, where applicable (e.g., alum,
cationic polymer, anionic polymer, ozone, monochloramine, scale inhibitor, etc.);
Rate of flow through system, volume waste production as percent finished water flow,
cumulative flow through system in terms of bed volumes (BV) (where applicable);
Transmembrane pressure, membrane flux and element recovery (for membrane processes
where applicable);
Chemical cleaning frequency or regeneration frequency (where applicable); and
Voltage requirements, current draw and power consumption at specific operating conditions.
4.6 Recording Statistical Uncertainty
For the analytical data obtained during verification testing, 95% confidence intervals shall be calculated
by the FTO for water quality parameters in which eight or more samples are collected. The FTO shall
ensure in the PSTP that sufficient water quality data and operational data are collected to allow
estimation of statistical uncertainty for critical parameters. The specific TSTP(s) that may be employed
with the protocol stipulate only a minimum frequency for monitoring of SOCs. The FTO shall therefore
ensure that sufficient water quality and operational data is collected during verification testing for the
statistical analysis described herein. The specific TSTP(s) shall specify which water quality parameters
shall be subjected to the requirements of confidence interval calculation. The specific TSTP(s) shall
specify which water quality parameters shall be subjected to the requirements of confidence interval
calculation. DQOs and the vendor's performance objectives shall be used to assess which water
quality parameters are critical and thus require confidence interval statistics. As the name implies, a
confidence interval describes a population range in which any individual population measurement may
exist with a specified percent confidence. The following formula shall be employed for confidence
interval calculation:
where: x = sample mean;
S = sample standard deviation;
n = number of independent measurements included in the data set;
t = Student's t distribution value with n-1 degrees of freedom; and
a = 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:
With input of the analytical results for pertinent water quality parameters into the 95% confidence
interval equation, the output will appear as the sample mean value plus or minus the confidence term.
Confidence Interval =
95% Confidence
Interval = x ฑ t
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The results of this statistical calculation may also be presented as a range of values falling within the 95%
confidence interval. For example, the results of the confidence interval calculation may provide the
following information: 520 ฑ38.4 mg/L, with a 95% confidence interval range described as (482, 558).
Calculation of confidence intervals shall not be required for equipment performance results (e.g., filter
run length, cleaning efficiency, in-line turbidity or in-line particle counts, etc.) obtained during the
equipment verification testing. However, as specified by the FTO, calculation of confidence intervals
may be required for analytical parameters such as SOC and non-purgeable dissolved organic carbon
(NPDOC). To provide sufficient analytical data fir statistical analysis, the FTO shall collect three
discrete water samples at one set of operational conditions for each of the specified water quality
parameters during a designated testing period. The procedures and sampling requirements shall be
provided in detail in the PSTP.
4.7 Verification Testing Schedule
Verification testing activities include equipment set-up, initial operation, verification operation, and
sampling and analysis. Initial operations are to be conducted so that equipment can be tested to be sure
it is functioning as intended. If feedwater (or source water) quality influences operation and
performance of the equipment being tested, the initial operations period serves as the shakedown period
for determining appropriate operating parameters. The schedule of testing may also be influenced by
coordination requirements with a utility.
For water treatment equipment involving removal of SOCs, an initial period of bench-scale testing of
feedwater followed by treatment equipment operation may be needed to determine the appropriate
operational parameters for testing equipment. A number of operational parameters may require
adjustment to achieve successful functioning of the process train. These parameters may include but are
not limited to the following: process rates; feedwater pH; chemical dosages, chemical types (where
appropriate) and other parameters that may result in successful functioning of the process train.
Chemical type, chemical dosages, and other operations that result in successful functioning of the
process should be included.
It is recommended under this protocol that a minimum of one 60-day test period of verification testing
be conducted to allow testing over a period of time to collect representative data. The specific
operating and water quality parameters shall be stipulated by the selected TSTP(s) under this protocol
and shall be used in development of the experimental plan and the preparation of the PSTP.
Content of PSTP Regarding Experimental Design
The PSTP shall include the following elements:
Identification of the qualitative and quantitative factors of equipment operation to be
addressed in the verification testing;
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Identification and discussion of the particular water treatment issues and SOC
concentrations that the equipment is designed to address, how the equipment will solve
the problem, and who would be the potential users of the equipment;
Identification of the range of key water quality parameters, given in applicable TSTPs,
which the equipment is intended to address andfor which the equipment is applicable;
Identification of the key parameters of treated water quality and analytical methods that
will be used for evaluation of equipment performance during the removal of SOCs.
Parameters of significance for treated water quality are listed in applicable TSTPs;
Description of data recording protocol for equipment operation, feedwater quality
parameters, and treated water quality parameters;
Description of the confidence interval calculation procedure for selected water quality
parameters; and
Detailed outline of the verification testing schedule, with regard to annual testing periods
that will cover an appropriate range of annual climatic conditions, (i.e., different
temperature conditions, seasonal differences between rainy and dry conditions).
5.0 FIELD OPERATIONS PROCEDURES
5.1 Equipment Operations and Design
The TSTP specifies procedures that shall be used to provide accurate documentation of both equipment
performance and treated water quality. Careful adherence to these procedures will result in definition of
verifiable performance of equipment. The specific reporting techniques, methods of statistical analysis
and the QA/QC of reporting SOC removal data shall be stated explicitly by the FTO in the PSTP
before initiation of the verification test. (Note that this protocol may be associated with a number of
different TSTPs for different types of process equipment capable of achieving removal of SOCs).
The design aspects of water treatment process equipment often provide a basis for approval by state
regulatory officials and can be used to ascertain if process equipment intended for larger or smaller
flows involves the same operating parameters that were relevant to the verification testing. The field
operations procedures and testing conditions provided by the FTO shall therefore be specified to
demonstrate treatment capabilities over a broad range of operational conditions and feedwater qualities.
Initial operations of the SOC removal equipment will allow FTOs to refine the equipment operating
procedures and to make operational adjustments as needed to successfully treat the feedwater.
Information generated through this period of operation may be used to revise the PSTP, if necessary. A
failure at this point in the verification test could indicate a lack of capability of the process equipment and
verification testing might be cancelled. Specific design aspects to be included in the PSTP are provided
in detail, in the Manufacturer Responsibilities section below.
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5.2 Selection of Analytical Laboratory and Field Testing Organization
To assess the performance of the equipment, the quality of the treated water produced using the
equipment shall be determined by analysis at a state-certified, third-party accredited or EPA-accredited
analytical laboratory with proven experience in detection and measurement of SOCs. In all cases,
current EPA Standard Methods procedures shall be used in analysis of specified water quality
parameters. Because of the variability of acceptance of laboratories from state to state, use of analytical
laboratories certified in a large number of states is recommended. Furthermore, the selected analytical
laboratory must be certified by the state in which the verification testing is being performed. Analytical
results from the laboratory are to be provided directly to the NSF to maintain data integrity.
For field testing operations, the manufacturer shall employ an NSF-qualified FTO; the list of qualified
FTOs may include engineering consulting firms, universities, or other qualified scientific organizations
with experience operating drinking water treatment equipment. If a particular SOC does not have an
accepted standard method procedure, then an analytical testing plan describing the procedure shall be
submitted to NSF for approval.
5.3 Communications, Documentation, Logistics, and Equipment
NSF shall communicate regularly with the verification testing participants to coordinate all field activities
associated with the verification test and to resolve any logistical, technical, or QA/QC issues that may
arise as the verification testing progresses. The successful implementation of the verification test will
require detailed coordination and constant communication between all verification testing participants.
All field activities shall be thoroughly documented. Field documentation will include:
Field logbooks;
Photographs;
Field data sheets; and
Chain-of-custody forms.
The qualified FTO shall be responsible for maintaining all field documentation. The field logbook shall
have at least the following requirements.
Field notes shall be kept in a bound logbook;
Each page shall be sequentially numbered and labeled with the project name and number;
Field logbooks shall be used to record all water treatment equipment operating data;
Completed pages shall be signed and dated by the individual responsible for the entries; and
Errors shall have one line drawn through them and this line shall be initialed and dated.
All photographs shall be logged in the field logbook. These entries shall include the time, date, direction,
subject of the photograph, and the identity of the photographer. Deviations from the approved final
PSTP shall be thoroughly documented in the field logbook at the time of inspection and in the
verification report.
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Original field sheets and chain-of-custody forms shall accompany all samples shipped to the analytical
laboratory. Copies of field sheets and chain-of-custody forms for all samples shall be provided at the
time of the QA/QC inspection and included in the verification report.
As available, electronic data storage and retrieval capabilities shall be employed to maximize data
collection and minimize labor hours required for monitoring. The guidelines for use of data-loggers,
laptop computers, data acquisition systems etc., shall be detailed by the FTO in the PSTP.
5.4 Initial Operations
Initial operations will allow equipment manufacturers to refine their operating procedures and to make
operational adjustments as needed to successfully treat the feedwater. Information generated through
this period of operation may be used to revise the PSTP, if necessary. A failure at this point in the
verification testing could indicate a lack of capability of the process equipment and the verification test
might be canceled.
5.5 Equipment Operation and Water Quality Sampling for Verification Testing
All field activities shall conform to requirements provided in the PSTP that was developed and NSF-
approved for the verification test being conducted. All sampling and sample analyses conducted during
the verification test shall be performed according to the procedures detailed by the FTO in the PSTP.
As necessary for verification analyses, state-certified, third-party or EPA-qualified laboratories are
selected to perform analytical services using approved Standard or EPA Methods. If unanticipated or
unusual situations are encountered that may alter the plans for equipment operation, water quality
sampling, or data quality, the situation must be discussed with the NSF technical lead. Any deviations
from the approved final PSTP shall be thoroughly documented.
During routine operation of water treatment equipment, the total number of hours during which the
equipment is operated each day shall be documented. In addition, the number of hours each day during
which the operator was working at the treatment plant performing tasks related to water treatment and
the operation of the treatment equipment shall be documented. The qualified FTO, the water system, or
the plant operator shall describe the tasks performed during equipment operation.
Content of PSTP Regarding Field Operations Procedures
The PSTP shall include the following elements:
A table summary of the proposed time schedule for operating and testing;
Field operating procedures for the equipment and performance testing, based upon the
TSTP, including:
listing of operating parameters,
ranges for feedwater quality, and
sampling and analysis strategy;
Provision of all equipment neededfor field work associated with this verification testing;
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Provision of a complete list of all equipment to be used in the verification testing. A table
format is suggested;
Provision offield operating procedures; and
At a minimum, a table(s) showing all parameters to be analyzed, the analytical methods,
the laboratory reporting limits or quantification limits, sample volume, bottle type,
preservation method, and holding times.
Manufacturer Responsibilities:
Provision of all equipment neededfor field work associated with this verification testing;
Provision of a complete list of all equipment to be used in the verification testing. A table
format is suggested; and
Provision of field operating procedures.
6.0 QUALITY ASSURANCE PROJECT PLAN
Every PSTP for verification testing must include a Quality Assurance Project Plan (QAPP) that specifies
procedures that shall be used to ensure data quality and integrity. Careful adherence to these
procedures will ensure that data generated from verification testing will provide sound analytical results
that can serve as the basis for performance verification.
6.1 Purpose and Scope
The purpose of this section is to outline steps that shall be taken by operators of the equipment and by
the analytical laboratory to ensure that data resulting from verification testing is of known quality and that
a sufficient number of critical measurements are taken.
6.2 Quality Assurance Responsibilities
The FTO project manager is responsible for coordinating the preparation of the QAPP for the
verification test and for its approval by NSF. The FTO project manager, with oversight from NSF,
shall also ensure that the QAPP is implemented during all verification testing activities.
The manufacturer and NSF must approve the entire PSTP including the QAPP before the verification
test can proceed. NSF must review and either approve the QAPP or provide reasons for rejection of
the QAPP. NSF should also provide suggestions on how to modify the QAPP to make it acceptable,
provided that the FTO has made a good faith effort to develop an acceptable QAPP (i.e., the QAPP is
75 to 80% acceptable with only minor changes needed to produce an acceptable PSTP. NSF will not
write QAPPs for manufacturers.).
A number of individuals may be responsible for monitoring equipment operating parameters and for
sampling and analysis QA/QC throughout the verification testing. Primary responsibility for ensuring that
both equipment operation and sampling and analysis activities comply with the QA/QC requirements of
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the PSTP shall rest with the FTO. QA/QC activities for the equipment shall include those activities
recommended by the manufacturer and those required by NSF to assure the verification testing will
provide data of the necessary quality.
QA/QC activities for the state-certified or third-party or EPA-qualified analytical laboratory that
analyzes samples sent off-site shall be the responsibility of that analytical laboratory's supervisor. If
problems arise or any data appear unusual, they shall be thoroughly documented and corrective actions
shall be implemented as specified in this section. The QA/QC measurements made by the off-site
analytical laboratory are dependent on the analytical methods being used.
6.3 Data Quality Indicators
The data obtained during verification testing must be of sound quality for conclusions to be drawn on the
equipment. For all measurement and monitoring activities conducted for equipment verification, NSF
and the EPA require that data quality parameters be established based on the proposed end uses of the
data. Data quality parameters include four indicators of data quality:
Accuracy;
Precision;
Completeness;
Representativeness; and
Statistical Uncertainty.
Treatment results generated by the equipment and by the laboratory analyses must be verifiable for the
purposes of the verification testing program to be fulfilled. High quality, well-documented analytical
laboratory results are essential for meeting the purpose and objectives of verification testing. Therefore,
the following indicators of data quality shall be closely evaluated to determine the performance of the
equipment when measured against data generated by the analytical laboratory.
6.3.1 Accuracy
For water quality analyses, accuracy refers to the difference between a sample result and the
reference or true value for the sample. Loss of accuracy can be caused by such processes as:
Errors in standards preparation;
Equipment calibrations;
Loss of target analyte in the extraction process;
Interferences; and
Systematic or carryover contamination from one sample to the next.
In verification testing, accuracy will be ensured by:
Maintaining consistent sample collection procedures, including sample locations;
Timing of sample collection;
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Sampling procedures;
Sample preservation;
Sample packaging;
Sample shipping; and
Random spiking procedures for the specific inorganic constituents chosen for testing.
The FTO shall discuss the applicable ways of determining the accuracy of the chemical and
microbiological sampling and analytical techniques in the PSTP.
For water quality analysis, accuracy is usually expressed as the percent recovery. Percent
recovery is the amount recovered during analysis. In general percent recovery can be
calculated by dividing the measured amount added by the amount actually added.
Percent Recovery =
f MeasuredSample+ Spike- Measured Sample'
Actual Spike j
(Measured ^
100% =
Spike
Actual Spike j
100%
For equipment operating parameters, accuracy refers to the difference between the reported
operating condition and the actual operating condition. For equipment operating data, accuracy
entails collecting a sufficient quantity of data during operation to be able to detect a change in
operations. For water flow, accuracy may be 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 (bucket and stopwatch technique) as practiced in hydraulics
laboratories or water meter calibration shops. For mixing equipment, accuracy is the difference
between an electronic readout for equipment rotations per minute (rpms) and the actual
measurement based on counted revolutions and measured time. Accuracy of head loss
measurement can be determined by using measuring tapes to check the calibration of
piezometers for gravity filters or by checking the calibration of pressure gauges for pressure
filters. Meters and gauges must be checked periodically for accuracy, and when proven to be
dependable over time, the time interval between accuracy checks can be increased. In the
PSTP, the FTO shall discuss the applicable ways of determining the accuracy of the operational
conditions and procedures.
6.3.2 Precision
Precision refers to the degree of mutual agreement among individual measurements and provides
an estimate of random error. The standard deviation and the relative percent deviation
recorded from sample analyses may be reported as a means to quantify sample precision.
Precision measures the repeatability of measurement. It is usually expressed as the percent
relative standard deviation (percent RSD). In general percent RSD can be calculated by
dividing the standard deviation by the average. The methods to be employed for use of
deviation shall be described by the FTO in the PSTP.
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(
Percent RSD
'Standard Deviation x
Average y
100%
100%
v
y
y1 = sample measuremen t
n = number of samples
For acceptable analytical precision under the verification testing program, the percent RSD for
drinking water samples must be less than 30%. If the data generated during the ETV test does
not meet the DQOs defined in this QA/QC section, additional testing and sampling will be
required. If the DQOs are still not met through additional testing and the collection of additional
samples, then a retest will be required.
6.3.3 Completeness
Completeness refers to the amount of data collected from a measurement process compared to
the amount that was expected to be obtained. Completeness refers to the proportion of valid,
acceptable data generated using each method. This portion of the required data for the selected
test plan will be reported at the conclusion of each testing period.
The completeness objective for data generated during verification testing is based on the number
of samples collected and analyzed for each parameter and/or method. The test plans will likely
require a large number of samples to be collected for key and most important parameters
and/or methods. The following chart illustrates the completeness objectives for performance
parameter and/or method based on the sample frequency:
Number of Samples Per
Parameter and/or Method
Percent Completeness
0-10
11-50
>50
80%
90%
95%
Completeness is defined as follows for all measurements:
%C = (V/T) X 100
where: %C = percent completeness;
V = number of measurements judged valid; and
T = total number of measurements.
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Additional testing and collection of additional sample will be required if the percent
completeness objectives are not met. If the completeness objectives are still not met through
the collection of additional samples, then a retest will be required.
The following are examples of instances that might cause a sample analysis to be incomplete:
Instrument failure;
Calibration requirement not being met; and
Elevated analyte levels in the method blank.
6.3.4 Representativeness
Representativeness refers to the degree to which the data accurately and precisely represent the
conditions or characteristics of the parameter represented by the data. In verification testing,
representativeness will be ensured by maintaining consistent sample collection procedures,
including:
Sample locations;
Timing of sample collection;
Sampling procedures;
Sample preservation;
Sample packaging;
Sample shipping;
Sample equipment decontamination; and
Blind spikes.
Using each method at its optimum capability to provide results that represent the most accurate
and precise measurement that it is capable of achieving also will ensure representativeness. For
equipment operating data, representativeness entails collecting a sufficient quantity of data during
operation to be able to detect a change in operations.
6.3.5 Statistical Uncertainty
Statistical uncertainty of the water quality parameters analyzed shall be evaluated through
calculation of the 95% confidence interval around the sample mean. Description of the
confidence interval calculation is provided in Section 4.6 - Recording Statistical Uncertainty.
6.4 Quality Control Checks
This section describes the QC requirements that apply to both the treatment equipment and the on-site
measurement of water quality parameters. It also contains a discussion of the corrective action to be
taken if the QC parameters fall outside of the evaluation criteria.
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The QC checks provide a means of measuring the quality of data produced. The FTO may not need to
use all of the checks identified in this section. The selection of the appropriate QC checks depends on
the following:
Equipment;
Experimental design; and
Performance goals
The selection of QC checks will be based on discussions between the FTO and NSF. Some types of
QC checks applicable to operating water treatment equipment were described in Section 6.3.
6.4.1 Quality Control for Equipment Operation
This section will explain the methods to be used to check on the accuracy of equipment
operating parameters and the frequency with which these QC checks will be made. A key
aspect of verification testing is to provide operating results that will be widely accepted by state
regulatory officials. If the quality of the equipment operating data cannot be verified, then the
water quality analytical results may be of no value. Because water cannot be treated if
equipment is not operating within specification, obtaining valid equipment operating data is a
prime concern for verification testing.
An example of the need for QC for equipment operations is an incident of rejection of test data
because the treatment equipment had no flow meter to use for determining engineering and
operating parameters related to flow.
6.4.2 Water Quality Data
After treatment equipment is operating within specifications and water is being treated, the
results of the treatment are interpreted in terms of water quality. The quality of water sample
analytical results is just as important as the quality of the equipment operating data. Therefore,
the QAPP must emphasize the methods to be employed for sampling and analytical QA.
Analytical methods for on-site and off-site monitoring are presented within each TSTP. If new
methods are published and approved or current methods updated, the most current methods
shall be used. The important aspects of sampling and analytical QA are given below:
6.4.2.1 Duplicate Samples. Duplicate samples shall be analyzed for selected water quality
parameters at specified intervals to determine the precision of analysis. The procedure for
determining samples to be analyzed in duplicate shall be provided in the PSTP with the required
frequency of analysis and the approximate number. Duplicate samples must include field
duplicates and laboratory duplicates. Field duplicates measure the precision of the overall
sampling and analysis procedures. Laboratory duplicates measure the precision associated only
with the lab procedures.
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6.4.2.2 Method Blanks. Method blanks are used for selected water quality parameters to
evaluate analytical method-induced contamination, which may cause false positive results.
6.4.2.3 Spiked Samples. The use of spiked samples will depend on the testing program,
and the contaminants to be removed. If spiked samples are to be used, specify the procedure,
frequency, acceptance criteria, and actions if criteria are not met.
6.4.2.4 Travel Blanks. Travel blanks for selected water quality parameters shall be
provided to the analytical laboratory to evaluate travel-related contamination.
6.4.2.5 Performance Evaluation Samples for On-Site Water Quality Testing.
Performance evaluation (PE) samples are samples of unknown concentration prepared by an
independent performance evaluation lab and are provided as unknowns to an analyst to evaluate
his or her analytical performance. Analysis of PE samples shall be conducted onsite by the
FTO and by the offsite laboratory before testing is initiated. If recent PE reports from the
laboratory are not available, PE samples shall be submitted by the FTO to the analytical
laboratory. The control limits for the PE samples shall be used to evaluate the FTO's and
analytical laboratory's method performance. One kind of PE sample that would be used for
on-site QA in most studies performed under this protocol would be an SOC PE sample.
A PE sample comes with statistics that have been derived from the analysis of the sample by a
number of laboratories using EPA-approved methods. These statistics include a true value of
the PE sample, a mean of the laboratory results obtained from the analysis of the PE sample,
and an acceptance range for sample values. The analytical laboratory is expected to provide
results from the analysis of the PE samples that meet the performance capabilities of the
verification testing.
6.5 Data Reduction, Validation, and Reporting
To maintain good data quality, specific procedures shall be followed during data reduction, validation,
and reporting. These procedures are detailed below.
6.5.1 Data Reduction
Data reduction refers to the process of converting the raw results from the equipment into
concentration or other data in a form to be used in the comparison. The procedures to be used
will be equipment dependent. The purpose of this step is to provide data that will be used to
verify the statement of performance objectives. These data shall be obtained from logbooks,
instrument outputs, and computer outputs as appropriate.
6.5.2 Data Validation
The operator shall confirm the completeness of the appropriate data forms and the
completeness and correctness of data acquisition and reduction. The field team supervisor or
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another technical person shall review calculations and inspect laboratory logbooks and data
sheets to confirm precision, accuracy and completeness. The individual operators and the
laboratory supervisor shall examine calibration and QC data. Laboratory and project managers
shall confirm that all instrument systems are in control and those QA objectives for precision,
accuracy, completeness, and method detection limits have been met.
Analytical outlier data are defined as those QC data lying outside a specific QC objective
window for precision and accuracy for a given analytical method. Should QC data be outside
of control limits, the analytical laboratory or field team supervisor will investigate the cause of the
problem. If the problem involves an analytical problem, the sample will be reanalyzed. If the
problem can be attributed to the sample matrix, the result will be flagged with a data qualifier.
This data qualifier will be included and explained in the final analytical report.
6.5.3 Data Reporting
The data reported during verification testing shall be explicitly defined by the FTO in the PSTP.
At a minimum, the data tabulation shall list the results for feedwater and treated water quality
analyses, the results of SOC removal analyses, and equipment operating data. All QC
information such as calibrations, blanks and reference samples are to be included in an
appendix. All raw analytical data shall also be reported in an appendix. All data shall be
reported in hardcopy and electronically in a common spreadsheet or database format.
6.6 Calculation of Data Quality Indicators
The equations for any data quality indicator calculations employed shall be provided. These include:
precision, relative percent deviation, standard deviation, accuracy, and completeness.
6.7 System Inspections
On-site system inspections for sampling activities, field operations, and laboratories shall be conducted
as specified by the TSTP. These inspections will be performed by the verification entity to determine if
the TSTP and PSTP are being implemented as intended. At a minimum, NSF shall conduct one
inspection of the sampling activities, field operations program and laboratories during the verification
test. Separate inspection reports will be completed after the inspections and provided to the
participating parties.
6.8 Reports
6.8.1 Status Reports
The FTO shall prepare periodic reports for distribution to pertinent parties, e.g., manufacturer,
EPA, and the community. These reports shall discuss project progress, problems and
associated corrective actions, and future scheduled activities associated with the verification
testing. When problems occur, the manufacturer and FTO project managers shall discuss them
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and estimate the type and degree of impact, and describe the corrective actions taken to
mitigate the impact and to prevent a recurrence of the problems. The frequency, format, and
content of these reports shall be outlined in the PSTP.
6.8.2 Inspection Reports
Any QA inspections that take place in the field or at the analytical laboratory while the
verification testing is being conducted shall be formally reported by the FTO to the verification
entity and manufacturer.
6.9 Corrective Action
Each PSTP must incorporate a corrective action plan. This plan must include the predetermined
acceptance limits, tie corrective action to be initiated whenever such acceptance criteria are not met,
and the names of the individuals responsible for implementation.
Routine corrective action may result from common monitoring activities, such as:
Routine site performance evaluation audits and
Routine technical systems audits.
Content of PSTP Regarding the QAPP
The PSTP shall include the following elements:
Description of methodology for measurement of accuracy;
Description of methodology for measurement ofprecision;
Description of the methodology for use of blanks, the materials used, the frequency, the
criteria for acceptable method blanks and the actions if criteria are not met;
Description of any specific procedures appropriate to the analysis of the PE samples;
Outline of the procedure for determining samples to be analyzed in triplicate, the
frequency and approximate number;
Description of the procedures used to assure that the data are correct;
Listing of techniques and/or equations used to quantify any necessary data quality
indicator calculations in the analysis of water quality parameters. These include
accuracy, precision, and completeness (e.g., relative percent deviation, standard
deviation, and confidence interval calculation);
Outline of the frequency, format, and content of reports in the PSTP; and
Development of a corrective action plan in the PSTP.
The FTO shall be responsible for the following:
Provision of all QC information such as calibrations, blanks and reference samples in an
appendix. All raw analytical data shall also be reported in an appendix;
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Provision of all data in hardcopy and electronic form in a common spreadsheet or database
format.
7.0 DATA MANAGEMENT, ANALYSIS AND REPORTING
7.1 Data Management and Analysis
The responsibilities of the FTO for data management and analysis have been provided in the
Responsibilities Summary Sheet, the Project Guidance Manual, and/or the Terms and Conditions cited
earlier in this protocol. The manufacturer, FTO, and NSF each have distinct responsibilities for
managing and analyzing verification testing data. The FTO is responsible for managing all the data and
information generated during verification testing. The FTO will also be responsible for analyzing and
reporting the data in the verification report. The manufacturer is responsible for furnishing those records
generated by the equipment FTO. NSF will be responsible for verification of the data.
A variety of data will be generated during verification testing. Each piece of data or information
identified for collection in the approved PSTP shall be provided in the report. The data management
section of the PSTP shall describe what types of data and information needs to be collected and
managed, and shall also describe how the data will be reported for evaluation.
The raw data and the validated data must be reported These data shall be provided in hard copy and
in electronic format As with the data generated by the innovative equipment, the electronic copy of the
laboratory data shall be provided in a spreadsheet and a data dictionary shall be provided In addition
to the sample results, all QA/QC summary forms must be provided.
Other items that must be provided include:
Field notebooks;
Photographs, slides and videotapes (copies); and
Results from the use of other field analytical methods.
7.2 Report of Equipment Testing
The FTO shall prepare a draft report describing the verification testing that was carried out and the
results of that testing. This report shall include the following topics:
Introduction;
Executive Summary;
Description and Identification of Product Tested;
Procedures and Methods Used in Testing;
Results and Discussion (discussion of results should be kept at a minimum to a avoid
conclusions and recommendations);
References;
Appendices;
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QA/QC Results; and
Inspection Report.
Content of PSTP Regarding Data Management and Analysis, and Reporting
The PSTP shall include the following:
Description of what types of data and information needs to be collected and managed
and
Description of how the data will be reported.
8.0 SAFETY AND MAINTENANCE CONSIDERATIONS
The safety procedures shall address safety considerations and include adherence to all local, state and
Federal regulations relative to safety and operational hazards. The safety procedures shall address
safety considerations, which relate to the health and safety of personnel required to work on the site of
the test equipment and persons visiting the site. Many of these items will be covered by site inspections
and construction and operating permits issued by responsible agencies. The safety procedures shall
address safety considerations, including the following as applicable:
Regulations covering the transport, storage, handling and disposal of hazardous chemicals
including acids, caustic and oxidizing agents;
Chemical hazards and biohazards;
Conformance with the National Electric Code;
Provision of and access to fire extinguishers;
Provision of sanitary facilities;
Regulations covering site security;
Conformance to any building permit requirements, such as provision of handicap access or
other health and safety requirements; and
Ventilation of equipment or of trailers or buildings housing equipment, if gases generated by the
equipment could present a safety hazard.
For additional information on pilot plant and laboratory safety, please refer to:
Palluzi, R. P. Pilot Plant and Laboratory Safety. New York: McGraw-Hill, 1994.
Fuscaldo, A. A., et al. Laboratory Safety, Theory and Practice. New York: Academic Press.
1980.
Content of PSTP Regarding Safety
The manufacturer shall be responsible for:
Provisions of required written material (such as Material Data Safety Sheets);
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Compliance with all safety requirements of local, state and Federal laws and regulators;
and
Provisions of maintenance information and troubleshooting guidelines and instructions
relative to the equipment to be verified.
The PS TP shall include the following:
Address safety considerations that are appropriate for the equipment being tested andfor
the chemicals employed in the verification test.
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CHAPTER 2
EPA/NSF ETV
EQUIPMENT VERIFICATION TESTING PLAN
FOR THE REMOVAL OF SYNTHETIC ORGANIC CHEMICAL CONTAMINANTS
BY MEMBRANE FILTRATION PROCESSES
Prepared by:
NSF International
789 Dixboro Road
Ann Arbor, MI 48105
Copyright 2002 NSF International 40CFR35.6450.
Permission is hereby granted to reproduce all or part of this work,
subject to the limitation that users may not sell all or any part of the
work and may not create any derivative work therefrom. Contact ETV
Drinking Water Systems Center Manager at (800) NSF-MARK with
any questions regarding authorized or unauthorized uses of this work.
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TABLE OF CONTENTS
LIST OF ABBREVIATIONS
1.0 APPLICATION OF THIS EQUIPMENT VERIFICATION TESTING PLAN 2-6
2.0 INTRODUCTION 2-6
3.0 GENERAL APPROACH 2-7
4.0 BACKGROUND 2-8
4.1 Regulatory and Health Effects 2-8
4.2 SOC Removal by Membrane Processes 2-9
4.3 Membrane System Design Considerations 2-11
4.3.1 Pretreatment 2-12
4.3.2 Advanced Pretreatment 2-13
4.3.3 Membrane Processes 2-13
4.3.4 Post-Treatment 2-14
4.3.5 Waste Disposal 2-14
5.0 DEFINITION OF OPERATIONAL PARAMETERS 2-15
6.0 OVERVIEW OF TASKS 2-25
7.0 TESTING PERIODS 2-26
8.0 TASK 1: CHARACTERIZATION OF RAW WATER 2-27
8.1 Introduction 2-27
8.2 Objectives 2-27
8.3 Work Plan 2-27
8.4 Schedule 2-28
8.5 Evaluation Criteria 2-28
9.0 TASK 2: MEMBRANE PRODUCTIVITY 2-29
9.1 Introduction 2-29
9.2 Experimental Objectives 2-29
9.3 Work Plan 2-30
9.3.1 Operational Data Collection 2-30
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TABLE OF CONTENTS (continued)
9.3.2 Feedwater Quality Limitations 2-31
10.0 TASK 3: FINISHED WATER QUALITY 2-36
10.1 Introduction 2-36
10.2 Obj ectives 2-36
10.3 Work Plan 2-36
10.4 Analytical Schedule 2-39
10.4.1 Removal of SOCs 2-39
10.4.2 Feed and Permeate Water Characterization 2-40
10.4.3 Water Quality Sample Collection 2-440
10.4.4 Raw Water Quality Limitations 2-40
10.5 Evaluation Criteria and Minimum Reporting Requirements 2-40
11.0 TASK 4: CLEANING EFFICIENCY 2-40
11.1 Introduction 2-40
11.2 Experimental Objectives 2-41
11.3 Work Plan 2-41
11.4 Recommended Disposal Procedures 2-41
11.5 Analytical Schedule 2-42
11.5.1 Sampling 2-42
11.5.2 Operational Data Collection 2-42
12.0 TASK 5: OPERATIONS AND MAINTENANCE MANUAL 2-42
12.1 Objectives 2-42
12.2 O&M Work Plan 2-46
13.0 TASK 6: DATA COLLECTION AND MANAGEMENT 2-48
13.1 Introduction 2-48
13.2 Objectives 2-48
13.3 Work Plan 2-48
13.3.1 Data Handling Work Plan 2-48
13.3.2 Data Management 2-49
13.3.3 Statistical Analysis 2-49
14.0 TASK 7: QUALITY ASSURANCE/ QUALITY CONTROL 2-50
14.1 Introduction 2-50
14.2 Experimental Obj ectives 2-50
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TABLE OF CONTENTS (continued)
14.3 QA/QC Work Plan 2-50
14.3.1 Daily QA/QC Verifications 2-51
14.3.2 QA/QC Verifications Performed Every Two Weeks 2-51
14.3.3 QA/QC Verifications Performed Every Testing Period 2-51
14.4 On-Site Analytical Methods 2-51
14.4.1 pH 2-51
14.4.2 Turbidity 2-52
14.4.3 Temperature 2-53
14.4.4 Dissolved Oxygen 2-53
14.5 Chemical Samples Shipped Off-Site for Analysis 2-53
14.5.1 Organic Samples 2-53
14.5.2 Inorganic Samples 2-54
14.5.3 SOC Analysis 2-54
14.6 Trip Control 2-55
15.0 TASK 8: COST EVALUATION 2-55
16.0 SUGGESTED READING 2-57
TABLES
Table 9.1 NF Membrane Pretreatment Data 2-32
Table 9.2 Daily Operations Log Sheet for a Two-Stage Membrane System 2-33
Table 9.3 Operating and Water Quality Data Requirements for Membrane Processes 2-35
Table 10.1 Water Quality and Analytical Methods 2-37
Table 12.1 Operations and Maintenance Manual Criteria - NF Membrance Process
Systems 2-43
Table 12.2 Requirements for Maintenance and Operability of NF Membrane Process
Systems 2-45
Table 12.3 NF Membrane Plant Design Criteria Reporting Itmes 2-46
Table 12.4 NF Membrane Element Characterisitics 2-47
Table 15.1 Design Parameters for Cost Analysis 2-56
Table 15.2 Operations and Maintenance Costs 2-57
FIGURE
Figure 9.1 Sample Locations for a Two-Stage Membrane Process 2-34
LIST OF APPENDICES
APPENDIX A - SOC HEALTH EFFECTS INFORMATION 2-59
APPENDIX B - PROPOSED SOCs FOR REGULATION 2-61
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LIST OF ABBREVIATIONS
DIC
dissolved inorganic carbon
EPA
Environmental Protection Agency
PSTP
Product-Specific Test Plan
FTO
Field Testing Organization
GAC
granular activated carbon
HF
hollow fiber
HSD
homogeneous solution diffusion model
IMS
Integrated Membrane Systems
IOC
inorganic compounds
MCL
maximum contaminant level
MCLG
maximum contaminant level goal
MF
microfiltration
MFI
modified fouling index
MTC
mass transfer coefficient
MWCO
molecular weight cut-off"
NF
nanofiltration
NPDES
National Pollutant Discharge Elimination System
O&M
operation and maintenance
PEG
polyethlene glycol
QA/QC
Quality Assurance/Quality Control
RO
reverse osmosis
SCADA
Supervisory Control and Data Acquisition
SDI
silt density index
SDWA
Safe Drinking Water Act
SOC
synthetic organic chemical
SW
surface water
TFC
thin-film composite
TOC
total organic carbon
IDS
total dissolved solids
UF
ultrafiltration
WTP
water treatment plant
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1.0 APPLICATION OF THIS EQUIPMENTVERIFICATION TESTING PLAN
This document is the ETV Testing Plan (Plan) for evaluation of membrane processes to be used within
the structure provided by the "EPA/NSF ETV Protocol For Equipment Verification Testing For The
Removal Of Synthetic Organic Chemical Contaminants: Requirements For All Studies". This Plan is to
be used as a guide in the development of the Product-Specific Test Plan (PSTP) for testing of
membrane process equipment to achieve removal of synthetic organic chemical contaminants (SOCs).
In order to participate in the equipment verification process for membrane processes, the equipment
Manufacturer and their designated Field Testing Organization (FTO) shall employ the procedures and
methods described in this test plan and in the referenced ETV Protocol Document as guidelines for the
development of a PSTP. The FTO shall clearly specify in its PSTP the SOCs targeted for removal and
sampling program that shall be followed during Verification Testing. The PSTP should generally follow
the Verification Testing Tasks outlined herein, with changes and modifications made for adaptations to
specific membrane equipment. At a minimum, the format of the procedures written for each Task in the
PSTP should consist of the following sections:
Introduction
Objectives
Work Plan
Analytical Schedule
Evaluation Criteria
The primary treatment goal of the equipment employed in this Verification Testing program is to remove
SOCs present in water supplies. Therefore, experimental design of the PSTP shall be developed so
that relevant performance specifications for membrane process related to SOC removal are addressed.
The Manufacturer shall establish a Statement of Performance Objectives (Section 3.0 General
Approach) that is based upon removal of target SOCs from feedwaters. The experimental design of the
PSTP shall be developed to address the specific Statement of Performance Objectives established by
the Manufacturer. Each PSTP shall include all of the included tasks, Tasks 1 to 9.
2.0 INTRODUCTION
Membrane processes are currently in use for a number of water treatment applications ranging from
removal of inorganic constituents; total dissolved solids (TDS), total organic carbon (TOC), synthetic
organic chemicals (SOCs), radionuclides and other constituents.
In order to establish appropriate operations conditions such as permeate flux, recovery, cross-flow
velocity, the Manufacturer may be able to apply some experience with his equipment on a similar water
source. This may not be the case for suppliers with new products. In this case, it is advisable to require
a pre-test optimization period so that reasonable operating criteria can be established. This would aid in
preventing the unintentional but unavoidable optimization during the Verification Testing. The need of
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pre-test optimization should be carefully reviewed with NSF, the FTO and the Manufacturer early in the
process.
Pretreatment processes ahead of RO systems are generally required to remove particulate material and
to ensure provision of high quality water to the membrane systems. For example, RO membranes
cannot generally be applied to treatment of surface waters without pretreatment of the feedwater to the
membrane system. For surface water applications, appropriate pretreatment, primarily for removal of
particulate and microbiological species, must be applied as specified by the Manufacturer. In the design
of the PSTP, the Manufacturer shall stipulate which feedwater pretreatments are appropriate for
application upstream of the RO membrane process. The stipulated feedwater pretreatment process(es)
shall be employed for upstream of the membrane process at all times during the Equipment Verification
Testing Program.
3.0 GENERALAPPROACH
Testing of equipment covered by this Verification Testing Plan will be conducted by an NSF-qualified
FTO that is selected by the equipment Manufacturer. Analytical water quality work to be carried out as
a part of this Verification Testing Plan will be contracted with a laboratory certified by a State or
accredited by a third-party organization (i.e., NSF) or the EPA for the appropriate water quality
parameters.
For this Verification Testing, the Manufacturer shall identify in a Statement of Performance Objectives
the specific performance criteria to be verified and the specific operational conditions under which the
Verification Testing shall be performed. The Statement of Performance Objectives must be specific and
verifiable by a statistical analysis of the data. Statements should also be made regarding the applications
of the equipment, the known limitations of the equipment and under what conditions the equipment is
likely to fail or underperform. Two examples of Statements of Performance Objectives that may be
verified in this testing are:
1. This system is capable of achieving 98 percent removal of the SOC chlordane 60-day
operation period at a flux of 15 gpm/sf (75 percent recovery; temperature between 20 and 25
ฐC) in feedwaters with chlordane concentrations less than 0.1 mg/L and total dissolved solids
concentrations less than 500 mg/L.
2. This system is capable of producing a product water with a chlordane concentration less
than 2 jig/L during a 60-day cperation period at a flux of 15 gpm/sf (75 percent recovery;
temperature between 20 and 25 ฐC) in feedwaters with chlordane concentrations less than 0.1
mg/L and total dissolved solids concentrations less than 500 mg/L.
During Verification Testing, the FTO must demonstrate that the equipment is operating at a steady-state
prior to collection of data to be used in verification of the Statement of Performance Objectives. For
each Statement of Performance Objectives proposed by the FTO and the Manufacturer in the PSTP,
the following information shall be provided:
percent removal of the targeted SOCs;
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rate of treated water production (i.e., flux);
recovery;
feedwater quality regarding pertinent water quality parameters;
temperature;
concentration of target SOC; and
other pertinent water quality and operational conditions.
This ETV Testing Plan is broken down into 9 tasks, as shown in the Section 6.0, Overview of Tasks.
These Tasks shall be performed by any Manufacturer wanting the performance of their equipment
verified under the ETV Program. The Manufacturer's designated FTO shall provide full detail of the
procedures to be followed in each Task in the PSTP. The FTO shall specify the operational conditions
to be verified during the Verification Testing Plan. All permeate flux values shall be reported in terms of
temperature-corrected flux values, as either gallons per square foot per day (gfd) at 77 ฐF or liters per
square meter per hour (L/(m2-hr)) at 25 ฐC.
4.0 BACKGROUND
This section provides an overview of the literature review related to SOC regulations, health effects and
contaminant removal by membrane processes and membrane system design. These items will assist in
recognizing the vast number of SOC contaminants, identifying the ability to remove SOCs from water
supplies using membrane processes, defining membrane systems and describing the mechanisms that will
help in qualifying and quantifying the removal efficiency of the membrane process tested.
4.1 Regulatory and Health Effects
Since the passage of the Safe Drinking Water Act of 1974 (SDWA) requiring the establishment of
recommended maximum contaminant levels (MCLs) for compounds that are deemed undesirable for
consumption in public water supplies. Since that time there has been a growing awareness of the need
for the control and removal of organic and inorganic contaminants from potable drinking water supplies.
At the time of the passage of the SDWA of 1974, there were more than 12,000 chemical compounds
known to be in commercial use. Many of these synthetic compounds are finding their way into potable
water sources and ultimately into finished drinking water.
Within the past decade, several hundred specific organic chemicals have been identified in minute
amounts in various drinking water supplies in the United States and abroad. Although at the present
time the specific cause(s) of cancer are little understood, many of these commercially used organic
compounds have been found to cause both acute and chronic adverse health effects in humans at
various exposure levels. Therefore, in order to minimize risks to human health, the exposure levels to
these compounds must be reduced to the lowest level possible that is both technologically and
economically feasible.
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The chronic health hazards associated with the presence of SOCs in drinking water have become a
major concern of United States governmental agencies in more recent times. Consequently,
contamination of potable water by SOCs is a significant national problem. Phase II and V of the
SDWA have promulgated MCLs for 32 SOCs, of which 15 have been identified as carcinogenic.
Appendix A lists the MCL, source of contamination and potential health effects for each regulated
SOC. In addition, Appendix B lists the 46 SOCs proposed in the Drinking Water Regulations and
Health Advisories and the Federal Register to be considered for regulation (USEPA 1996, 1997).
4.2 SOC Removal by Membrane Processes
This ETV Testing Plan is applicable to any pressure-driven membrane process used to achieve removal
of SOCs. Furthermore, this testing plan is applicable to spiral-wound (SW) and hollow-fiber (HF)
membrane configurations.
Membrane processes have been shown to be highly effective for the removal of SOCs. However,
removal is a function of membrane mass transfer coefficients (MTCs), flux, recovery and feed
concentration and will be expected to vary by membrane type. RO is also effective in producing a
better overall quality of water.
Some advantages to the use of membrane processes for the removal of SOCs include:
a small space requirement;
removal of contaminant ions, dissolved solids, bacteria, and particles; and
relative insensitivity to flow and IDS levels, and low effluent concentration.
Disadvantages include:
higher capital and operating costs;
higher level of pretreatment required;
possible membrane fouling; and
large reject streams.
Pressure-driven membrane processes are currently in use for a broad number of water treatment
applications including the removal of pesticides and herbicides (i.e. SOCs), natural organic matter
(NOM) which contributes to disinfection by-product formation, dissolved minerals, radionuclides and
microbial contaminants such as Giardia and Cryptosporidium. Typically, higher pressure membrane
applications such as nanofiltration (NF) and reverse osmosis (RO) are capable of removing SOCs, as
well as ions contributing to hardness.
In contrast, low-pressure membrane processes, such as microfiltration (MF) and ultrafiltration (UF) are
typically employed to provide a physical barrier for removal of microbial and particulate contaminants
from drinking waters. However, the MF and UF membrane processes have not been shown to be
effective for removal of SOCs unless another unit operation such as granular activated or powdered
activated carbon is employed.
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Suppliers of drinking water are subject to stringent government regulations for potable water quality
regarding allowable pesticide and herbicide (i.e. SOCs) concentrations. In particular, European
standards require less than 0.1 |j,g/L for any one particular pesticide or herbicide and no greater than
0.5 |j,g/L for total pesticides and herbicides in drinking water. Many investigators have shown that
RO/NF are effective techniques for pesticide and herbicide removal (Duranceau 1992, Camp 1995,
Takigawa et.al. 1995, and Kruithof et.al. 1995). However, specific mechanisms underlying SOC
rejection are largely unknown. In the paragraphs to follow, results from published accounts of pesticide
reduction and the inferences regarding suspected mechanisms for removal are presented.
It has been demonstrated that membrane processes are effective for SOC removal (Duranceau and
Taylor 1992, and Hofman et.al. 1993). However the mechanisms for SOC removal are still under
investigation and are a subject of research. Intensive research efforts have investigated the associated
rejection mechanisms for various pesticides and herbicides. Included among these mechanisms are:
size exclusion,
steric hindrance (shape)
electrostatic repulsion
adsorption
matrix effects
In general, uncharged pesticide and herbicide rejection by RO/NF has been observed to decrease with
decreasing molecular size (i.e. molecular weight or molecular cross-sectional area) (Kruithof et.al 1995,
Chen et.al 1997, and Berg and Gimbel 1997). Since molecular weight and molecular cross-sectional
area are not always directly related, distinguishing between these two parameters is an important
consideration for determination of a size exclusion rejection mechanism for uncharged SOCs (Berg and
Gimbel 1997).
A study where NF treatability of a mixture of Elbe River (Germany) water and ground water with high
sulfate and hardness content spiked with trace amounts of several SOCs (Cfeed ~ 1 pig/L) was conducted
with both flat-sheet membrane films and spiral wound elements. Simazine, atrazine, terbutylazine,
diuron, metazachlorine, TCA, and mecoprop composed the pesticide "cocktail" with which the surface
water was spiked. Rejection of uncharged species terbutylazine, atrazine and simazine were reported to
be in order of increasing size (Berg and Gimbel 1997). With the only difference between these species
being the number of methyl groups, terbutylazine, with three methyl groups, was the highest rejected.
Atrazine being the next largest in size was better rejected than simazine. Charged organic species were
found to be significantly more rejected (predominately >85% for all membranes) by the negatively
charged membranes than the polar SOCs despite substantial size differences. However, a combination
of both electrostatic repulsion and size was suspected to influence rejection as demonstrated by higher
rejection of the SOC mecoprop as compared to its smaller charged counterpart TCA. By adjusting the
feed pH to 3, added insight was provided by analyzing the rejections of mecoprop in its dissociated and
undissociated form. These results showed greater rejection for the dissociated form of mecoprop. The
rejection of the undissociated form was less than in its dissociated form and was comparable to the
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rejection of uncharged diuron, which suggested a removal mechanism for these non-polar species to be
that of steric hindrance.
Additional flat-sheet testing has been performed to evaluate the effects of matrix conditions upon
pesticide rejection as applied to different membrane polymers. Reported evaluations (Chen et.al. 1997)
have demonstrated general pesticide rejection in order of highest to lowest by membrane film to be
polyamide, amine, and cellulose acetate based polymers. This conclusion resulted from an overall
assessment of pesticides commonly used in both the U.S and Europe and their rejection in separate
distilled, inorganic, organic and inorganic-organic matrices. These pesticides included simazine, atrazine,
cyanazine, bentazone, diuron, DNOC, pirimicarb, metamitron, metribuzin, MCPA, mecoprop, and
vinchlozolin at feed concentrations of approximately 10 |_ig/L. These investigators also demonstrated
that solvent properties, inorganic versus organic in particular, did not have a large influence upon SOC
rejection. The order of pesticide rejection by matrix listed in order of increasing to decreasing rejection
of pesticides was reported to be inorganics, organics, distilled water and combination of inorganic and
organic. Among all four matrices, overall rejection varied by less than 10%. While the flat-sheet film
tests were able to detect significant performance differences among cellulose acetate versus thin-film
composite membranes, "finite differences (using similar types of membranes) were not detected using
cell tests because of variations in membrane films due to manufacturing or analytical limitations."
SOC removal has also been the focus of attention for several Dutch Utilities. The PWN Water Supply
Company of North Holland has studied cellulose acetate membrane polymers as applied to surface
water for over 15 years (Camp 1995). Joint research between PWN and KIWA has shown thin-film
composite (TFC) membranes to have better rejection properties than cellulose acetate (CA)
membranes, but have the disadvantage of being more prone to fouling when surface water sources are
used. As a single barrier, CA membranes were demonstrated to be inadequate for pesticide removal
and they recommend granular activated carbon (GAC) post treatment (Kruithof et.al. 1995). However,
at PWN, TFC membranes were shown to reject 90 to 95% of applied pesticide cocktails while CA
membranes offered, as expected, less rejection of the SOCs. Moreover, chlorophenols were removed
25 to 90%) with CA membranes. Experiments conducted in Leiduin, the Netherlands also showed
significant pesticide rejection. Using a 4-2-1 array equipped with six 4" single elements, Toray SU 710
L type membranes achieved 97 to greater than 99% rejection for all pesticides except 2,4
dichlorophenol (50%) and diuron (87%). Specifically, the highly rejected SOCs in this mixture were
atrazine (99%), bentazone (>99%), DNOC (97%), and isoproturon (97%) with feed concentrations
ranging from 5.1 to 6.3 |J,g/L. Bench-scale experiments conducted at PWN, which compared
Hydranautics CPA2 and Toray SU 710 L, revealed comparable pesticide rejection for the two
composite membranes. The least rejected SOCs were diuron and simazine of the trace concentration
SOC mixture that included atrazine, bentazone, and DNOC. Fbwever, each individual SOC was
rejected at or greater than 96% by both membranes except for diuron as treated by the Toray SU 710
L single element.
4.3 Membrane System Design Considerations
Conventional NF or RO membrane systems consist of pretreatment, membrane processing and post-
treatment. These processes are discussed in the following sections.
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4.3.1 Pretreatment
The purpose of pretreatment is to control and minimize membrane fouling and reduce flux
decline. The conventional pretreatment process consists of scale inhibitor (anti-sealant) and/or
acid addition in combination with microfiltration. These pretreatment process are used to
control scaling and protect the membrane elements; they are required for conventional RO or
NF membrane systems. The membranes can be fouled or scaled during operation. Fouling is
caused by particulate materials such as colloids and organics that are present in the raw water
attaching to the membrane surface, and will reduce the productivity of the membrane. Scaling is
caused by the precipitation of a sparingly soluble salt within the membrane because of the solute
concentration exceeding solubility. If a raw water is excessively fouling, additional or advanced
pretreatment is required.
Flux decline indicated by a reduction in membrane process productivity can be a result of
scaling, colloidal fouling, microbiological fouling and organic chemical fouling. Scaling can be
approximated by chemical analysis and equilibrium calculations. Fouling indices can
approximate colloidal fouling. Microbiological and organic chemical fouling can only be
approximated at this time by pilot testing. These mechanisms should be recognized and
understood, and are presented below in order to develop strategies to control flux decline.
4.3.1.1 Scaling. In an RO/NF membrane process, salts present in the feedwater are
concentrated on the feed side of the membrane. This concentration process continues until
saturation and salt precipitation (scaling) occurs. Scaling will reduce membrane productivity,
and consequently, will limit the rate of water that may be recovered as permeate on a sustained
basis. The maximum recovery is the recovery at which the limiting salt first begins to precipitate.
Limiting salts can be identified from the solubility products of potential limiting salts in the raw
feedwater. Since ionic strength increases on the feed side of the membrane, the effect of ionic
strength upon the solubility products must also be considered and taken into account for these
calculations. Some limiting salts may be controlled via the addition of acid or scale inhibitor or
both to the feedwater prior to membrane treatment. Typical sparingly soluble salts that may
limit recovery in pressure-driven membrane processes include, but are not limited to, CaC03,
CaS04, BaS04, SrS04, CaF2 and Si02.
As the feedwater passes through the membrane element from the feed side to the concentrate
end of the membrane system, and the permeate water is removed, the feedwater salts become
more concentrated. For instance, in a 75% recovery membrane system, the concentrate
contains almost four times the concentration of salts that were present in the feedwater. This is
called concentration polarization. Concentration polarization is the term used to describe 1he
increased salt concentration that occurs at the surface of the membrane elements. As the
permeate water passes through the membrane, the concentration of the rejected salts build up
on the high-pressure side of the membrane surface. The amount of increased salt concentration
over the bulk stream depends on how quickly the salts diffuse back into the bulk stream.
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A high salt concentration at the membrane surface results in an increase in salt passage through
the membrane. The increase in local salt concentration can lead to saturation of solution
components resulting in precipitation on the membrane surface.
4.3.1.2 Colloidal Fouling. Colloidal fouling results from particles that exist in the influent
which buildup on the surface of the membrane. The build-up forms a cake, which eventually is
compressed and reduces flow through the membrane. Initially, cake formation does not
significantly reduce productivity. However, after the cake compresses, the productivity
decreases and the compressed cake must be removed. MF or UF membranes can be
backwashed to remove the cake. However, spiral-wound RO and NF membranes require
chemical cleaning to remove the cake. Advanced pretreatment processes such as cross-flow
MF and multi-media filtration should control colloidal fouling.
4.3.1.3 Microbiological Fouling. Microbiological fouling results from biological growth in
the membrane element, which results in a reduction in membrane productivity or an increase in
pressure drop through an element. No reliable methods have been demonstrated for prediction
of biofouling. Microbiological growth can occur in the feed spacers or on the membrane
surface. Microbiological growth will occur in membranes but this growth does not always result
in significant productivity loss. Advanced pretreatment processes may aid in the control of
microbiological fouling.
4.3.1.4 Chemical Fouling. Chemical fouling results from the interaction of dissolved
solutes in the feed stream with the membrane surface, which results in a reduction in membrane
productivity. Chemical interaction between solute and the membrane surface will occur to some
degree, but membrane productivity may not be reduced. Advanced pretreatment processes
may aid in the control of chemical fouling.
4.3.2 Advanced Pretreatment
Advanced pretreatment would include unit operations that precede scaling control and cartridge
filtration. By definition, unit operations that precede conventional pretreatment would be
advanced pretreatment. Examples of advanced pretreatment would be
coagulation/flocculation/sedimentation, oxidation followed by greensand filtration, continuous
cross-flow microfiltration, multi-media filtration, and granular activated carbon (GAC) filtration.
4.3.3 Membrane Processes
The membrane process follows pretreatment. The majority of dissolved contaminants are
removed in the membrane process. If the membrane scales or fouls, the productivity of the
membrane system declines and eventually the membranes must be chemically cleaned to restore
productivity. Cleaning frequencies for RO or NF systems average about 6 months when
treating ground waters (Taylor et.al. 1990) and can be as low as 1 to 2 weeks when treating
surface water with integrated membrane systems (IMSs).
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UF or MF membranes as a stand alone process cannot remove SOCs. However, powdered
activated carbon (PAC) can used for SOC adsorption followed by UF or MF to remove the
PAC from the flow stream. MF and UF membranes are sieving controlled and do not have a
low enough molecular weight cut-off (MWCO) range to reject many of the known SOCs or
inorganic compounds (IOCs). RO and NF membranes can achieve significant SOC rejection
because the MWCO of these membranes are low and many SOCs cannot pass (Duranceau
1992). This is also the case with IOCs and radionuclides. Although RO and NF have been
shown to be among the most promising processes for SOC and IOC removal, not all SOCs or
IOCs are rejected by these processes. RO and NF membranes use both sieving and diffusion
mechanisms to reject SOCs and IOCs from drinking water and rejection will increase as the
MW and charge of the contaminant increases. Typically, charged solutes and solutes with
MWCOs greater than 200 mg/mmol are highly rejected by RO and NF.
UF and MF membranes do not affect corrosivity because inorganic ions are not removed;
however, RO and NF do remove inorganic solutes from water, and this can impact the
corrosivity of the permeate water.
4.3.4 Post-Treatment
Typical post-treatment unit operations can consist of disinfection, aeration, stabilization and
storage. Aeration may be required to strip dissolved gases (Duranceau 1993). Stabilization
may be required to produce a non-corrosive finished water since membrane permeate can be
corrosive. Alkalinity recovery is an effective process for recovering dissolved inorganic carbon
(DIC) in the permeate. Alkalinity can be recovered by lowering the pH prior to membrane
filtration converting the alkalinity to C02, and then raising the pH of the permeate in a closed
system to recover dissolved C02 as alkalinity. Bypassing feedwater and blending it with
membrane permeate is another way of stabilizing the finished water; however, blending would
negate the benefit of the membrane treatment system to act as a physical barrier against
microbial contaminants.
4.3.5 Waste Disposal
In addition to post treatment, the concentrate stream from the membrane processes must be
treated and/or disposed of in some manner. Although membrane processes are at present often
technically and economically well suited to produce drinking water, the disposal of membrane
concentrate will become more difficult and more expensive because of increased regulation.
Effective concentrate disposal methods depend on the concentrate water quality, local
regulations and site-specific factors (AWWARF 1993). The handling and disposal of the
wastes generated by treatment technologies removing SOCs from drinking water pose concerns
to the water supplier, to local and State governments and to the public at large. The potential
handling hazards associated with SOCs warrant the development of a viable membrane
concentrate disposal method. Information regarding concentrate disposal options can be found
in Membrane Concentrate Disposal (AWWARF 1993). The document investigates the
application of regulations to the disposal of membrane concentrate. The document first
addresses membrane concentrate and its characteristics, including the definitions and natures of
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the wastes that are being generated. Then the disposal methods that are being regulated are
addressed, including descriptions of how to dispose of the concentrate. Finally, the regulations
and permits that apply to the various disposal options are addressed. The following are
disposal options that must be approved by the State or local government prior to
implementation of a waste disposal program.
Liquid Waste Disposal
Direct discharge into storm sewers or surface water.
Discharge into sanitary sewer.
Deep well injection.
Drying or chemical precipitation.
Solid Waste Disposal
Temporary lagooning (surface impoundment).
Disposal in landfill.
Disposal without prior treatment.
a) With prior temporary lagooning.
b) With prior mechanical dewatering.
c) Application to land (soil spreading/conditioning).
Disposal at State licensed waste facility.
5.0 DEFINITION OF OPERATIONAL PARAMETERS
The following terms are presented here for subsequent reference in this test plan:
Array - An array is the series flow stream configuration of pressure vessels through a train defined by
stages (4:2:1 array).
Bulk Rejection - Percent solute concentration retained by the membrane relative to the bulk stream
concentration. 1 -
Cf
where:
Cf = feedwater concentration of specific constituent (mg/L)
Cp = permeate concentration of specific constituent (mg/L)
Bulk Solution - The solution on the high-pressure side of the membrane that has a water quality
between that of the influent and concentrate streams.
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Cleaning Frequency - The loss or decrease of the mass transfer coefficient (MTC) for water
measures membrane productivity over time of production. Membranes foul during operation. Constant
production is achieved in membrane plants by increasing pressure. Cleaning is done when the pressure
increases by 10 to 15 percent. Cleaning frequency (CF) and a measurement of productivity can be
determined from the MTC decline.
CF = OK'"
dK
dt
where:
CF = cleaning frequency (days)
Q = acceptable rate of MTC loss
dKw/dt = rate of MTC decline (gsfd/psi-d)
Concentrate (Q G) - One of the membrane output streams that has a more concentrated water
quality than the feed stream.
Conventional RO/NF Process - A treatment system consisting of acid and/or scale inhibitor addition
for scale control, cartridge filtration, RO/NF membrane filtration, aeration, chlorination and corrosion
control.
Feed (Qf, Cf) - Input stream to the membrane process after pretreatment.
Feedwater- Water introduced to the membrane module.
Field Testing Organization (FDO) - An organization qualified to conduct studies and testing of
drinking water treatment systems in accordance with protocols and test plans. The role of the field
testing organization is to complete the application on behalf of the Company; to enter into contracts with
NSF, as discussed herein; and arrange for a conduct the skilled operation of equipment during the
intense periods of testing during the study and the tasks required by the Protocol.
Flux (Fw) - Mass (lb/ft2-day) or volume (gal/ft2-day, gsfd, gfd) rate of transfer through membrane
surface.
Fw = Kw [AP - An] = %
A
where:
Fw = water flux (M/L2-t)
Kw = global water mass transfer coefficient (t )
2
AP = transmembrane pressure gradient (M/L )
2
All = osmotic pressure gradient (M/L )
3
Qp = permeate flow (L /t)
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A = membrane surface area (L )
Fouling - Reduction of productivity measured by a decrease in the temperature normalized water
MTC.
Fouling Indices - Fouling indices are simple measurements that provide an estimate of the required
pretreatment for membrane processes. Fouling indices are determined from membrane tests and are
similar to mass transfer coefficients for membranes used to produce drinking water. Fouling indices can
be quickly developed from simple filtration tests, are used to qualitatively estimate pretreatment
requirements and possibly could be used to predict membrane fouling. The silt-density index (SDI),
modified fouling index (MFI) and mini plugging factor index (MPFI) are the most common fouling
indices. The SDI, MFI and the MPFI are defined using the basic resistance model, and are
quantitatively related to water quality and NF membrane fouling.
Some approximations for required indices prior to conventional membrane treatment are given below
(Sung et. al. 1994).
Fouling Index
Range
SDI
<3
MFI
< 10 s/L2
Silt-Density Index (SDI): The SDI is the most commonly used test to predict a water's potential to
foul a membrane by colloidal particles smaller than 0.45 microns. SDI is only a guide for
pretreatment and is not an indication of adequate pretreatment. The SDI is a static measurement of
resistance, which is determined by samples taken at the beginning and the end of the test. The SDI
test is performed by timing the anaerobic hydraulic flow through a 47 mm diameter, 0.45 micron
membrane filter at a constant pressure of 30 psi. The time required for 500 mL of the feedwater to
pass through the filter is measured when the test is first initiated, and is also measured at time
intervals of 5, 10, and 15 minutes after the start of the test. The value of the SDI is then calculated
as follows (ASTM D-4189-82).
SDI =
tf
tT
(ioo%)
where:
t. = time to collect initial 500 mL sample
tf = time to collect 500 mL sample at time t = T
tT = total running time of the test; 5, 10, or 15 minutes.
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If the index is below a value of 3 then the water should be suitable for reverse osmosis. If the SDI
is below 3, the impact of colloidal fouling is minimized.
Modified Fouling Index (MFI): The MFI is determined using the same equipment and procedure
used for the SDI, except that the volume is recorded every 30 seconds over a 15 minute filtration
period (Schippers and Verdouw 1980). The development of the MFI is consistent with Darcy's
Law in that the thickness of the cake layer formed on the membrane surface is assumed to be
directly proportional to the filtrate volume. The total resistance is the sum of the filter and cake
resistance. The MFI is defined graphically as the slope of an inverse flow verses cumulative volume
curve as shown in the following equations:
dV AP A
dt \i (Rf+Rk)
|iVRf nV2I
APA 2APA2
= (a + MFl)v
Q
where:
Rf = resistance of the filter
Rk = resistance of the cake
I = measure of the fouling potential
Q = average flow (liters/second)
a = constant
Typically the cake formation, build-up and compaction or failure can be seen in three distinct
regions on a MFI plot. The regions corresponding to blocking filtration and cake filtration represent
productive operation, whereas compaction would be indicative of the end of a productive cycle.
Hollow-Fiber - Fine hollow fibers of membrane material are extruded in either a cellulose triacetate or
a polyamide. The ends of the fibers are sealed in an epoxy bock connected with the outside of the
housing. The epoxy block is cut to allow the flow from the inside of the fine fibers to the other side of
the epoxy block, where it is collected. The pressurized feedwater passes across the outside of the
fibers. Pure water permeates the fibers and is collected at the end of the element.
The hollow-fiber housings are capable of holding a large quantity of fibers, this allowing a single element
to produce a large permeate flow rate. Hollow-fiber elements are typically used for seawater
desalination, and for brackish-water applications
Influent - Input stream to the membrane array after the recycle stream has been blended with the feed
stream. If there is no concentrate recycle then the feed and influent streams are identical.
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Mass Transfer Coefficient (MTC) (Kw) - Mass or volume unit transfer through membrane based on
Q
driving force (gfd/psi). Kw = 5
A(? P - ? ? )
where:
. -i
Kw = global water mass transfer coefficient (t )
2S
AP = transmembrane pressure gradient (M/L )
2
AIT = osmotic pressure gradient (M/L )
3 ,
Qp = permeate flow (L /t)
2_
A = membrane surface area (L )
Membrane Element - A single membrane unit containing a bound group of spiral wound or hollow-
fiber membranes to provide a nominal surface area for treatment.
Membrane Molecular Weight Cutoff Determination - The membrane molecular weight cutoff
(MWCO) of membranes a commonly used to characterize membrane rejection capability. Membrane
MWCO is typically determined by measuring the rejection of different molecular weight nonionic
polymers. Solute rejection is defined as:
( C ^
% Solute Rejection = 1 (l 00%)
v Cf J
Given the narrow molecular weight bands of polyethylene glycol (PEG) solutions, these nonionic
random coil polymers can be applied to membranes for MWCO estimation. Although the percent PEG
rejection varies by manufacturer, 80 to 90 percent PEG rejection has been used. Neither the percent
rejection nor the material is fixed except by membrane manufacturer. The standard molecular weight
solutions can be measured as TOC and correlated to PEG concentration. This correlation can then be
applied for assessment of PEG rejection by the membrane and subsequent MWCO determination.
Membrane Productivity - Membrane productivity will be assessed by the rate of mass transfer
coefficient (MTCW) decline over time of operation. As flux declines, a constant product can be
achieved by increasing pressure to maintain a constant flux.
Net Driving Pressure (NDP): The net driving pressure (NDP) is calculated using the influent,
concentrate and permeate pressure.
NDP =
(p,+p.)
-P -??
p
where:
NDP = net driving pressure for solvent transport across the membrane (psi, bar)
Pf = feedwater pressure to the feed side of the membrane (psi, bar)
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Pc = concentrate pressure on the reject side of the membrane (psi, bar)
Pp = permeate pressure on the treated water side of the membrane (psi, bar)
A7i = osmotic pressure (psi)
Osmotic Pressure Gradient (An):: The term osmotic pressure gradient refers to the difference in
osmotic pressure generated across the membrane barrier as a result of different concentrations of
dissolved salts. In order to determine the NDP, the osmotic pressure gradient must be estimated
from the influent, concentrate and permeate IDS.
?? =
(lDSf +TDSJ
-IDS.
lpsi
v L
where:
TDSf = feedwater total dissolved solids (IDS) concentration (mg/L)
TDSC = concentrate IDS concentration (mg/L)
TDSp = permeate TDS concentration (mg/L)
Mass Transfer Coefficient (MTCW): The MTCW is calculated by dividing the permeate flow by the
membrane surface area.
F. =% = (MTCw)NDP)
A
From this the MTCW can be calculated. However, given the relationship between temperature and
the viscosity of water, flux should be normalized to a standard temperature condition (25ฐC).
These relationships should be provided by the membrane manufacturer and used to normalize the
flux data set as shown below.
F .
MTC . = w-25 c
w'25 c NDP
Temperature Adjustment for Flux Calculation: If manufacture does not specify a temperature
correction equation the following equation may be used so that water production can be compared
on an equivalent basis.
F . =F . (l.03(25ฐc-rc))
w, 25 C w, T C \ /
Recovery: Recovery should also be calculated using the permeate and influent flow.
r = ^l
Qi
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Using the above equations the MTCW, normalized flux and recovery for each stage and the system can
be calculated for each set of operational data and plotted as a function of cumulative operating time.
Package Plant - A complete water treatment system including all components from the connection to
the raw water(s) intake through discharge to the distribution system.
Permeate (Qp, Cp) - The membrane output stream that has convected through the membrane.
QpCp = QfCf - QcCc
Permeate - Water produced by the membrane process.
Permeate Flux - The average permeate flux is the flow of permeate divided by the surface area of the
membrane. Permeate flux is calculated according to the following formula:
1,=^
S
where:
Jt = permeate flux at time t (gfd, L/(h-m2))
Qp = permeate flow (gpd, L/h)
S = membrane surface area (ft2, m2)
It should be noted that only gfd and L/(h-m2) shall be considered acceptable units of flux for this testing
plan.
Pressure Vessel - A single tube or housing that contains several membrane elements in series.
Product-Specific Test Plan (PSTP) - A written document of procedures for on-site/in-line testing,
sample collection, preservation, and shipment and other on-site activities described in the EPA/NSF
ETV Protocol(s) and Test Plan(s) that apply to a specific make and model of equipment.
Raw - Input stream to the membrane process prior to any pretreatment.
Recovery - The recovery of feedwater as permeate water is given as the ratio of permeate flow to
Qp
feedwater flow: % System Recovery =
where:
Qf
(100%)
Qf = feedwater flow to the membrane (gpm, L/h)
Qp = permeate flow (gpm, L/h)
Recycle Ratio (r) - The recycle ratio represents the ratio of the total flow of water that is used for
cross-flow and the net feedwater flow to the membrane. This ratio provides an idea of the recirculation
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pumping that is applied to the membrane system to reduce membrane fouling and specific flux decline.
Qr
Recycle Ratio =
where:
Qf
Qf = feedwater flow to the membrane (gpm, L/h)
Qr = recycle hydraulic flow in the membrane element (gpm, L/h)
Rejection (mass) - The mass of a specific solute entering a membrane system that does not pass
through the membrane.
( O C ^
v QfCf j
Scaling Control - Controlling precipitation or scaling within the membrane element requires
identification of a limiting salt, acid addition for prevention of CaC03 and/or addition of a scale inhibitor.
The limiting salt determines the amount of scale inhibitor or acid addition. A diffusion controlled
membrane process will concentrate salts on the feed side of the membrane. If excessive water is
passed through the membrane, this concentration process will continue until a salt precipitates and
scaling occurs. Scaling will reduce membrane productivity and consequently recovery is limited by the
allowable recovery just before the limiting salt precipitates. The limiting salt can be determined from the
solubility products of potential limiting salts and the actual feed stream water quality. Ionic strength must
also be considered in these calculations as the natural concentration of the feed stream during the
membrane process increases the ionic strength, allowable solubility and recovery.
Calcium carbonate scaling is commonly controlled by sulfuric acid addition however sulfate salts are
often the limiting salts. Commercially available scale inhibitors can be used to control scaling by
complexing the metal ions in the feed stream and preventing precipitation. Equilibrium constants for
these scale inhibitors are not available which prevents direct calculation. However some manufacturers
provide computer programs for estimating the required scale inhibitor dose for a given recovery, water
quality and membrane. The following are general equations for the solubility products and ionic strength
approximations.
Solubility Product: Calculation of the solubility product of selected sparingly soluble salts will be
important exercise for the test plan in order to determine if there are operational limitations caused
by the accumulation of limiting salts at the membrane surface. Text book equilibrium values of the
solubility product should be compared with solubility values calculated from the results of
experimental Verification Testing, as determined from use of the following equation:
i- V I |u I
sp
where:
Ksp = solubility product for the limiting salt being considered
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y = free ion activity coefficient for the ion considered (i.e., A or B)
[A] = molal solution concentration of the anion A for sparingly soluble salt AXBV
[B] = solution concentration of the anion B
x, y = stiochiometric coefficients for the precipitation reaction of A and B
Mean Activity Coefficient: The mean activity coefficients for each of the salt constituents may be
estimated for the concentrated solutions as a function of the ionic strength:
log?A,B =-0.509ZaZbVm"
where:
y = free ion activity coefficient for the ion considered (i.e., A or B)
ZA = ion charge of anion A
ZB = ion charge of cation B
\x = ionic strength
Ionic Strength: A simple approximation of the ionic strength can calculated based upon the
concentration of the total dissolved solids in the feedwater stream:
|i = (2.5-KT5)(TDS)
where:
\x = ionic strength
TDS = total dissolved solids concentration (mg/L)
Solute - The dissolved constituent (mg/L) in a solution or process stream.
Solute Rejection - Solute rejection is controlled by a number of operational variables that must be
reported at the time of water sample collection. Bulk rejection of a targeted inorganic chemical
contaminant may be calculated by the following equation.
cf-cp
cf
(100%)
% Solute Rejection =
where:
Cf = feedwater concentration of specific constituent (mg/L)
Cp = permeate concentration of specific constituent (mg/L)
Solvent - A substance, usually a liquid such as water, capable of dissolving other substances.
Solvent and Solute Mass Balance - Calculation of solvent mass balance is performed to verify the
reliability of flow measurements through the membrane. Calculation of solute mass balance across the
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membrane system is performed to estimate the concentration of limiting salts at the membrane surface.
Qf = Qp + Qc
QfCf = QpCp + QcCc
where:
Qf = feedwater flow to the membrane (gpm, L/h)
Qp = permeate flow (gpm, L/h)
Qc = concentrate flow (gpm, L/h)
Cf = feedwater concentration of specific constituent (mg/L)
Cp = permeate concentration of specific constituent (mg/L)
Cf = concentrate concentration of specific constituent (mg/L)
Specific Flux - At the conclusion of each chemical cleaning event and upon return to membrane
operation, the initial condition of transmembrane pressure shall be recorded and the specific flux
calculated. The efficiency of chemical cleaning shall be evaluated by the recovery of specific flux after
chemical cleaning as noted below, with comparison drawn from the cleaning efficiency achieved during
previous cleaning evaluations. Comparison between chemical cleanings shall allow an evaluation of
irreversible fouling. Two primary indicators of cleaning efficiency and restoration of membrane
productivity will be examined in this task.
Percent Recovery of Specific Flux: The immediate recovery of membrane productivity, as
expressed by the ratio between the final specific flux (Fsf) and the initial specific flux (Fsi) measured
for the subsequent run.
% Re cov ery of Specific Flux =
1-5l
(100%)
where:
Fsf = Specific flux (gfd/psi, L/(h-m2)/bar) at end of run (final)
Fsi = Specific flux (gfd/psi, L/(h-m2)/bar) at beginning of run (initial).
Percent Loss of Original Specific Flux: The loss of original specific flux capabilities, as expressed
by the ratio between the initial specific flux for any given filtration run (Fsi) divided by the original
specific flux (Fsio), as measured at the initiation of the first filtration run in a series.
% Loss of Original Specific Flux =
(100%)
Spiral-Wound - Spiral-wound membrane elements are constructed of flat sheet membranes folded and
glued on three edges to create several membrane envelopes. The open edge of the each envelope is
glued to a central collection pipe with perforations to allow water from inside the envelope to pass into
the pipe. The envelopes are spun around the central collection pipe. Layered inside each envelope is a
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thin layer of fabric that prevents the envelope from sealing itself off when the outside of the envelope is
exposed to high pressure. The fabric allows the passage of permeate water to the center collection tube.
The feed water enters the end of the spiral-wound element and moves across the surface of the rolled-
up membrane envelopes. Spacers between the envelopes promote turbulence so that pure water
permeates the envelopes, any salts left behind will diffuse back into the bulk solution. Inside the
envelope the pressure is near atmospheric, whereas the pressure on the feedwater side can be as high
as 1,000 psi. The pressure differential drives the pure water into the membrane envelope. In the
envelope the permeate passes through fabric material and finds its way into the central collection pipe.
The water in the collection pipe travels to the end where it either enters the collection tube of another
element, or is transferred to the permeate port of the end cap of the housing.
Stage - A stage is the configuration of an array.
Train - A train is a parallel flow stream through the membrane system. For instance a 5 MGD
membrane system may be comprised of five 1 MGD trains.
Verification Statement - A written document that summarizes a final report reviewed and approved
by NSF on behalf of the USEPA or directly by the USEPA.
Water System - The water system that operates using water treatment equipment to provide potable
water to its customers.
6.0 OVERVIEW OF TASKS
This Plan is applicable to the testing of water treatment equipment utilizing membrane processes.
Testing of membrane processes will be conducted by a NSF-qualified Field Testing Organization that is
selected by the Manufacturer. Water quality analyses will be performed by a state-certified or third
party-, or EPA-qualified analytical laboratory. This Plan provides objectives, work plans, schedules,
and evaluation criteria for the required tasks associated with the equipment testing procedure.
The following is a brief overview of the tasks that shall be included as components of the Verification
Testing Program and PSTP for removal of SOCs.
Task 1: Characterization of Raw Water - Obtain chemical, biological and physical
characterization of the raw water. Provide a brief description of the watershed that provides the
raw water to the water treatment plant.
Task 2: Membrane Productivity - Demonstrate operational conditions for the membrane
equipment; permeate water recovery achieved by the membrane equipment; and rate of flux decline
observed over an extended membrane process operation.
Task 3: Finished Water Quality - Evaluate the water quality produced by membrane processes
as it relates to raw water quality and operational conditions.
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Task 4: Cleaning Efficiency - Evaluate the effectiveness of chemical cleaning to the membrane
system and confirm that the Manufacturer-recommended cleaning practices are sufficient to restore
membrane productivity.
Task 5: Operations and Maintenance (O&M) - Develop an O&M manual for each system
submitted. The O&M manual shall characterize membrane process design, outline a membrane
process cleaning procedure or procedures, and provide a concentrate disposal plan.
Task 6: Data Collection and Management - Establish an effective field protocol for data
management between the Field Testing Organization and NSF.
Task 7: Quality Assurance / Quality Control (QA/QC) - Develop a QA/QC protocol for
Verification Testing. This is an important item that will assist in obtaining an accurate measurement
of operational and water quality parameters during membrane equipment Verification Testing.
Task 8: Cost Evaluation - Develop capital and O&M costs for the submitted NF membrane
technology and equipment.
7.0 TESTING PERIODS
The required tasks of the ETV Testing Plan (Tasks 1 through 9) are designed to be completed over a
60-day period, not including mobilization, shakedown and start-up. The schedule for equipment
monitoring during the 60-day testing period shall be stipulated by the FTO in the PSTP, and shall meet
or exceed the minimum monitoring requirements of this testing plan. The FTO shall ensure in the PSTP
that sufficient water quality data and operational data will be collected to allow estimation of statistical
uncertainty in the Verification Testing data, as described in the "EPA/NSF ETV Protocol For
Equipment Verification Testing For The Removal Of Synthetic Organic Chemical Contaminants:
Requirements For All Studies". The FTO shall therefore ensure that sufficient water quality and
operational data is collected during Verification Testing for the statistical analysis described herein.
For membrane process treatment equipment, factors that can influence treatment performance include:
Feedwaters with high seasonal concentrations of inorganic constituents and TDS. These
conditions may increase finished water concentrations of inorganic chemical contaminants
and may promote precipitation of inorganic materials in the membrane;
Feedwaters with variable pH; increases in feedwater pH may increase the tendency for
precipitation of sparingly soluble salts in the membrane module and may require variable
strategies in anti-sealant addition and pH adjustment;
Cold water, encountered in winter or at high altitude locations;
High concentrations of natural organic matter (measured as TOC), which may be higher in
some waters during different seasonal periods;
High turbidity, often occurring in spring, as a result of high runoff resulting from heavy rains
or snowmelt.
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It is highly unlikely that all of the above problems would occur in a water source during a single 60-day
period during the Verification Testing Program. Membrane testing conducted beyond the required 60-
day testing may be used for fine-tuning of membrane performance or for evaluation of additional
operational conditions. During the testing periods, evaluation of cleaning efficiency and finished water
quality can be performed concurrent with membrane operation testing procedures.
During the time intervals between equipment verification runs, the water treatment equipment may be
used for production of potable water. If the equipment is being used for the production of potable
water, routine operation for water production is expected. The operating and water quality data
collected and furnished to the local regulatory agency should also be supplied to the NSF-qualified
8.0 TASK 1: CHARACTERIZATION OF RAW WATER
8.1 Introduction
A characterization of raw water quality is needed to determine if the concentrations of SOCs or other
raw water contaminants are appropriate for the use of NF membrane processes. The feedwater quality
can influence the performance of the equipment as well as the usefulness of testing results to readers of
the verification report.
8.2 Objectives
One reason for performing a raw water characterization is to obtain at least one-year of historical raw
water quality data from the raw water source. The objective is to:
demonstrate seasonal effects on the concentration of SOCs; and
develop maximum and minimum concentrations for the contaminant.
If historical raw water quality is not available, a raw water quality analysis of the proposed feedwater
shall be performed prior to equipment Verification Testing.
8.3 Work Plan
The characterization of raw water quality is best accomplished through the performance of laboratory
testing and the review of historical records. Sources for historical records may include municipalities,
laboratories, USGS (United States Geographical Survey), USEPA, and local regulatory agencies. If
historical records are not available preliminary raw water quality testing shall be performed prior to
equipment Verification Testing. The specific parameters of characterization will depend on the NF
membrane process that is being tested. The following characteristics should be reviewed and
documented:
FTO.
Specific SOC
Temperature
True Color
Chloride
Nitrate
Sodium
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PH
TDS/Conductivity
Total Hardness
Calcium Hardness
Fluoride
Potassium
Sulfate
Strontium
Ammonia
Phosphate
Iron
SDI
Total Organic Carbon
Total Alkalinity
Turbidity
Manganese
Silica
Barium
MFI
Data collected should reflect seasonal variations in the above data if applicable. This will determine
variations in water quality parameters that will occur during Verification Testing. The data that is
collected will be shared with NSF so that the FTO can determine the significance of the data for use in
developing a test plan. If the raw water source is not characterized, the testing program may fail, or
results of a testing program may not be considered acceptable. A description of the raw water source
should also be included with the feedwater characterization. The description may include items such as:
size of watershed;
topography;
land use;
nature of the water source; and
potential sources of pollution.
8.4 Schedule
The schedule for compilation of adequate water quality data will be determined by the availability and
accessibility of historical data. The historical water quality data can be used to determine the suitability
of NF membrane processes for the treatment for the raw source water. If raw water quality data is not
available, a preliminary raw water quality testing should be performed prior to the Verification Testing of
the NF membrane equipment.
8.5 Evaluation Criteria
The feedwater quality shall be evaluated in the context of the Manufacturer's Statement of Performance
Objectives for the removal of SOCs. The feedwater should challenge the capabilities of the chosen
equipment, but should not be beyond the range of water quality suitable for treatment by the chosen
equipment. For NF membrane processes, a complete scan of water quality parameters may be
required in order to determine limiting salt concentrations, necessary for establishing pretreatment
criteria.
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9.0 TASK 2: MEMBRANE PRODUCTIVITY
9.1 Introduction
The removal of SOCs from drinking water supplies is accomplished by NF membrane filtration. The
effectiveness of NF membrane processes for SOC removal will be evaluated in this task. Membrane
mass transfer coefficient, flux and recovery will be evaluated in this task. After installation of a NF
membrane, compaction and ripening of the membrane will cause a characteristic flux decline with time
until the membrane stabilizes. After this initial flux decline, the rate of flux decline will be used to
demonstrate membrane performance for the specific operating conditions to be verified. The
operational conditions to be verified shall be specified by the Manufacturer in terms of a temperature-
corrected flux (normalized flux) value (e.g., gsfd at 77ฐF or L/(m2hr) at 25ฐC) before the initiation of the
Program.
Flux decline is a function of water quality, membrane type, configuration and operational conditions. In
establishing the range of operation for the membrane performance evaluations, limiting salt information
should be used to define the run scenarios. The run conditions should include operating scenarios,
which approach and exceed these projected limits. Subsequent water quality analysis will allow for
assessment of the degree of saturation of the sparingly soluble salts in the final concentrate. The degree
of saturation of the salts should then be compared to resulting membrane productivity decline. Table
9.1 presents an example of membrane pretreatment data required to provide baseline conditions and
assist in evaluating membrane productivity.
Some Manufacturers may wish to employ the NF membrane process with a pretreatment process in
order to reduce flux decline and improve removal of SOCs. Any pretreatment included in the
membrane treatment system that is designed for removal of SOCs shall be considered an integral part of
the membrane treatment system and shall not be tested independently. In such cases, the system shall
be considered as a single unit and the pretreatment process shall not be separated for optional
evaluation purposes.
9.2 Experimental Objectives
The objectives of this task are to demonstrate:
Operational conditions for the membrane equipment;
Permeate water recovery achieved by the membrane equipment; and
Rate of flux decline observed over extended membrane process operation.
Raw water quality shall be measured prior to system operation and then monitored every two weeks
during the 60-day testing period at a minimum. It should be noted that the objective of this task is not
process optimization, but rather verification of membrane operation at the operating conditions specified
by the Manufacturer, as it pertains to permeate flux and transmembrane pressure, and SOC removal.
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9.3 Work Plan
Determination of ideal membrane operating conditions for a particular water may require as long as one
year of operation. For this task the Manufacturer shall specify the operating conditions to be evaluated
in this Verification Testing Plan and shall supply written procedures on the operation and maintenance of
the membrane treatment system. The Manufacturer shall evaluate flux decline. The Manufacturer shall
also determine the limiting salt and identify possible foulants and sealants, and use this for performance
evaluation for their particular membrane equipment. The set of operating conditions shall be maintained
for the 60-day testing period (24-hour continuous operation). The Manufacturer shall specify the
primary permeate flux at which the equipment is to be verified. Additional operating conditions can be
verified in separate 60-day testing periods.
After set-up and "shakedown" of membrane equipment, membrane operation should be established at
the flux condition to be verified. Testing of additional operational conditions could be performed by
extending the number of 60-day testing periods beyond the initial 60-day period required by the
Verification Testing Program at the discretion of the Manufacturer and their designated FTO.
Additional 60-day periods of testing may also be included in the Verification Testing Plan in order to
demonstrate membrane performance under different feedwater quality conditions. For membrane
processes, extremes of feedwater quality (e.g., low temperature, high TOC concentration, variable
SOC concentrations, high SDI and high turbidity) are the conditions under which membranes are most
prone to fouling and subsequent failure. At a minimum the performance of the NF membrane equipment
relative to SOC removal shall be documented during those periods of variable feedwater conditions.
The Manufacturer shall perform testing with as many different water quality conditions as desired for
verification status. Testing under each different water quality condition shall be performed during an
additional 60-day testing period, as required above for each additional set of operating conditions.
The testing runs conducted under this task shall be performed in conjunction with finished water quality
and if applicable, cleaning efficiency. With the exception of additional testing periods conducted at the
Manufacturer's discretion, no additional membrane test runs are required for performance of cleaning
efficiency and finished water quality. A continuous yearlong evaluation, although not required, may be
of benefit to the Manufacturer for verification of long term trends.
9.3.1 Operational Data Collection
Measurement of membrane feedwater flow and permeate flow (recycle flow where applicable)
and system pressures shall be collected at a minimum of 3 eight-hour shifts per day. Table 9.2 is
an example of a daily operational data sheet for a two-stage membrane system. This table is
presented for informational purposes only. Figure 9.1 presents the sample locations for the
daily operational data sheet. The actual forms will be submitted as part of the test plan and may
be site-specific. Measurement of feedwater temperature to the membranes shall be made along
with these three daily measurements in order to provide data for normalizing flux with respect to
temperature
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Water quality should be analyzed from the same locations identified for IDS in Table 9.2 prior
to start-up and then twice a month for the parameters identified in Table 9.3, except for each
SOC, which will be monitored weekly. Power costs for operation of the membrane equipment
(pumping requirements, chemical usage, etc.) shall also be closely monitored and recorded by
FTO during the 60-day testing period. Power usage shall be estimated by inclusion of the
following details regarding equipment operation requirements: pumping requirements; size of
pumps; name-plate; voltage; current draw; power factor; peak usage; etc. In addition,
measurement of power consumption and chemical consumption shall be quantified by recording
such items as day tank concentration, daily volume consumption and unit cost of chemicals.
9.3.2 Feedwater Quality Limitations
The characteristics of feedwaters used during the 60-day testing period (and any additional 60-
day testing periods) shall be explicitly stated in reporting the membrane flux and recovery data
for each period. Accurate reporting of such feedwater characteristics are critical for the
Verification Testing Program, as these parameters can substantially influence the range of
achievable membrane performance and treated water quality under variable raw water quality
conditions. The following criteria and trends should also be presented in the Verification Testing
Program:
Evaluation criteria and minimum reporting requirements.
Plot graph of SOC removed over time for each 30-day period of operation.
Plot graph of NDP over time for each 30-day period of operation.
Plot graph of IDS over time for each 30-day period of operation.
Plot graph of Fw25ฐc over time for each 30-day period of operation.
Plot graph of MTCW over time for each 30-day period of operation.
Plot graph of recovery over time for each 30-day period of operation.
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TABLE 9.1: NF Membrane Pretreatment Data
Foulants and Fouling Indices of the Feedwater Prior to Pretreatment
Alkalinity (mg/L of CaC03)
Ca Hardness (mg/L of CaCCh)
LSI
Dissolved iron (mg/L)
Total iron (mg/L)
Dissolved aluminum (mg/L)
Total aluminum (mg/L)
Fluoride (mg/L)
Phosphate (mg/L)
Sulfate (mg/L)
Calcium (mg/L)
Barium (mg/L)
Strontium (mg/L)
Reactive silica (mg/L as Si02)
Turbidity (NTU)
SDI
Pretreatment Processes Used Prior to Nanofiltration or Reverse Osmosis
Pre-filter listed pore size (|_im)
Type of acid used
Acid concentration (units)
mL of acid per L of feed
Type of scale inhibitor used
Scale inhibitor concentration (units)
mL of scale inhibitor per L of feed
Type of coagulant used
Coagulant dose (mg/L)
Type of polymer used during coagulation.
Polymer dose (mg/L)
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TABLE 9.2: Daily Operations Log Sheet for a Two-Stage Membrane System
Date:
Parameter
Shift 1
Shift 2
Shift 3
Time
Initial
Feed
Qfeed (gpm)
TDSfeed (before pretreatment) (mg/L)
TDSfeed (after pretreatment) (mg/L)
Pfeed(psi)
pHfeed (before pretreatment)
pHfeed (after pretreatment)
Tfeed (ฐC)
Permeate - Stage 1
Qp-si (gpm)
TDSp-Si (mg/L)
Pp-si (psi)
Concentrate - Stage 1
Qc-si (gpm)
TDSc.si (mg/L)
Pc-si (psi)
Tc-si (ฐC)
Permeate - Stage 2
Qp-S2 (gpm)
TDSp_s2 (mg/L)
PP-s2 (psi)
Concentrate - Stage 2
Qc-s2 (gpm)
TDSc_s2 (mg/L)
Pc-S2 (psi)
Finished
Qfin (gpm)
TDSfm (mg/L)
Recovery (Qfm/Qfeed) (%)
Recycle
Q recycle (gpm)
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FIGURE 9.1: Sample Locations for a Two-Stage Membrane Process
Feed
(before)
Feed
(after)
Stage 1
S1-Permeate
Finished
Pretreatmen
Stage 2
S1-Concentrate
S2-Permeate
S2-Concentrate
Recycle (optional^
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TABLE 9.3: Operating and Water Quality Data Requirements for Membrane Processes
Parameter
Frequency and Importance for
Sampling
Feedwater Flow
3 * Daily (1)
Permeate Water Flow
3 * Daily (1)
Concentrate Water Flow
3 * Daily (1)
Feedwater Pressure
3 * Daily (1)
Permeate Water Pressure
3 * Daily (1)
Concentrate Water Pressure
3 * Daily (1)
List Each Chemical Used, And Dosage
Daily Data Or Monthly Average (1)
Hours Operated Per Day
Daily (1)
Hours Operator Present Per Day
Monthly Average (2)
Power Costs (Kwh/Million Gallons)
Monthly (2)
Independent check on rates of flow
Weekly (1)
Independent check on pressure gages
Weekly (2)
Verification of chemical dosages
Monthly (1)
SOCs
1, Weekly
Temperature
3 * Daily (1)
pH
3 * Daily (1)
TDS/Conductivity
3 * Daily (1)
Turbidity
Every two weeks (1)
True Color
Every two weeks (1)
Total Organic Carbon
Every two weeks (1)
UV Absorbance (254 nm)
Every two weeks (1)
Total Alkalinity
Every two weeks (1)
Total Hardness
Every two weeks (1)
Calcium Hardness
Every two weeks (1)
Sodium
Every two weeks (1)
Chloride
Every two weeks (1)
Iron
Every two weeks (1)
Manganese
Every two weeks (1)
Sulfate
Every two weeks (1)
Fluoride
Every two weeks (1)
Silica
Every two weeks (1)
Ammonia
Every two weeks (1)
Potassium
Every two weeks (1)
Strontium
Every two weeks (1)
Barium
Every two weeks (1)
Nitrate
Every two weeks (1)
TTHM
Every two weeks (2)
THAA
Every two weeks (2)
TOX
Every two weeks (2)
1 = Required 2 = Desired But Not Necessary
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10.0 TASK 3: FINISHED WATER QUALTIY
10.1 Introduction
Water quality data shall be collected for the raw and finished water as provided previously in Table 9.3.
(Note, in some instances sampling concentrate water quality may be required because detection limits
may be too low for a specified parameter.) At a minimum, the required sampling shall be one sampling
at start-up and two sampling events per month while raw water samples are collected. Water quality
goals and target removal goals for the membrane equipment should be proved and reported in the
PSTP.
10.2 Objectives
The objective of this task is to verily the Manufacturer's performance objectives. Table 9.3 presented a
list of the minimum number of water quality parameters to be monitored during equipment Verification
Testing has been provided in this document. The actual water quality parameters selected for testing
and monitoring shall be stipulated in the PSTP.
10.3 Work Plan
The PSTP shall identify the treated water quality objectives to be achieved in the Statement of
Performance Objectives of the equipment to be evaluated in the Verification Testing Program. The
PSTP shall also identify in the Statement of Performance Objectives the specific SOCs that shall be
monitored during equipment testing. The Statement of Performance Objectives prepared by the PSTP
shall indicate the range of water qualities and operating conditions under which the equipment can be
challenged while successfully treating the contaminated water supply.
It should be noted that many of the drinking water treatment systems participating in the SOC Removal
Verification Testing Program will be capable of achieving multiple water treatment objectives. Although
the SOC Verification Testing Plan is oriented towards removal of SOCs, the Manufacturer may want to
look at the treatment system's removal capabilities for additional water quality parameters.
Many of the water quality parameters described in this task shall be measured on-site by the NSF-
qualified FTO. A state-certified or third-party- or EPA-qualified analytical laboratory shall perform
analysis of the remaining water quality parameters. Representative methods to be used for measurement
of water quality parameters in the field and lab are identified in Table 10.1. The analytical methods
utilized in this study for on-site monitoring of raw and finished water qualities are described in Quality
Assurance/ Quality Control (QA/QC). Where appropriate, the Standard Methods reference numbers
and EPA method numbers for water quality parameters are provided for both the field and laboratory
analytical procedures.
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TABLE 10.1: Water Quality Analytical Methods
Parameter
Standard Method 1
EPA Method 2
Phase II SOCs
2,4,5-TP (Silvex)
6640 B
515.1; 515.2; 555
2,4-D (Formula 40, Weedar 64)
6640 B
515.1; 515.2; 555
Acrylamide
Alachlor (Lasso)
505; 507; 525.2; 508.1
Aldicarb
6610 B
531.1
Aldicarb sulfone
6610 B
531.1
Aldicarb sulfoxide
6610 B
531.1
Atrazine
505; 507; 508.1; 525.2
Carbofuran (Furdan 4F)
6610 B
531.1
Chlordane
6410B; 6630 B,C
505; 508; 508.1; 525.2
Dibromochloropropane (DBCP, Nemafume))
6210 C,D; 6230D; 6231 B
504.1; 551
Ethylene dibromide (EDB, Bromofume)
504.1; 551
Heptachlor (H-34, Heptox)
6410B; 6630 B, C
505; 508; 508.1; 525.2
Heptachlor epoxide
6410B; 6630 B, C
505; 508; 508.1; 525.2
Lindane
6630 B
505; 508; 508.1; 525.2
Methoxychlor (DMDT, Marlate)
6630 B
505; 508; 508.1; 525.2
Pentachlorophenol
6410B; 6420 B; 6640B
515.1; 515.2; 525.2; 555
Polychlorinated biphenyls (PCBs, Aroclor)
6410B; 6630 C
505; 508; 508A
Toxaphene
6410 B; 6630 B, C
505; 508; 525.2
Phase V SOCs
Adipate (diethylhexyl)
506; 525.2
Dalapon
6640 B
515.1; 552.1
Dichloromethane
Dinoseb
6640 B
515.1; 515.2; 555
Dioxin
1613
Diquat
549.1
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TABLE 10.1: Water Quality Analytical Methods (Cont.)
Parameter
Standard Method 1
EPA Method 2
Endothall
548.1
Endrin
6410 B; 6630 B, C
505; 508; 508.1; 525.2
Glyphosate
6651 B
547
Hexachlorobenzene
6040B; 6410B
505; 508; 508.1; 525.2
Hexachlorocyclopentadiene
6410 B
505; 508; 508.1; 525.2
Oxamyl (Vydate)
6610 B
531.1
Phathalate
506; 525.2
Phenanthrene (PAH)
6040B; 6410 B; 6440B
525.1; 550; 550.1
Picloram
6640 B
515.1; 515.2; 555
Simazine
505; 507; 508.1; 525.2
Trichlorobenzene (1,2,4-)
6040 B; 6210 D; 6220 C; 6230
D; 6410B
Trichloroethane (1,1,2,-)
6040 B; 6210 B, C, D; 6220
C; 6230 B, C, D
Physical Parameters
Temperature
2550 B
pH
4500-lT B
150.1; 150.2
Conductivity
2510 B
120.1
Total Dissolved Solids
2540 C
Total Suspended Solids
2540 D
Turbidity
2130 B; Method 2
180.1
Dissolved Oxygen
4500-0 B
Organics
True color
2120 B
Total Organic Carbon
5310 C
UV254 absorbance
5910 B
Total Trihalomethanes (TTHMs)
6232 B
524.3
Total Haloacetic Acids (THAAs)
6251 B
552.1
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TABLE 10.1: Water Quality Analytical Methods (Cont.)
Parameter
Standard Method 1
EPA Method 2
Total Organic Halogens (TOX)
5320 B
Inorganics
Total Alkalinity
2320 B
Total Hardness
2340 C
Calcium Hardness
3500-Ca+2 D
Sodium
3111 B
200.7
Chloride
4110 B; 4500-C1" D
300.0
Iron
3111 D; 3113 B; 3120B
200.7; 200.8; 200.9
Manganese
3111 D; 3113 B; 3120B
200.7; 200.8; 200.9
Sulfate
4110 B; 4500-S04"2 C, D, F
300.0; 375.2
Fluoride
4110 B; 4500-F" B, C, D, E
300.0
Silica (total and dissolved)
3120 B; 4500-Si D, E, F
200.7
Ammonia, NH3
4500-NHs B, C, D
350.3
Potassium
3111 B; 3500-K C, D, E
200.7
Strontium
3111 B; 3500-Sr C,D,E
200.7
Barium
3111 D; 3113 B; 3120B
200.7; 200.8
Nitrate
4110 B; 45OO-NO3" D, F
300.0; 353.2
1) AWWA, Standard Methods for the Examination of Water and Wastewater, 20th Edition, 1999.
2) EPA, Methods and Guidance for Analysis of Water, EPA 82 l-C-97-001, April 1997.
For the water qaality parameters requiring analysis at an off-site laboratory, water samples shall be
collected in appropriate containers (containing necessary preservatives as applicable) prepared by the
state-certified or third-party- or EPA-qualified laboratory. These samples shall be preserved, stored,
shipped and analyzed in accordance with appropriate procedures and holding times, including chain-of
custody requirements, as specified by the analytical lab.
10.4 Analytical Schedule
10.4.1 Removal of SOCs
During the steady-state operation of each membrane testing period, SOC mass balances shall
be performed on the membrane feed, permeate and concentrate water in order to determine the
SOC removal capabilities of the membrane system.
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10.4.2 Feed and Permeate Water Characterization
At the beginning of each membrane testing period, the raw water, permeate and in some cases
concentrate water shall be characterized at a single set of operating conditions by measurement
of the water quality parameters identified in Table 9.3.
10.4.3 Water Quality Sample Collection
Water quality data shall be collected at regular intervals during each period of membrane
equipment testing. The minimum monitoring frequency for the required water quality parameters
is once at start-up and weekly for SOCs and every two weeks for the remaining water quality
parameters. The water quality sampling program may be expanded to include a greater number
of water quality parameters and to require a greater frequency of parameter sampling. Analyses
for organic water quality parameters shall be performed on water sample aliquots that were
obtained simultaneously from the same sampling location, in order to provide the maximum
degree of comparability between water quality analytes.
No monitoring of microbial populations shall be required in this Equipment Verification Testing
Plan. However, the Manufacturer may include optional monitoring of indigenous microbial
populations to demonstrate removal capabilities.
10.4.4 Raw Water Quality Limitations
The characteristics of feedwaters encountered during each 60-day testing period shall be
explicitly stated. Accurate reporting of such raw water characteristics such as those identified in
Table 9.3 are critical for the Verification Testing Program, as these parameters can substantially
influence membrane performance.
10.5 Evaluation Criteria and Minimum Reporting Requirements
Removal or reduction of SOCs.
Water quality and removal goals specified by the Manufacturer.
11.0 TASK 4: CLEANING EFFICIENCY
11.1 Introduction
There are certain types of foulant scales that pose an immediate threat to the operational integrity of a
membrane process. Examples of scale include calcium carbonate scale and silica or sulfate scale.
Should scaling or fouling occur during or following the test runs, the membrane equipment shall require
chemical cleaning to restore membrane productivity. The number of cleaning efficiency evaluations shall
be determined by the fouling frequency of the membrane during each specified test period. In the case
where the membrane does not fully reach the operational criteria for fouling as specified by the
Manufacturer, chemical cleaning shall be performed after the 30 days of operation, with a record made
of the operational conditions before and after cleaning.
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The membrane treatment process will be optimized for sustained production under high product water
recovery and solvent flux. Productivity goals shall be stated in the PSTP in terms of productivity decline
and/or operational time.
Either normalized flux decline or solvent mass transfer (MTCw) reduction will determine productivity
decline. The use of the normalized MTCW for productivity decline would eliminate the need for constant
system pressure for productivity decline determination. Chemical cleaning of the membranes will be
performed as necessary for the removal of reversible foulants per Manufacturer specifications. These
cleaning events are to be documented and used as an aid in determining the nature of the fouling or
scaling conditions experienced by the system. The cleaning solutions should also be analyzed to
determine which constituents may have adsorbed or precipitated onto the membrane surface during
cleaning. This may also prove useful for establishing the mechanism of removal for some SOCs.
11.2 Experimental Objectives
The objective of this task is to evaluate the effectiveness of chemical cleaning to the membrane systems.
The intent of this task is to confirm that standard Manufacturer-recommended cleaning practices are
sufficient to restore membrane productivity for the systems under consideration. Cleaning chemicals and
cleaning routines shall be based on the Manufacturer recommendations. This task is considered a
"proof of concept" effort, not an optimization effort.
11.3 Work Plan
The membrane systems may become fouled during the membrane test runs. These fouled membranes
shall be utilized for the cleaning assessments herein. Each system shall be chemically cleaned using the
recommended cleaning solutions and procedures specified by the Manufacturer, which will vary
according to identified foulants or scale. After each chemical cleaning of the membranes, the system
shall be restarted and then returned to the flux condition being tested.
The Manufacturer shall specify in detail the procedure(s) for chemical cleaning of the membranes. At a
minimum, the following shall be specified:
cleaning chemicals
quantities and costs of cleaning chemicals
hydraulic conditions of cleaning
duration of each cleaning step
chemical cleaning solution
quantity and characteristics of residual waste volume to be disposed
11.4 Recommended Disposal Procedures
Methods of disposal of membrane concentrate include, but are limited to the following:
Public works wastewater plant;
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Deep well injection; or
Discharge to a surface water with accordance to the National Pollutant Discharge
Elimination System (NPDES) Program.
However SOCs are considered a potentially hazardous waste and the effluent must be monitored since
it is concentrated. The concentrate disposal may require other State and/or Federal permits. In
addition, a description of all cleaning equipment and its operation shall be described and included in the
O&M manual.
11.5 Analytical Schedule
11.5.1 Sampling
The pH of each cleaning solution shall be determined and recorded during various periods of the
chemical cleaning procedure. Conductivity and turbidity should also be used to monitor flush
periods.
11.5.2 Operational Data Collection
Flow and pressure data shall be collected before system shutdown due to membrane fouling;
flow and pressure data shall also be collected after chemical cleaning.
12.0TASK5: OPERATIONS AND MAINTENANCE MANUAL
An operations and maintenance (O&M) manual for the membrane system to be tested for SOC
removal shall be included in the Verification Testing evaluation.
12.1 Objectives
The objective of this task is to provide an O&M manual that will assist in operating, troubleshooting and
maintaining the membrane system performance. The O&M manual shall:
characterize the membrane process design;
outline a membrane process cleaning procedure or procedures; and
provide a concentrate disposal plan.
The concentrate disposal plan must be approved by the State in question for permanent installation. A
fully developed concentrate disposal plan would be required because of the SOCs that have been
concentrated in the waste stream. Criteria for evaluation of the equipment's O&M Manual shall be
compiled and then evaluated and commented upon during verification by the FTO. An example is
provided in Table 12.1.
Each specific test plan will include a list of criteria for evaluating O&M information. This shall be
compiled and submitted for evaluation by EPA, NSF and technical peer reviewers. An example is
provided in Table 12.2. The purpose of this O&M information is to allow utilities to effectively choose
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a technology that their operators are capable of operating, and provide information on how many hours
the operators can be expected to work on the system. Information about obtaining replacement parts
and ease of operation of the system would also be valuable.
TABLE 12.1: OPERATIONS & MAINTENANCE MANUAL CRITERIA -
NF Membrane Process Systems
MAINTENANCE:
The manufacturer should provide readily understood information on the recommended or required
maintenance schedule for each piece of operating equipment such as:
flow meters
pressure gauges
pumps
motors
valves
chemical feeders
mixers
The manufacturer should provide readily understood information on the recommended or required
maintenance for non-mechanical or non-electrical equipment such as:
membranes
pressure vessels
* piping
OPERATION:
The manufacturer should provide readily understood recommendation for procedures related to proper
operation of the equipment. Among the operating aspects that should be discussed are:
Chemical feeders:
calibration check
settings and adjustments - how they should be made
dilution of chemicals and scale inhibitors - proper procedures
Monitoring and observing operation:
mass balance calculations
recovery calculation
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TABLE 12.1: OPERATIONS & MAINTENANCE MANUAL CRITERIA -
NF Membrane Process Systems (continued)
OPERATION (continued):
Monitoring and observing operation (continued):
pressure losses
The manufacturer should provide a troubleshooting guide; a simple check-list of what to do for a variety of
problems including:
flux decline;
no raw water (feedwater) flow to plant;
when the water flow rate through the equipment can not be measured;
no chemical feed;
automatic operation (if provided) not functioning;
no electric power; and
sand or silt entrainment (such as plugging of prefilters).
The following are recommendations regarding operability aspects of membrane processes. These aspects
of plant operation should be included if possible in reviews of historical data, and should be included to the
extent practical in reports of equipment testing when the testing is done under the ETV Program. During
Verification Testing and during compilation of historical equipment operating data, attention shall be given to
equipment operability aspects.
are chemical feed pumps calibrated?
are flow meters present and have they been calibrated?
are pressure gauges calibrated?
are pH meters calibrated?
are IDS or conductivity meters calibrated?
can cleaning be done automatically?
can membrane seals be easily replaced?
does remote notification occur (alarm) when pressure increases > 15% or flow drops > 15%?
The reports on Verification Testing should address the above questions in the written reports. The issues of operability should be dealt with
in the portion of the reports that are written in response to Operating Conditions and Treatment Equipment Performance, in the
Membrane Process Test Plan.
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TABLE 12.2: Requirements for Maintenance and Operability of
NF Membrane Process Systems
MAINTENANCE INFORMATION
Equipment
Maintenance Frequency
Replacement Frequency
Membranes
Pumps
Valves
Motors
Mixers
chemical mixers
water meters
pressure gauges
cartridge filters
Seals
Piping
OPERABILITY INFORMATION: (rank from 1 (easy) to 3 (difficult), or N/A)
Operation Aspect
Response
Chemical feed pumps calibration
Flow meters calibration
Pressure gauges calibration
pH meters calibration
IDS or conductivity meters calibration
Cleaning
Replacement of membrane seals
Measurement and control of flux decline
Notes:
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12.2 O&M Work Plan
Descriptions for pretreatment, membrane process, and post-treatment to characterize the membrane
system unit process design shall be developed. Membrane processes shall include the design criteria
and membrane element characteristics. Examples of information required relative to the membrane
design criteria and element characteristics are presented in Tables 12.3 and 12.4, respectively.
TABLE 12.3: NF Membrane Plant Design Criteria Reporting Items
Parameter
Value
Number of trains
Number of stages
Stage configuration
Number of pressure vessels in stage 1
Number of pressure vessels in stage 2
Number of elements per pressure vessel
Recovery per stage (%)
Recovery for system (%)
Design flow (gpm)
Design temperature (ฐC)
Design flux (gsfd)
Surface area per element (ft2)
MTCw (gsfd/psi)
Maximum flow rate to an element (gpm)
Mnimum flow rate to an element (gpm)
Pressure loss per element (psi)
Pressure loss in stage entrance and exit (psi)
Feed stream TDS (mg/L)
SOC rejection (%) *
* Specify SOC name(s), chemical and trade name(s).
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TABLE 12.4: NF Membrane Element Characteristics
Membrane manufacturer
Membrane module model number
Size of element used in study (e.g. 4" x 40")
Active membrane area of element used in study
Active membrane area of an equivalent 8" x 40"
element
Purchase price for an equivalent 8" x 40"
element ($)
Molecular weight cutoff (Daltons)
Membrane material / construction
Membrane hydrophobicity (circle one)
Hydrophilic Hydrophobic
Membrane charge (circle one)
Negative Neutral Positive
Design pressure (psi)
Design flux at the design pressure (gfd)
Variability of design flux (%)
MTCw (gfd/psi)
Standard testing recovery (%)
Standard testing pH
Standard testing temperature (ฐC)
Design cross-flow velocity (fps)
Maximum flow rate to the element (gpm)
Minimum flow rate to the element (gpm)
Required feed flow to permeate flow rate ratio
Maximum element recovery (%)
Rejection of reference solute and conditions of
test (e.g. solute type and concentration)
Variability of rejection of reference solute (%)
Spacer thickness (ft)
Scroll width (ft)
Acceptable range of operating pressures
Acceptable range of operating pH values
Typical pressure drop across a single element
Maximum permissible SDI
Maximum permissible turbidity (NTU)
Chlorine/oxidant tolerance
Suggested cleaning procedures
Note: Some of this information may not be available, but this table should be filled out as completely as possible for
each membrane tested.
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The membrane treatment process will be optimized for sustained production under high product water
recovery and solvent flux. Productivity goals shall be stated in the PSTP.
Productivity decline will be indicated and signaled by either normalized flux decline or normalized
solvent mass transfer (MTCW) reduction. Normalized means that the flux has been adjusted for
temperature and pressure. The use of the normalized MTCW for productivity decline would eliminate
the need for constant system pressure for productivity decline determination.
Chemical cleaning of the membranes will be performed as necessary for the removal of reversible
foulants per manufacturer specifications. These cleaning events are to be documented and used as an
aid in determining the nature of the fouling or scaling conditions experienced by the system. The
cleaning solutions could also be analyzed for determining which constituents may have adsorbed or
precipitated onto the membrane surface. Analysis of cleaning solutions can be coupled with mass
balances on the same solutes monitored during operation to determine solute accrual in membrane
elements. This may prove useful for establishing the mechanism of removal for some SOCs. A cleaning
efficiency evaluation is described in Section 11.0.
The potential handling hazards associated with SOCs warrant the development of a -viable membrane
concentrate disposal method and safety program. Provisions for concentrate disposal from the system
must be developed as part of the work plan.
13.0 TASK 6: DATA COLLECTION AND MANAGEMENT
13.1 Introduction
The data management system used in the Verification Testing Program shall involve the use of computer
spreadsheets, in addition to manual recording of operational parameters for the membrane processes on
a daily basis.
13.2 Objectives
The objective of this task is to establish a viable structure for the recording and transmission of field
testing data such that the FTO provides sufficient and reliable operational data for verification purposes.
Chain-of-Custody protocols will be developed and adhered to.
13.3 Work Plan
13.3.1 Data Handling Work Plan
The following protocol has been developed for data handling and data verification by the FTO.
In addition to daily operational data sheets, a Supervisory Control and Data Acquisition
(SCADA) system could be used for automatic entry of testing data into computer databases.
Specific parcels of the computer database for operational and water quality parameters should
then be downloaded by manual importation into electronic spreadsheets. These specific
database parcels shall be identified based upon discrete time spans and monitoring parameters.
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In spreadsheet form, the data shall be manipulated into a convenient framework to allow
analysis of membrane process operation. At a minimum, backup of the computer databases to
diskette should be performed on a monthly basis.
Field testing operators shall record data and calculations by hand in laboratory notebooks for
three eight-hour shifts per day. (Daily measurements shall be recorded on specially prepared
data log sheets as appropriate. Table 9.2 presents an example of a daily log sheet). The
laboratory notebook shall provide copies of each page. The original notebooks shall be stored
on-site; the copied sheets shall be forwarded to the project engineer of the FTO at least once
per week during the 60-day testing period. This protocol will not only ease referencing the
original data, but offer protection of the original record of results. Operating logs shall include
descriptions of the and test runs;
names of visitors; and
descriptions of any problems.
Such descriptions shall be provided in addition to experimental calculations and other items.
13.3.2 Data Management
The database for the project shall be set up in the form of custom designed spreadsheets. The
spreadsheets shall be 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 field laboratory analysis notebooks and data log sheets shall be entered into the
appropriate spreadsheet. Data entry shall be conducted on-site by the designated field testing
operators. All recorded calculations shall also be checked at this time.
Following data entry, the spreadsheet shall be printed and the printout shall be checked against
the handwritten data sheet. Any corrections shall be noted on the hardcopies and corrected on
the screen, and then the corrected recorded calculations will also be checked and confirmed.
The field testing operator or engineer performing the data entry or verification step shall initial
each step of the verification process.
Each experiment (e.g. each membrane process test run) shall be assigned a run number, which
will then be tied to the data from that experiment through each step of data entry and analysis.
As samples are collected and sent to state-certified or third-party- or EPA-qualified
laboratories, the data shall be tracked by use of the same system of run numbers. Data from the
outside laboratories shall be received and reviewed by the FTO. These data shall be entered
into the data spreadsheets, corrected, and verified in the same manner as the field data.
13.3.3 Statistical Analysis
For the analytical data obtained during Verification Testing, 95 percent confidence intervals shall
be calculated by the FTO for selected water quality parameters. The specific Plans shall specify
which water quality parameters shall be subjected to the requirements of confidence interval
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calculation. As the name implies, a confidence interval describes a population range in which
any individual population measurement may exist with a specified percent confidence. When
presenting the data, maximum, minimum, average and standard deviation should be included.
Calculation of confidence intervals shall not be required for equipment performance obtained
during the equipment Verification Testing Program. In order to provide sufficient analytical data
for statistical analysis, the FTO shall collect three discrete water samples at one set of
operational conditions for each of the specified water quality parameters during a designated
testing period.
14.0 TASK 7: QUALTIY ASSURANCE/ QUALITY CONTROL
14.1 Introduction
Quality assurance and quality control (QAQC) of the operation of the membrane process equipment
and the measured water quality parameters shall be maintained during the Equipment Verification
Testing Program.
14.2 Experimental Objectives
The objective of this task is to maintain strict QA/QC methods and procedures during the Equipment
Verification Testing Program. Maintenance of strict QA/QC procedures is important, in that if a
question arises when analyzing or interpreting data collected for a given experiment, it will be possible to
verify exact conditions at the time of testing.
14.3 QA/QC Work Plan
Equipment flow rates should be calibrated and verified and verification recorded on a routine basis. A
routine daily walk through during testing shall be established to check that each piece of equipment or
instrumentation is operating properly. Particular care shall be taken to verify that chemicals are being
fed at the defined flow rate, and into a flow stream that is operating at the expected flow rate. This will
provide correct chemical concentrations in the flow stream. In-line monitoring equipment such as flow
meters, etc. shall be checked as indicated below to verify that the readout matches with the actual
measurement (i.e. flow rate) and that the signal being recorded is correct. The items listed are in
addition to any specified checks outlined in the analytical methods.
When collecting water quantity data, all system flow meters will be calibrated using the classic bucket
and stopwatch method where appropriate. Hydraulic data collection will include the measurement of
the finished water flow rate by the "bucket test" method. This would consist of filling a calibrated vessel
to a known volume and measuring the time to fill the vessel with a stopwatch. This will allow for a direct
check of the system flow measuring devices.
Mass balances will be performed on the system for water quality parameters measured in the feed,
permeate and concentrate streams. This will enable an additional quality control check on the accuracy
and reliability of the analyzed data. SOCs in particular will be analyzed in each process stream.
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However, the difficulty in measuring some low level SOCs may limit the mass balance to be calculated
based on feed and concentrate. Mass balances may provide insight into the mechanism for rejection of
individual SOCs. For example, mass balances showing incomplete recovery for a particular SOC may
suggest possible adsorption onto the membrane surface.
14.3.1 Daily QA/QC Verifications
Chemical feed pump flow rates (check and verify components)
On-line conductivity meters (check and verify components)
On-line pH meters (standardize and recalibrate)
On-line turbidimeter flowrates (verified volumetrically over a specific period of time)
On-line turbidimeter readings checked against a properly calibrated bench model
14.3.2 QA/QC Verifications Performed Every Two Weeks
Chemical feed pump flow rates (verify volumetrically over a specific time period)
On-line conductivity meters (recalibrate)
On-line flow meters/rotameters (clean equipment to remove any debris or biological buildup
and verify flow volumetrically to avoid erroneous readings)
14.3.3 QA/QC Verifications Performed Every Testing Period
Differential pressure transmitters (verify gauge readings and electrical signal using a pressure
meter)
Tubing (verify good condition of all tubing and connections, replace if necessary)
14.4 On-Site Analytical Methods
Use of either bench-top field analytical equipment will be acceptable for the Verification Testing;
however, on-line equipment is recommended for ease of operation. Use of on-line equipment is also
preferable because it reduces the introduction of error and the variability of analytical results generated
by inconsistent sampling techniques. However, standard and uniform calibration and standardization
techniques that are approved should be employed. Table 10.1 lists Standard Methods and EPA
methods of analysis.
14.4.1 pH
Analysis for pH shall be performed according to Standard Method 4500-H . A three-point
calibration of the pH meter used in this study will be performed once per day when the
instrument is in use. Certified pH buffers in the expected range shall be used. The pH probe
shall be stored in the appropriate solution defined in the instrument manual. Transport of carbon
dioxide across the air-water interface can confound pH measurement in poorly buffered waters.
Therefore, measure the pH under a continuous stream of sample by placing the tip of the probe
in the sample container allowing the sample to overflow the container while the probe reaches
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equilibrium. If this is a problem, measurement of pH in a confined vessel is recommended to
minimize the effects of carbon dioxide loss with the atmosphere.
14.4.2 Turbidity
Turbidity analyses shall be performed according to Standard Method 2130 or EPA Method
180.1 with either a bench-top or in-line turbidimeter. Grab samples shall be analyzed using a
bench-top turbidimeter; readings from this instrument will serve as reference measurements
throughout the study. The bench-top turbidimeter shall be calibrated within the expected range
of sample measurements at the beginning of Verification Testing and on a weekly basis using
primary turbidity standards of 0.1, 0.5 and 3.0 NTU. Secondary turbidity standards shall be
used on a daily basis to verify calibration of the turbidimeter and to recalibrate when more than
one turbidity range is used.
During each verification testing period, the bench-top and in-line turbidimeters will be left on
continuously. Once each turbidity measurement is complete, the unit will be switched back to
its lowest setting. All glassware used for turbidity measurements will be cleaned and handled
using lint-free tissues to prevent scratching. Sample vials will be stored inverted to prevent
deposits from forming on the bottom surface of the cell.
The Field Testing Organization shall be required to document any problems experienced with
the monitoring turbidity instruments, and shall also be required to document any subsequent
modifications or enhancements made to monitoring instruments.
14.4.2.1 Bench-Top Turbidimeters. The method for collecting grab samples will consist
of running a slow, steady stream from the sample tap, triple-rinsing a dedicated sample beaker
in this stream, allowing the sample to flow down the side of the beaker to minimize bubble
entrainment, double-rinsing the sample vial with the sample, carefully pouring from the beaker
down the side of the sample vial, wiping the sample vial clean, inserting the sample vial into the
turbidimeter, and recording the measured turbidity.
When cold water samples cause the vial to fog and prevent accurate readings, allow the vial to
warm up by submersing partially into a warm water bath for approximately 30 seconds.
14.4.2.2 In-Line Turbidimeters. In-line turbidimeters may be used during verification
testing and must be calibrated as specified in the manufacturer's operation and maintenance
manual. It will be necessary to periodically verify the in-line readings using a bench-top
turbidimeter; although the mechanism of analysis is not identical between the two instruments the
readings should be comparable. Should these readings suggest inaccurate readings then all in-
line turbidimeters should be recalibrated. In addition to calibration, periodic cleaning of the lens
should be conducted using lint-free paper, to prevent any particle or microbiological build-up
that could produce inaccurate readings. Periodic verification of the sample flow should also be
performed using a volumetric measurement. Instrument bulbs should be replaced on an as-
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needed basis. It should also be verified that the LED readout matches the data recorded on the
data acquisition system, if the latter is employed.
14.4.3 Temperature
Readings for temperature shall be conducted in accordance with Standard Method 2550.
Raw water temperatures shall be obtained at least once daily. The thermometer shall have a
scale marked for every 0.1ฐC, as a minimum, and should be calibrated weekly against a
precision thermometer certified by the National Institute of Standards and Technology (NIST).
(A thermometer having a range of -1ฐC to +51ฐC, subdivided in 0.1ฐ increments, would be
appropriate for this work.)
14.4.4 Dissolved Oxygen
Analysis for dissolved oxygen shall be performed on raw ground water samples according to
Standard Method 4500-0 using an iodometric method or the membrane electrode method.
The techniques described for sample collection must be followed very carefully to avoid causing
changes in dissolved oxygen during the sampling event. Sampling for dissolved oxygen does not
need to be coordinated with sampling for other water quality parameters, so dissolved oxygen
samples should be taken at times when immediate analysis is going to be possible. This will
eliminate problems that may be associated with holding samples for a period of time before the
determination is made.
If the sampling probe is not mounted such that the probe is continuously exposed to the process
stream, then care must be taken when measuring the dissolved oxygen concentration. For best
results, collect the dissolved oxygen sample with minimal agitation and measure the dissolved
oxygen concentration immediately. If possible, measure the dissolved oxygen under a
continuous stream of sample by placing the tip of the probe in the sample container, allowing the
sample to overflow the container while the probe reaches equilibrium (usually less than 5
minutes).
14.5 Chemical Samples Shipped Off-Site for Analysis
The analytical methods that shall be used during testing for chemical samples that are shipped off-site for
analyses are described in the section below.
14.5.1 Organic Samples
Samples for analysis of total organic carbon (TOC), UV254 absorbance, and dissolved organic
carbon (DOC) shall be collected in glass bottles supplied by the state-certified or third party- or
EPA-accredited laboratory and shipped at 4 ฐC to the analytical laboratory within 24 hours of
sampling. These samples shall be preserved in accordance with Standard Method 5010 B.
Storage time before analysis shall be minimized, according to Standard Methods.
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14.5.2 Inorganic Samples
Inorganic chemical samples shall be collected and preserved in accordance with Standard
Methods or EPA-approved methods. The samples shall be refrigerated at approximately 2 to
8ฐC. Samples shall be processed for analysis by a state-certified or third party- or EPA-
accredited laboratory within 24 hours of collection. The laboratory shall keep the samples at
approximately 2 to 8ฐC until initiation of analysis.
14.5.3 SOC Analysis
Analysis of SOCs requires a trained analyst using sophisticated instrumentation. Only state-
certified or third party- or EPA-accredited laboratories shall analyze SOC samples that are
collected during Initial Operations and Verification Testing. As stated in the " EPA/NSF ETV
Protocol For Equipment Verification Testing For The Removal Of Synthetic Organic Chemical
Contaminants: Requirements For All Studies," approved methods for some SOCs may not be
available, and for these SOCs, a proposed, peer-reviewed method may be used.
There are many approved methods for analyzing Phase II and Phase V SOCs. Depending on
the laboratory, gas chromatography (GC) or high performance liquid chromatography (HPLC)
methods can be used to analyze SOCs. For both methods, the equipment is highly specialized
and proper operation of these instruments requires a skilled laboratory technician.
Mass spectrometry is not required for all SOCs, however it is recommended for SOC
identification. Retention times relative to the internal standard can also be used to identify
SOCs. Either peak height or peak area can be used to determine the SOC concentrations.
SOCs shall be analyzed with an internal standard similar in analytical behavior and not affected
by the matrix for QA/QC. An appropriate surrogate standard shall also be used during SOC
analysis. Data pertaining to the internal and surrogate standards shall be reported with the SOC
concentrations of the samples being analyzed. A method blank shall also be prepared and
analyzed by the state-certified or third party- or EPA-accredited laboratory to verify minimal
contamination in the laboratory.
At least three standards shall be used to develop the standard curve for SOC quantification and
these three standards shall be extracted and analyzed (by GC or HPLC) on the same day as the
samples.
During each Verification Test period, one treated water sample shall be analyzed by scanning
for the presence and concentration of potential by-products of SOC disinfection by oxidation.
Gas chromatography followed by mass spectrometry can be used to identify many of the
organic by-products formed during oxidation disinfection. The spectra obtained by this analysis
can be matched to a compound library in a computer database to identify the various by-
products. This analysis shall be performed by a state-certified or third party- or EPA-
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accredited analytical laboratory. The scan should be targeted toward the SOC of interest, and
the potential by-products associated with oxidation of that SOC.
Spiked samples shall be analyzed once, at the beginning of each Verification Test Run. The
laboratory shall spike a feed water sample with a known quantity of the SOC(s) of interest and
analyze this spiked sample. SOC analysis of the spiked sample will indicate if there are any
interferences present in the feed water. The broad scan can be a performance-based scan (i.e.,
the scan is not used for compliance, and therefore undergoes less rigorous QA/QC and is less
expensive than a compliance based scan analysis.)
14.6 Trip Control
For tests utilizing spiked SOCs, a replicate or subsample of the spiking solution shall accompany the
actual spiking solution from the analytical laboratory. This replicate sample shall undergo all of the
processes used on the actual solution including dose preparation, shipping, preparation for spiking, and
return to the laboratory for analysis. The trip control samples should show minimal loss of SOC(s).
Significant decreases in the SOC concentration of the trip control sample indicates that some step in
handling the solution contributed to the reduction in the SOC concentration. The seeding tests must be
repeated when significant loss of SOCs in the trip control sample is observed.
15.0 TASK 8: COST EVALUATION
This Plan includes the assessment of costs of verification with the benefits of testing NF membrane
processes over a wide range of operating conditions. Therefore, this Plan requires that one set of
operating conditions be tested over a 60-day testing period. The equipment Verification Tests will
provide information relative to systems, which provide desired results and the cost, associated with the
systems. Design parameters are summarized in Table 15.1. These parameters will be used with the
equipment Verification Test costs to prepare cost comparisons for Verification Testing purposes.
Capital and operation and maintenance (O & M) costs realized in the equipment Verification Test may
be utilized for calculating cost estimates. O & M costs for each system will be determined during the
equipment Verification Tests. The equipment costs will vary based on the cost of membrane equipment.
The O & M costs that will be recorded and compared during the Verification Test include:
Labor;
Electricity;
Chemical Dosage, and
Equipment Replacement Frequency.
The capital and O & M costs will vary based on geographic location.
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Table 15.1: Design Parameters for Cost Analysis
Design Parameter
Specific Utility Values
Raw water feed rate(mgd)
Total required plant production rate(mgd)
By-pass flow rate (mgd)
Membrane flow rate (mgd)
High/Low plant feedwater temperature (ฐC)
Average Flux (gsfd/psi)
Maximum Flux (gsfd/psi)
Average cleaning frequency (days)
High/Low feed TDS (mg/L)
O & M costs should be provided for each membrane process that is tested. In order to receive the full
benefit of the equipment Verification Test Programs, these costs should be considered along with quality
of system operations. Other cost considerations may be added to the cost tables presented in this
section as is needed prior to the start-up of the Verification Tests. A summary of O & M costs are
outlined in Table 15.2.
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Table 15.2: Operations and Maintenance Cost
Cost Parameter
Specific Values
Labor rate + fringe ($/personnel-hour)
Labor overhead factor (% of labor)
Number of O&M personnel hours per week
Electric rate ($/kWh)
Membrane replacement frequency (%/year)
Chemical Dosage (per week)
O&M cost ($/Kgal)
Dose
Bulk Chemical Cost
Chlorine (Disinfectant)
Sulfuric acid (Pretreatment)
Alum (Pretreatment)
Hydrochloric acid (Pretreatment)
Scale inhibitor 2(Pretreatment)
Caustic (Post-treatment)
Sodium hydroxide (Membrane cleaning)
Phosphoric acid (Membrane cleaning)
'information for cleaning chemicals and pretreatment chemicals (such as alum) should also be
provided in this table. For cleaning agents, the concentration of the cleaning solution used to
clean the membranes should be reported as the chemical dosed.
2Report the product name and manufacturer of the specific scale inhibitor used.
16.0 SUGGESTED READING
AWWARF. Membrane Concentrate Disposal. Denver, CO, 1993.
Berg, P. and Gimbel, R. "Rejection of Trace Organics by Nanofiltration." Proceedings 1997
Membrane Technology Conference. New Orleans, LA, 1997.
Camp, P. "Integral Approach of Surface Water Treatment Using Ultrafiltration and Reveres Osmosis."
Proceedings 1995 AWWA Membrane Technology Conference. Reno, NV, 1995.
Chen, S.S., Taylor, J.S., Norris, C.D. and Hofman, J.A.M.H. "Flat-sheet Testing for Pesticide
Removal by Varying RO/NF Membranes." Proceedings 1997 Membrane Technology Conference.
New Orleans, LA, 1997.
Duranceau, S.J., Taylor, J.S. and Mulford, L.A. "SOC Removal in a Membrane Softening Process."
JAWWA. January 1992.
April 2002
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Duranceau, S.J. "Membrane process Post-Treatment." Supplement to AWWA Seminar Proceedings:
Membrane Technology Conference. Baltimore, MD, 1993.
Hofman, J.A.M.H., Kruithof, J.C., Noij, Th.H.M. and Schippers, J.C. "Removal of Pesticides and
Other Contaminants with Nanofiltration." H?Q. March 1993.
Kedem, O. and Katchalsky, A. "Thermodynamic Analysis of the Permeability of Biological
Membranes to Non-electrolytes." Biochemical et Biophysical Acta, 27:123. 1958.
Kruithof, J.C., Hofman, J.A.M.H., Hopman, R., Hoek, J.P. and Schultink, L. J. "Rejection of
Pesticides and Other Micropollutants by Reverse Osmosis." Proceedings 1995 Membrane
Technology Conference. Reno, NV, 1995.
Lonsdale, H.K., Merten, U. and Tagami, M. "Phenol Transport in Cellulose Acetate Membranes."
Journal of. Applied. Polymer Science. November, 1967
Merten, U. Desalination by Reverse Osmosis. Cambridge, MA: MIT Press. 1966.
Schippers, J.C. and Verdouw. "The Modified Fouling Index: A Method of Determining the
Characteristics of Water." Desalination, 32: 137-148. 1980.
Sung L.K., Morris, K.E. and Taylor J.S. "Predicting Colloidal Fouling." International Desalination and
Water Reuse Journal. November/December, 1994.
Takigawa, D.Y., Metcalfe, P.F., Chu, H.C., Light, W.G., Murrer, J. and Holden, P. "Ultra-Low
Pressure Reverse Osmosis Membranes." Proceedings 1995 Membrane Technology Conference.
Reno, NV, 1995.
Taylor, J.S., Mulford, L.A. Duranceau S.J. and Barrett W.M. "Cost and Performance of a Membrane
Pilot Plant." JAWWA. November 1989.
Taylor, J.S., Duranceau, S.J., Barrett, W.M. and Goigel, J.F. Assessment of Potable Water
Membrane Applications and Research Needs. Denver: AWWA Research Foundation. 1990.
Taylor, J.S., Hofman, J.A.M.H, Duranceau, S.J., Kruithof J.C. and Schippers, J.C. "Simplified
Modeling of Diffusion Controlled Membrane Systems." J. Water, SRJ-Aqua. May 1994.
USEPA. Guidance Manual for Compliance with Filtration and Disinfection Requirements for Public
Water Systems Using Surface Water Sources. Cincinnati, OH. Science and Technology Branch.
1989.
USEPA, AWWA. Guidance Manual for Compliance with the Filtration and Disinfection Requirements
for Public Water Systems Using Surface Waters. Washington, D.C. 1990.
USEPA. ICR Manual for Bench- and Pilot-Scale Treatment Studies. Office of Ground Water and
Drinking Water, Cincinnati, OH, Technical Support Division. 1996.
Weber, W.J. Physicochemical Processes for Water Quality Control. New York: John-Wiley & Sons.
1972.
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APPENDIX A - SCX HEALTH EFFECTS INFORMATION
TABLE A.l: Regulated SOCs under Phase II of the SDWA
PARAMETER
MCLG
(mg/L)
MCL
(mg/L)
Sources of Drinking Water
Contamination
Potential Health
Effects
2,4,5-TP (Silvex)
0.05
0.05
Herbicide on crops, right-of-ways, golf
courses; canceled in 1982
Liver and kidney damage
2,4-D (Formula 40,
Weedar 64)
0.07
0.07
Runoff from herbicide on wheat, corn,
range lands, lawns
Liver and kidney damage
Acrylamide
Zero
XT
Polymers used in sewage and wastewater
treatment
Cancer, nervous system
effects
Alachlor (Lasso)
Zero
0.002
Runoff from herbicide on com, soybeans,
other crops
Cancer
Aldicarb
0.007
0.007
Insecticide on cotton, potatoes, other crops;
widely restricted
Nervous system effects
Aldicarb sulfone
0.007
0.007
Biodegradation of Aldicarb
Nervous system effects
Aldicarb sulfoxide
0.007
0.007
Biodegradation of Aldicarb
Nervous system effects
Atrazine
0.003
0.003
Runoff from use as herbicide on com and
non-crop land
Mammary gland tumors
Carbofuran (Furdan 4F)
0.04
0.04
Soil fumigant on com and cotton; restricted
in some areas
Nervous, reproductivity
effects
Chlordane
Zero
0.002
Leaching from soil treatment for termites
Cancer
Dibromochloropropane
(DBCP, Nemafume))
Zero
0.0002
Soil fumigant on soybeans, cotton,
pineapple, orchards
Cancer
Ethyl benzene
0.7
0.7
Gasoline, insecticides, chemical
manufacturing wastes
Liver, kidney, nervous
system effects
Ethylene dibromide
(EDB, Bromofume)
Zero
0.00005
Leaded gas additives, leaching of soil
fumigant
Cancer
Heptachlor (H-34,
Heptox)
Zero
0.0004
Leaching of insecticide for termites, very
few crops
Cancer
Heptachlor epoxide
Zero
0.0002
Biodegradation of heptachlor
Cancer
Lindane
0.0002
0.0002
Insecticides for cattle, lumber, gardens;
restricted in 1983
Liver, kidney, nervous
system, immune system
and circulatory system
effects
Methoxychlor (DMDT,
Marlate)
0.04
0.04
Insecticides for fruits, vegetables, alfalfa,
livestock, pets
Growth, liver, kidney, and
nervous system effects
Pentachlorophenol
Zero
0.001
Wood preservatives, herbicides, cooling
tower wastes
Cancer, liver and kidney
effects
Polychlorinated biphenyls
(PCBs, Aroclor)
Zero
0.0005
Coolant oils from electrical transformers,
plasticizers
Cancer
Toxaphene
Zero
0.003
Insecticide on cattle , cotton soybeans;
canceled in 1982
Cancer
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TABLE A.2: Regulated SOCs under Phase V of the SDWA
PARAMETER
MCLG
(mg/L)
MCL
(mg/L)
Sources of Drinking Water
Contamination
Potential Health Effects
Adipate (diethylhexyl)
0.4
0.4
Synthetic rubber, food packaging,
cosmetics
Decreased body weight
Dalapon
0.2
0.2
Herbicides on orchards, beans,
coffee, lawns, roads, railways
Liver, kidney effects
Dinoseb
0.007
0.007
Runoff of herbicide from crop
and non-crop allocations
Thyroid, reproductive organ
damage
Dioxin
Zero
3 * 10"8
Chemical production by-product,
impurity in herbicides
Cancer
Diquat
0.02
0.02
Runoff of herbicides on land and
aquatic weeds
Liver, kidney, eye effects
Endothall
0.1
0.1
Herbicide on crops and land and
aquatic weeds; rapidly degraded
Liver, kidney, gastrointestinal
effects
Endrin
0.002
0.002
Pesticides on insects, rodents,
birds; restricted since 1980
Liver, kidney, heart damage
Glyphosate
0.7
0.7
Herbicide on grasses, weeds,
brush
Liver, kidney damage
Hexachlorobenzene
Zero
0.001
Pesticide production waste by-
product
Cancer
Hexachlorocyclopentadie
ne
0.05
0.05
Pesticide production intermediate
Kidney, stomach damage
Oxamyl (Vydate)
0.2
0.2
Insecticide on apples, potatoes,
tomatoes
Kidney damage
Phathalate
Zero
0.006
PVC and other plastics
Cancer
Pheneanthrene (PAH)
Zero
0.0002
Coal tar coatings, burning organic
matter, volcanoes, fossil fuels
Cancer
Picloram
0.5
0.5
Herbicide on broadleaf and
woody plants
Kidney, liver damage
Simazine
0.004
0.004
herbicide on grass sod, some
crops, aquatic algae
Cancer
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APPENDIX B - PROPOSED SOCS FOR REGULATION
TABLE B.l: Proposed SOCs for Regulation
Parameters
Regulatory
Status.
MCLG
(mg/L)
MCI
(mg/L)
Status HA
RID
(mg/kg/day)
DWEL
(mg/L)
Acetochlor
Acifluorfen
Tentative
zero
Final
0.013
0.4
Acrylonitrile
Tentative
zero
Draft
Aldrin
Draft
0.00003
0.001
Bromobenzene
Listed
Draft
Bromomethane
Tentative
Final
0.001
0.05
Cyanazine
Tentative
0.001
Draft
0.002
0.07
Diazinon
Final
0.00009
0.003
Dicamba
Listed
Final
0.03
1
Dichloroethane (1,1)
Dichloropropane (1,3-)
Listed
Draft
Dichloropropane (2,2-)
Listed
Draft
Dichloropropene (1,1-)
Listed
Draft
Dichloropropene (1,3-)
Tentative
zero
Final
0.0003
0.01
Dieldrin
Final
0.00005
0.002
Dinitrophenol (2,4)
Dinitrotoluene (2,4-)
Listed
Final
0.002
0.1
Dinitrotoluene (2,6-)
Listed
Final
0.001
0.04
Diphenylhydrazine (1,2)
Disulfoton
Final
0.00004
0.001
Diuron
Final
0.002
0.07
Fonofos
Final
0.002
0.07
Hexachlorobutadiene
Tentative
0.001
Final
0.002
0.07
Isopropyltoluene (p-)
Linuron
Methomyl
Listed
Final
0.025
0.9
Methyl Bromide
Methyl-Phenol (2-)
Methyl tert butyl ether (MTBE)
Listed
Draft
0.03
1
Metolachlor
Listed
Final
0.1
3.5
Metribuzin
Listed
Final
0.013
0.5
Molinate
Naphthalene
Final
0.004
0.1
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TABLE B.l: Proposed SOCs for Regulation (Cont.)
Parameters
Regulatory
Status.
MCLG
(mg/L)
MCI
(mg/L)
Status HA
RID
(mg/kg/day)
DWEL
(mg/L)
Nitrobenzene
Organotins
Perchlorate
Prometon
Listed
Final
0.015
0.5
RDX
Final
0.003
0.1
Terbacil
Final
0.013
0.4
Terbufos
Final
0.00013
0.005
Tetrachoroethane (1,1,2,2-)
Listed
Draft
Triazine
Trichlorophenol
Listed
Draft
Trichloropropane (1,2,3-)
Listed
Final
0.006
0.2
Trifluralin
Listed
Final
0.0075
0.3
Trimethylbenzene (1,2,4-)
Draft
Sources:
1. US EPA Office of Water, "Drinking Water Regulations and Health Advisories", EPA -822-B-96-002, October 1996.
2. Federal Register, Volume 62, Number 193, October 6, 1997.
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CHAPTER 3
EPA/NSF ETV
EQUIPMENT VERIFICATION TESTING PLAN FOR SOC OXIDATION BY OZONE
AND ADVANCED OXIDATION PROCESSES
Prepared By:
NSF International
789 Dixboro Road
Ann Arbor, MI 48105
Copyright 2002 NSF International 40CFR35.6450.
Permission is hereby granted to reproduce all or part of this work,
subject to the limitation that users may not sell all or any part of the
work and may not create any derivative work therefrom. Contact ETV
Drinking Water Systems Center Manager at (800) NSF-MARK with
any questions regarding authorized or unauthorized uses of this work.
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TABLE OF CONTENTS
1.0 APPLICATION OF THIS VERIFICATION TESTING PLAN
2.0 INTRODUCTION
3.0 GENERAL APPROACH 3-7
4.0 OV ERV IEW OF TASKS 3-7
4.1 Initial Operations: Overview 3-7
4.1.1 Task A: Characterization of Feed Water 3-7
4.1.2 Task B: Initial Test Runs 3-7
4.2 Verification Operations: Overview 3-7
4.2.1 Task 1: Verification Testing Runs and Routine Equipment Operation 3-8
4.2.2 Task 2: Feed Water and Finished Water Quality 3-8
4.2.3 Task 3: Documentation of Operating and Treatment Equipment Performance 3-8
4.2.4 Task 4: SOC Oxidation 3-8
4.2.5 Task 5: Data Management 3-8
4.2.6 Task 6: Quality Assurance/Quality Control (QA/QC) 3-9
5.0 TESTING PERIODS 3-9
6.0 DEFINITION OF OPERATIONAL PARAMETERS 3-9
6.1 Feed Gas or Ozone Production Concentration (% weight or g/m3 NTP) 3-9
6.2 Off Gas Concentration (% weight or g/m3 NTP) 3-10
6.3 Applied Ozone Dosage (mg/L) 3-10
6.4 Transfer Efficiency (percent) 3-10
6.5 Transferred Ozone Dosage (mg/L) 3-10
6.6 Dissolved Ozone Concentration (mg/L) 3-11
6.7 Ozone Decay Rate (1/min) 3-11
7.0 TASK A: CHARACTERIZATION OF FEED WATER 3-11
7.1 Introduction 3-11
7.2 Objectives 3-12
7.3 Work Plan 3-12
7.4 Analytical Schedule 3-12
7.5 Evaluation Criteria 3-13
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.3-6
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TABLE OF CONTENTS (continued)
8.0 TASK B: INITIAL TEST RUNS 3-13
8.1 Introduction 3-13
8.2 Objectives 3-13
8.3 Work Plan 3-13
8.4 Analytical Schedule 3-13
8.5 Evaluation Criteria 3-14
9.0 TASK 1: VERIFICATION TESTING RUNS AND ROUTINE
EQUIPMENT OPERATION 3-14
9.1 Introduction 3-14
9.2 Experimental Objectives 3-14
9.3 Work Plan 3-14
9.3.1 Verification Testing Runs 3-14
9.3.2 Routine Equipment Operation 3-15
9.4 Schedule 3-15
9.5 Evaluation Criteria 3-15
10.0 TASK 2: FEED WATER AND TREATED WATER QUALITY 3-15
10.1 Introduction 3-15
10.2 Experimental Objectives 3-16
10.3 Work Plan 3-16
10.4 Analytical Schedule 3-17
10.5 Evaluation Criteria 3-17
11.0 TASK 3: DOCUMENTATION OF OPERATING CONDITIONS AND
TREATMENT EQUIPMENT PERFORMANCE 3-17
11.1 Introduction 3-17
11.2 Objectives 3-17
11.3 Work Plan 3-18
11.4 Schedule 3-18
11.5 Evaluation Criteria 3-19
12.0 TASK 4: DOCUMENTATION OF EQUIPMENT PERFORMANCE:
SOC OXIDATION 3-19
12.1 Introduction 3-19
12.2 Experimental Obj ectives 3-19
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TABLE OF CONTENTS (continued)
12.3 Work Plan 3-19
12.3.1 Types of SOCs 3-20
12.3.2 Spiking Protocols 3-20
12.3.3 Test Operation and Sample Collection 3-21
12.3.4 Experimental Quality Control 3-21
12.3.5 Treatment of Effluent 3-22
12.4 Analytical Schedule 3-22
12.5 Evaluation Criteria 3-22
13.0 TASK 5: DATA MANAGEMENT 3-22
13.1 Introduction 3-22
13.2 Experimental Objectives 3-22
13.3 Work Plan 3-23
13.4 Statistical Analysis 3-24
14.0 TASK 6: QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) 3-24
14.1 Introduction 3-24
14.2 Experimental Obj ectives 3-24
14.3 Work Plan 3-24
14.3.1 Daily QA/QC Verifications 3-25
14.3.2 QA/QC Verifications Performed Every Two Weeks 3-25
14.3.3 QA/QC Verifications Performed Every Testing Period 3-25
14.4 On-Site Analytical Methods 3-25
14.4.1 pH 3-25
14.4.2 Turbidity Analysis 3-26
14.4.3 Dissolved Ozone 3-27
14.4.4 Gas Phase Ozone 3-27
14.4.5 Hydrogen Peroxide 3-28
14.4.6 Temperature 3-28
14.4.7 Color 3-28
14.4.8 Dissolved Oxygen 3-29
14.5 Chemical and Biological Samples Shipped Off-Site for Analysis 3-29
14.5.1 Organic Samples 3-29
14.5.2 Algae 3-29
14.5.3 Inorganic Samples 3-29
14.5.4 SOC Analysis 3-30
14.6 Experimental QA/QC Samples 3-31
14.6.1 Process Control 3-31
14.6.2 Trip Control 3-31
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TABLE OF CONTENTS (continued)
15.0 OPERATION AND MAINTENANCE 3-3 1
15.1 Maintenance 3-32
15.2 Operation 3-32
16.0 REFERENCES 3-34
TABLES
Table 1 Water Quality Sampling and Measurement Schedule 3-35
Table 2 Analytical Methods 3-38
Table 3 System Operating Data 3-40
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1.0 APPLICATION OF THIS VERIFICATION TESTING PLAN
This document is the ETV Testing Plan for evaluation of water treatment equipment utilizing ozone for
oxidation of man-made or synthetic organic chemicals (SOCs). This Testing Plan is to be used as a
guide in the development of the Product-Specific Test Plan (PSTP) for testing ozone equipment, within
the structure provided by the "EPA/NSF ETV Protocol For Equipment Verification Testing For The
Removal Of Synthetic Organic Chemical Contaminants: Requirements For All Studies." This ETV plan
is applicable only to treatment systems that rely on ozone to oxidize SOCs in water. Systems using
ozone oxidation for reasons other than SOC oxidation (i.e., taste and odor control, disinfection) are not
required to conduct the experiments outlined in this ETV plan. Systems may incorporate unique
strategies for enhancing the effect of ozone on SOC concentrations, such as the use of ozone/advanced
oxidation processes (ozone/AOPs) combining ozone with ultraviolet (UV) light or hydrogen peroxide.
All ozone technologies, including ozone/AOPs, may be tested under this plan.
In order to participate in the equipment verification process for SOC oxidation by ozone or
ozone/AOPs, the equipment Manufacturer and the designated Field Testing Organization shall use the
procedures and methods described in this test plan, and in the 'EPA/NSF ETV Protocol For
Equipment Verification Testing For The Removal Of Synthetic Organic Chemical Contaminants:
Requirements For All Studies" as guidelines for development of the PSTP.
This ETV test plan is applicable to the testing of water treatment equipment utilizing ozone or
ozone/AOPs for SOC oxidation in drinking water. This plan is applicable to both surface water and
groundwater supplies.
2.0 INTRODUCTION
The organic compounds present in source waters are characterized as either: 1) naturally occurring
(e.g., humic acid, fulvic acid); or 2) synthetic (e.g., pesticides, hydrocarbons, phenols, dyes, amines,
solvents, and plasticizers, etc.).
Ozone is a powerful oxidant that is applied during water treatment for microbial inactivation as well as
oxidation of organic compounds, metals, and taste and odor causing compounds. The use of ozone in
potable water treatment in the United States has increased substantially in the last 20 years, due to its
superior inactivation of microorganisms (i.e., cysts) relative to chlorine, chloramine, and chlorine dioxide
and its ability to reduce the concentrations of certain organics in drinking water.
Ozone is applied to drinking water as a gas, which is generated on-site. The ozone gas is transferred
into a dissolved state by either bubbling or injecting ozone gas into the process stream. Ozone can be
applied to untreated (raw) or treated (e.g., coagulated/settled or filtered) water. In this ETV plan, the
oxidation of SOCs by ozone or ozone/AOPs will be evaluated. Ozone/AOPs, which typically combine
ozonation with UV light or hydrogen peroxide, convert dissolved ozone to hydroxyl radicals. In many
instances, ozone/AOPs can be more effective than ozone used by itself for oxidation of SOCs.
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3.0 GENERAL APPROACH
Testing of equipment covered by this ETV plan will be performed by an NSF-qualified Field Testing
Organization (FTO) that is selected by the equipment Manufacturer. Water quality analytical work to
be carried out as part of this ETV plan will be contracted with a state-certified or third party- or EPA-
accredited qualified analytical laboratory.
4.0 OVERVIEW OF TASKS
4.1 Initial Operations: Overview
The purpose of these tasks is to provide preliminary information which will facilitate final test design and
data interpretation.
4.1.1 Task A: Characterization of Feed Water
The objective of this Initial Operations task is to obtain a chemical and physical characterization
of the feed water for those systems using ozone or ozone/AOPs for SOC oxidation. Historical
records of SOC concentrations in the feed water shall be reviewed to evaluate the use of ozone
or ozone/AOPs at the site.
A thorough description of the watershed or aquifer and any pretreatment modules that provide
the feed water should be prepared, to aid in interpretation of feed water characterization.
4.1.2 Task B: Initial Test Runs
During Initial Operations, the manufacturer may want to evaluate equipment operation and
determine flow rates, hydraulic retention time, ozone dosage, optimum pH, sequencing or timing
of UV light and/or hydrogen peroxide addition relative to ozonation, or other factors which
provide effective treatment of feed water. This is a recommended Initial Operations task.
The FTO may also want to work with the analytical laboratory to perform blank or preliminary
challenges and sampling routines to verily that sampling equipment can perform its required
functions. This is also a recommended Initial Operations Task.
4.2 Verification Operations: Overview
The objective of this task is to operate for a minimum of one test period the treatment equipment
provided by the FTO and to assess its ability to meet stated water quality goals and any other
performance objectives specified by the Manufacturer. The equipment shall be operated to collect data
on equipment performance and water quality for purposes of performance verification. The test period
selected should represent the worst-case for concentrations of ozone demanding contaminants (e.g.,
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iron, organics, hydrogen sulfide, pesticides, or turbidity) and for presence of synthetic organic
contaminants.
4.2.1 Task 1: Verification Testing Runs and Routine Equipment Operation
To characterize the technology in terms of efficiency and reliability, water treatment equipment
that includes ozone (or ozone/AOPs) shall be operated for Verification Testing purposes with
the operational parameters based on the results of the Initial Operations testing.
4.2.2 Task 2: Feed Water and Finished Water Quality
During each Verification Testing period, feed water and treated water samples shall be collected
and analyzed for those parameters relevant to oxidation performance and affecting equipment
performance, as outlined in Section 10, Table 1.
4.2.3 Task 3: Documentation of Operating Conditions and Treatment Equipment
Performance
During each Verification Testing period, operating conditions and performance of water
treatment equipment shall be documented. This includes ozone feed gas concentration, gas and
liquid pressures, gas and liquid temperatures, gas and liquid flow rates, ozone off-gas
concentration, applied and transferred ozone dosage, power usage for the ozone generator,
ozone transfer equipment, ozone feed-gas and off-gas monitors (if part of the ozone system)
and ozone destruct unit, as well as stability of the electrical power supply (surges, brown-outs,
etc.).
If ozone (or an AOP) is used following pretreatment (e.g., coagulation/settling), then a complete
description of the pretreatment process shall be provided. For AOP systems, the operating
conditions and parameters associated with hydrogen peroxide or UV light equipment must also
be documented.
4.2.4 Task 4: SOC Oxidation
The objective of this task is to evaluate SOC oxidation during Verification Testing by measuring
the SOCs of interest in the feed water and in the treated water. If the SOC concentration
naturally present in the feed water is not sufficiently high for testing, SOC spiking is needed.
Another requirement of this task is to provide a gas chromatography/mass spectrometry scan of
the organic by-products formed by ozonation of SOCs.
4.2.5 Task 5: Data Management
The objective of this task is to establish an effective field protocol for data management at the
field operations site and for data transmission between the FTO and the NSF for data obtained
during the Verification Testing. Prior to the beginning of field testing, the database design must
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be developed by the FTO and reviewed and approved by NSF. This will ensure fiat the
required data will be collected during the testing, and that it can be effectively transmitted to
NSF for review.
4.2.6 Task 6: Quality Assurance/Quality Control (QA/QC)
An important aspect of Verification Testing is the protocol developed for quality assurance and
quality control. The objective of this task is to assure accurate measurement of operating and
water quality parameters during ozone equipment Verification Testing. Prior to the beginning of
field testing, a QA/QC plan must be developed which addresses all aspects of the testing
process. Each water quality parameter and operational parameter must have appropriate QA
and QC measures in place and documented. For example, the protocol for ozone measurement
using a spectrophotometer should describe how the instrument is calibrated, what adjustments
are made, and provide a permanent record of all calibrations and maintenance for that
instrument.
5.0 TESTING PERIODS
The required tasks in the Verification Testing Plan (Tasks 1 through 6) are designed to be carried out
during one or more testing periods, each of which shall provide at least 200 hours of ozone equipment
operation. During this time, the performance and reliability of the equipment shall be documented.
Some systems may operate for less than 24 hours per day. Interruptions in ozone production are
allowed but the reason for and duration of all interruptions shall be fully described in the Verification
Testing report. Any testing conducted at intervals of less than 200 hours is considered a test run,
whereas the entire 200 hours (either continuous or as the sum of individual test runs) of ozone
equipment operation is considered the Verification Test period. If ozone production is interrupted
during a verification test run, that test run shall be considered to have been concluded at the time of
interruption of the ozone feed. After restart, all data collected are to be part of a new verification test
run.
6.0 DEFINITION OF OPERATIONAL PARAMETERS
Definitions that apply to ozone and ozone/AOP processes are given below. Refer to Appendix A of
Ozone in Water Treatment, Application and Engineering, by the American Water Works
Association Research Foundation and Compagnie Generate des Eaux, Lewis Publishers, 1991 for a
more detailed description of terms.
6.1 Feed Gas or Ozone Production Concentration (% weight or g/m3 NTP)
The feed gas or ozone production concentration (Yi) is the ozone concentration (in gaseous form) being
applied to the water being treated. It is expressed in units of g/m3 normal temperature and pressure
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(NTP) or as percent by weight. The temperature and pressure values associated with NTP are 0 ฐC
and one atmosphere (i.e., 14.696 psi, 760 mm Hg, or 101.325 kPa), respectively.
6.2 Off Gas Concentration (% weight or g/m3 NTP)
The off gas concentration (Y2) is the ozone concentration (in gaseous form) of the gas which is being
released (i.e., off gas) from the water being treated. This off gas contains ozone which was not
transferred into a dissolved form during treatment. It is expressed in units of g/m3 NTP or as percent by
weight.
6.3 Applied Ozone Dosage (mg/L)
The amount of ozone added to the water being treated is the applied ozone dosage. The equation for
calculating the applied ozone dosage is as follows:
D = P/(8.34*L)
where: D = applied ozone dosage (mg/L)
P = ozone production (lb/day)
L = water flow rate (MGD, million U.S. gallons per day )
6.4 Transfer Efficiency (percent)
The transfer efficiency is defined as the percentage of ozone that becomes dissolved into the water being
treated. The equation for calculating the transfer efficiency is as follows:
TE = [(Yi - Y2)/Y1]*100
where: TE = transfer efficiency (percent)
Yi = ozone production concentration (g/m3 NTP or percent by weight)
Y2 = off gas ozone concentration (g/m3 NTP or percent by weight)
This calculation assumes that the flow of the feed gas is equal to the flow of the off gas. The transfer
efficiency calculation can be refined by measuring both gas flow rates or by monitoring the dissolved gas
concentration in the liquid phase if the Manufacturer and their FTO desire.
6.5 Transferred Ozone Dosage (mg/L)
The transferred ozone dosage is the concentration of ozone that becomes dissolved into the water being
treated. The equation for calculating the transferred ozone dosage is as follows:
T = (D * TE)/100
where: T = transferred ozone dosage (mg/L)
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D = applied ozone dosage (mg/L)
TE = transfer efficiency (percent, i.e., 95.0 and not 0.95)
6.6 Dissolved Ozone Concentration (mg/L)
The concentration of ozone in solution is the dissolved ozone concentration. It is measured using an
indigo bleaching technique (e.g., HACH AccuVac or Standard Method 4500-03 B) or by inserting a
dissolved ozone probe into the process stream (e.g. Orbisphere, Orbisphere Laboratories, Emerson,
NJ).
6.7 Ozone Decay Rate (1/min)
After the initial ozone demand has been satisfied, the ozone decay rate is assumed to follow pseudo
first-order kinetics. Monitoring the decay rate will provide an indication of the level of ozone demanding
substances present in the feed water and the environmental conditions affecting oxidation (e.g., pH and
temperature). To calculate the decay rate, the initial ozone concentration (C0) at time zero and the
ozone concentration (C) after time, t, must be known. The equation for calculating the decay rate (k) is
as follows:
C = C0e"kt
where: C = ozone concentration at time t (mg/L)
Co = ozone concentration at time zero (mg/L)
t = contact time (minutes)
k = decay coefficient (1/minute)
If possible, the ozone residual should be measured after several contact times in the reactor. The best fit
line of ln(C/Co) versus t can be used to obtain the decay coefficient, k. If the plot does not fit a straight
line, the assumption of pseudo-first order kinetics is not valid.
7.0 TASK A: CHARACTERIZATION OF FEED WATER
7.1 Introduction
This recommended Initial Operations task is performed to determine if the chemical, biological, and
physical characteristics of the feed water are appropriate for the water treatment equipment to be
tested.
Initial Operations (Tasks A and B) are not mandatory but they are recommended as an aid to successful
completion of Verification Testing. If the verification entity conducts a site visit for QA purposes, then
Task B would need to be performed.
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7.2 Objectives
The objective of this task is to obtain a complete chemical and physical characterization of the source
water, or the feed water after pre-treatment, that will be entering the treatment system being tested.
7.3 Work Plan
During this Initial Operations task, the following water quality characteristics of the feed water to the
ozone system should be measured and recorded for both ground and surface waters: ozone demand,
turbidity, temperature, pH, alkalinity, calcium, total hardness, total sulfides, total organic carbon,
dissolved organic carbon, ultraviolet absorbance (at 254 nm), color, bromide, iron, and manganese.
Data on SOCs in the feed water (source water) should be obtained from existing databases or by
analysis of water samples, so a determination about the need for SOC spiking can be made.
Sufficient information shall be obtained to illustrate the variations expected to occur in these parameters
that will be measured during the Verification Testing for a typical annual cycle for the water source. This
information will be compiled and shared with NSF so NSF and the FTO can determine the adequacy of
the data for use as the basis to make decisions on the testing schedule.
A brief description of the watershed or aquifer source shall be provided, to aid in interpretation of feed
water characterization. The watershed description should include a statement of the approximate size of
the watershed, a description of the topography (i.e., flat, gently rolling, hilly, mountainous) and a
description of the kinds of human activity that take place (i.e., mining, manufacturing, cities or towns,
farming, wastewater treatment plants) with special attention to potential sources of pollution that might
influence feed water quality. The nature of the water source, such as stream, river, lake or man-made
reservoir, should be described as well. Aquifer description should include (if available) the above
characterization relative to the recharge zone, a description of the hydrogeology of the water bearing
stratum(a), well boring data, and any Microscopic Particulate Analysis data indicating whether the
groundwater is under the influence of surface waters.
Any pretreatment, including oxidation, coagulation or pH adjustment, of the water upstream of the
ozone equipment shall be completely documented and characterized. Any coagulant or other chemical
additions shall be identified and the chemical form and dosage shall be fully described.
7.4 Analytical Schedule
There is no recommended analytical schedule for characterization of the feed water. Any existing water
quality data should be reviewed to assess the character of the feed or source water as well as the range
of water quality that can be expected during each season. Water quality sampling can be performed if
there are data gaps in the existing information.
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7.5 Evaluation Criteria
Feed water quality will be evaluated in the context of the Manufacturer's statement of the equipment
performance objectives but should not be beyond the range of water quality suitable for treatment for
the equipment in question. The device shall be tested using water of the quality for which the equipment
was designed.
8.0 TASK B: INITIAL TEST RUNS
8.1 Introduction
During the Initial Operations, a Manufacturer and their FTO may choose to evaluate equipment
operations and determine flow rates, hydraulic residence time, ozone production, power supply
requirements, or other factors applicable to the technology and related to effective treatment of the feed
water, including the weight ratios of hydrogen peroxide to ozone dosages and/or the ratios of UV to
ozone dosages. The Manufacturer may also choose to work with the FTO and the analytical
laboratory to perform blank or preliminary challenges (if necessary) and sampling routines to verify that
sampling equipment can perform the required functions under normal operating conditions. This
information may also indicate operating conditions under which the Manufacturer's stated performance
objectives are not met. This is a recommended Initial Operations task. An NSF field inspection of
equipment operations and sampling and field analysis procedures may be carried out during the initial
test runs, and if this occurs, the Initial Operations task must be performed.
8.2 Objectives
The objective of these test runs is to bracket the proper operating parameters for treatment of feed
water during Verification Testing. The ability of ozone or ozone/AOP systems to effectively oxidize
SOCs and reduce their concentrations will vary depending on the quality of the feed water being treated
and the season. Therefore, conducting initial test runs is strongly recommended.
8.3 Work Plan
Because Initial Operations test runs are not a requirement of this ETV plan, the Manufacturer and FTO
can decide the duration of Initial Operations. Enough time should be available to establish optimal
operating conditions and to ensure that the system will be able to meet any performance objectives.
8.4 Analytical Schedule
Because these Initial Operations are being conducted to define future operating conditions for
Verification Testing, a strictly defined schedule for sampling and analysis does not need to be followed.
Adhering to the schedule for sampling and analysis to be followed during Verification Testing is
recommended, however, so the operator can gain familiarity with the time requirements that will be
applicable during Verification Testing. Also, during the Initial Operations phase, the verification
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organization may conduct an initial on-site inspection of field operations, sampling activities, and on-site
analyses. The sampling and analysis schedule that is to be used during Verification Testing shall be
followed during the on-site inspection.
8.5 Evaluation Criteria
The Manufacturer and the FTO should evaluate the data produced during the Initial Operations to
determine if the water treatment equipment performed in a manner that will meet or exceed the
statement of performance objectives. If performance is not as good as in the statement of performance
objectives, the FTO may conduct additional Initial Operations or cancel the remainder of the testing
program.
9.0 TASK 1: VERIFICATION TESTING RUNS AND ROUTINE EQUIPMENT
OPERATION
9.1 Introduction
Water treatment equipment that includes ozone or ozone/AOPs shall be operated for Verification
Testing purposes with operational parameters based on the manufacturer's statement of performance
objectives.
9.2 Experimental Objectives
The objective of this task is to operate the ozone or ozone/AOP equipment and characterize the
effectiveness and reliability of the equipment.
9.3 Work Plan
9.3.1 Verification Testing Runs
The Verification Testing Runs in this task consist of an evaluation of the treatment system, using
the most successful treatment parameters defined during Initial Operations. Performance and
reliability of the equipment shall be tested during one or more Verification Testing periods
consisting of at least 200 hours of ozone production at the test site.
Verification Testing should be conducted at times when worst-case seasonal water quality
conditions exist, including peak concentrations of SOCs or of hydroxyl free radical-demanding
contaminants or ozone-demanding contaminants. During each of these testing periods, Tasks 1
through 6 shall be conducted simultaneously.
Factors that can influence SOC oxidation include:
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the presence of ozone demanding substances that may be present in the form of
particulate matter, dissolved organic matter, or dissolved inorganic matter; often occurring in the
spring, or during reservoir or lake turn-over events, or also encountered in rivers carrying a high
sediment load or in surface waters during periods of Hgh runoff resulting from heavy rains or
snow melt. Algae also exert an ozone demand as do iron, manganese, and cyanide. The
presence of ozone demanding substances will affect the ability of ozone to effectively oxidize
SOCs and will react with hydroxyl free radicals needed to destroy the slower-to-oxidize SOCs.
pH and alkalinity, which can vary seasonally, will affect the decay rate of ozone in
natural waters, and may affect the amount of SOC oxidation achieved by the system.
temperature.
9.3.2 Routine Equipment Operation
If the water treatment equipment is being used for production of potable water during the time
intervals between verification runs, routine operation of the equipment will occur. In this
situation, the operating and water quality ckta collected and furnished to the Safe Drinking
Water Act (SDWA) primacy agency shall be supplied to the NSF-qualified FTO for use in
evaluating conditions during verification testing.
For equipment that is being used to treat water for distribution to customers, it is assumed that
the State has already issued a permit (if one is necessary) for installation and operation. If ETV
is being conducted to establish the SOC oxidation capabilities of the existing equipment,
permission by the State may be required if the system were taken off-line for verification testing.
9.4 Schedule
During Verification Testing, water treatment equipment shall be operated for a minimum of 200 hours.
The reason for and duration of any interruptions in ozone production during Verification Testing shall be
fully documented.
9.5 Evaluation Criteria
The goal of this task is to operate the equipment for 200 hours during Verification Testing. Data shall
be provided to substantiate that 200 hours of operation have been completed.
10.0 TASK 2: FEED WATER AND TREATED WATER QUALITY
10.1 Introduction
Water quality data shall be collected during Verification Testing for the feed water and treated water as
shown in Table 1. The Field Test Organization, on behalf of the equipment Manufacturer, shall assure
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the sampling or measuring of the water quality parameters in Table 1. The FTO may use local
personnel to assist in collection of samples or measurement of test parameters, but is responsible for
their training to assure proper techniques are used at all times.
10.2 Experimental Objectives
The objective of this task is to identify the presence and concentration of water quality characteristics
that might affect the ability of ozone to oxidize SOCs. This task will also provide data to ensure that the
use of ozone does not increase the risk of violating any existing or future SDWA regulations (e.g.,
THMs, bromate).
10.3 Work Plan
The Manufacturer or FTO will be responsible for establishing the testing operating parameters, on the
basis of the Initial Operations testing. Many of the water quality parameters described in this task will
be measured on-site by the NSF-qualified FTO or by local community personnel properly trained by
the FTO. Analysis of the remaining water quality parameters will be performed by a state-certified or
third party- or EPA-accredited analytical laboratory. The methods to be used for measurements of
water quality parameters in the field are listed in the Analytical Methods section in Table 2. The
analytical methods utilized in this study for on-site monitoring of feed water and treated water qualities
are described in Task 6, Quality Assurance/Quality Control (QA/QC). Where appropriate, the
Standard Methods reference numbers for water quality parameters are provided for both the field and
laboratory analytical procedures. EPA Methods for analysis of the parameters listed in Table 2 also
may be used.
Samples of the feed water shall be collected and analyzed for background SOC concentrations. Feed
water shall also be sent to the state-certified or third party- or EPA- accredited laboratory to conduct
spiking QA/QC analysis (see Task 6). The approved analytical methods for SOCs vary, depending on
the SOC(s) of interest. A state-certified or third party- or EPA-accredited laboratory should be using
an approved EPA or Standard Method for SOC analysis. Peer-reviewed and proposed methods for
SOC determination are also allowable if approved EPA or Standard Methods are not available. The
preservatives needed for sample collection also vary for different SOC(s) and the state-certified or third
party- or EPA-accredited should fully document sampling requirements for the FTO.
Any disinfectant added upstream of the ozone addition point will affect the ozone demand; therefore, an
agreement between NSF, the manufacturer, and the FTO must be made to determine whether or not to
allow pre-disinfection prior to ozonation during the Verification Testing Period. If a pre-disinfectant is
used, testing shall be conducted to verify that no disinfectant residual exists at the influent of the ozone
contactor, or if a disinfectant residual does exist, a quenching solution (e.g., sodium bisulfite or hydrogen
peroxide) shall be used. The latter option (quenching) is less desirable because the concentration of the
quenching agent will have to be carefully monitored during testing to minimize over-feeding of the
quenching agent (which would result in an ozone demand).
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10.4 Analytical Schedule
Water quality data shall be collected at the intervals specified in Table 1. Additional sampling and data
collection may be performed at the discretion of the Manufacturer and their designated FTO. Sample
collection protocol shall be defined by the FTO in the PSTP. Algae sampling is not required for
systems using groundwater sources.
For water quality samples that will be shipped to a state-certified or third party- or EPA-accredited
laboratory for analysis, the samples shall be collected in appropriate containers (containing preservatives
as needed) prepared by the laboratory. These samples shall be preserved, stored, shipped, and
analyzed in accordance with appropriate procedures and holding times, as specified by the laboratory.
Original field sheets and chain-of-custody forms shall accompany all samples shipped to the laboratory.
Copies of field sheets and chain-of custody forms for all samples shall be provided to NSF.
10.5 Evaluation Criteria
The performance of the ozone or ozone/AOP equipment will be compared to the Manufacturer's
statement of performance objectives for the equipment being tested.
11.0 TASK 3: DOCUMENTATION OF OPERATING CONDITIONS AND TREATMENT
EQUIPMENT PERFORMANCE
11.1 Introduction
Throughout the Verification Testing period, operating conditions shall be documented. This shall include
descriptions of pretreatment chemistry and filtration performance for the equipment processes, if used,
and their operating conditions. The performance of the ozone equipment (including ozone generators),
air preparation system(s), off-gas destruct unit(s), injection equipment, ozone monitor(s), and
contactor(s)) as well as UV light and hydrogen peroxide equipment shall be documented. The total
volume of water treated and the total power usage for all equipment associated with the ozone or
ozone/AOP system shall also be recorded.
11.2 Objectives
The objective of this task is to accurately and fully document the operating conditions during treatment,
and the performance of the equipment. This task is intended to collect data that describe operation of
the equipment and information that can be used to develop cost estimates for operation of the
equipment.
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11.3 Work Plan
During Verification Testing, treatment equipment operating parameters for both pretreatment and
ozonation shall be monitored and recorded on a routine basis by the NSF-qualified FTO or by local
community personnel properly trained by the FTO.
Table 3 outlines some of the operating parameters that shall be monitored throughout Verification
Testing. Operating parameters, in addition to those listed in Table 3, may be needed to adequately
assess the operating conditions of the ozone or ozone/AOP equipment. These additional parameters
shall be identified by the Manufacturer and the FTO and agreed upon by the Manufacturer and NSF.
Examples of operational parameters which shall be monitored are:
water flow rates
gas flow rates
water pressures
gas pressures
water temperatures
gas temperatures
ozone operating voltage
ozone production power consumption
air preparation power consumption or other consumables for air preparation
oxygen feed rate (if applicable) and other pertinent operation information
performance of oxygen generation or oxygen feed equipment
ozone electrical frequency, if variable
amperage of ozone equipment
weight ratio of hydrogen peroxide (if used) to ozone
On a daily basis, the operator shall note and record whether any visual effects of ozonation are apparent
in the treated water or on piping or vessels that convey or hold treated water. This may include surface
scum, precipitation of metals, color changes, etc. At the end of the test period if an ozone contact
chamber is provided with the equipment and if it is accessible, the contact chamber shall be inspected
for deposits of scum, precipitation of metals, or color changes, and this information shall be noted in the
Verification Testing report.
11.4 Schedule
Table 3 presents the schedule and recording data required for ozone and AOP systems. The length of
time (hours) of operation (during Verification Testing) shall be recorded for all of the ozone and AOP
equipment.
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11.5 Evaluation Criteria
Where applicable, the data developed from this task will be compared to statements of performance
objectives. If no relevant statement of performance capability exists, results of operating and
performance data will be tabulated for inclusion in the Verification Report.
12.0 TASK 4: DOCUMENTATION OF EQUIPMENT PERFORMANCE: SOC
OXIDATION
12.1 Introduction
The ability of ozone and AOP equipment to oxidize SOCs can be assessed by measuring the initial and
final SOC concentrations and computing the change (see Chapter 1 of the Protocol for Equipment
Verification Testing of Synthetic Organic Contamination Removal).
12.2 Experimental Objectives
The objective of this task is to determine the effectiveness of ozone or ozone/AOP equipment for SOC
oxidation at small systems.
12.3 Work Plan
The FTO shall conduct water quality sampling and calculate the reduction in SOC concentration(s)
resulting from ozone or AOP treatment. Task 4 shall be conducted during the Verification Testing runs
conducted in Task 1, 2, and 3.
The background or naturally occurring concentration of the SOC(s) of interest shall be determined
during either Task A or Task 2 so that the background concentration of SOC(s) in the feed water is
known prior to conducting Verification Testing. If the background SOC concentration is too low to
adequately show or calculate a percentage removal, spiking of SOC(s) during the 200 hours of
Verification Testing will be necessary.
Multiple SOC(s) can be simultaneously evaluated during Verification Testing; however, ozone or AOPs
may preferentially react with naturally occurring organics or other SOCs present in solution, thereby
reducing its ability to oxidize the SOC(s) of interest. Thus, it is possible that the desired outcome of
Verification Testing may not occur during some multiple SOC evaluations.
If the ozone or AOP equipment is already being used at a site and has been approved by the State (if
necessary), a manufacturer may want to verify its performance with Verification Testing. This can be
accomplished by conducting the tests at the location if naturally occurring or background SOC
concentrations are high enough for accurately and precisely calculating reductions. This would not
compromise the water quality in any way. However, if SOCs must be spiked for testing, this poses a
potential threat to the water quality. In this case, identical equipment would have to be brought on site
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and spiked SOC studies would have to be conducted with this additional equipment. The effluent of
this spiked SOC testing would be treated as described in Section 12.3.5.
12.3.1 Types of SOCs
This ETV plan is not designed to guide Verification Testing for volatile organic compounds
(VOCs). Examples of VOCs include benzene and vinyl chloride, and a list of regulated VOCs
(i.e., Phase I) can be found in Pontius (1998).
Oxidation of SOCs by ozone or AOPs can form by-products. The presence and concentration
of these by-products is of interest because some of the by-products are considered as potential
health concerns as a result of long-term exposure. Therefore, it is necessary that one treated
water sample be collected during each Verification Test period, and this sample will be analyzed
for the presence and concentration of by-products. This can be accomplished by conducting a
scan of semi-volatile organic by-products by using gas chromatography/mass spectrometry by a
state-certified or third party- or EPA-accredited analytical laboratory that has scanning and
compound library matching capabilities. Some of the common by-products include: aldehydes,
ketones, and for atrazine, deethylatrazine and deisopropylatrazine.
12.3.2 Spiking Protocols
Spiking of SOCs shall be used in concentrations sufficient to permit the highest level of stress for
the Manufacturer's equipment. Some guidelines for spiking include:
SOC spiking shall begin at start-up of the treatment equipment and shall continue for the
200 hours of Verification Testing.
The SOC(s) feed solution shall be prepared by diluting the SOC into dilution water that
is distilled or deionized and oxidant demand-free.
The container used for storing the feed SOC solutions shall be chemically inert (i.e., not
reactive or adsorbable with the SOC(s) of interest).
The feed solution shall be gently and continuously mixed throughout the Verification Test
Run.
The SOC spiked solution shall be fed using an adjustable rate chemical feed pump.
Use of an in-line static mixer to mix this solution into the feedwater is recommended.
SOC samples shall be collected in sample bottles prepared (i.e., preservatives added, if
necessary) by the analytical laboratory performing the analysis.
Multiple SOCs can be contained in the same stock feed container (i.e., having only one
feed solution).
The concentration of SOC(s) applied to the feed water shall be agreed upon by the
Manufacturer, NSF, and the FTO.
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12.3.3 Test Operation and Sample Collection
If spiking is necessary, the SOC(s) of interest shall be continuously applied to the feed water
during the 200 hours of Verification Testing. If an ozone or ozone/AOP system is temporarily
shut down, then the spiking solution feed equipment should also be shut down and then started
again when the ozone or ozone/AOP system is started again.
During the Verification Testing period, SOC samples of the feed water and treated water shall
be collected once per 25 hours of operation. If the ozone or ozone/AOP system is not
operating continuously, then the SOC samples shall be collected after the mid-point of the run in
which the equipment is being operated. For example, if the ozone system is operated in 8 hour
shifts, the SOC samples shall be collected after the fourth hour of operation.
During sample collection, minimal sample agitation and exposure to the atmosphere shall occur.
An overflowing technique for filling samples bottles is recommended. A piece of Tygon tubing
attached to the sample port can be placed such that the unattached end of the tubing rests at the
bottom of the sampling container. As the sample fills the bottle, the end of the tubing remains at
the bottom of the container. Once the sampling container is overflowing, the tubing can slowly
be removed from the container. The lid should be placed on the container immediately after the
sample tube is removed from the sample container.
Since some SOC samples require the use of a preservative in the sampling container, the
overflowing technique is not applicable to all SOC(s). If this is the case, the Tygon tubing is still
recommended (to minimize sample agitation during collection); however, the tubing should be
removed prior to the point at which the sample would overflow the container.
Samples shall be delivered to a state-certified or third party- or EPA-accredited analytical
laboratory for analysis using approved EPA or Standard Methods for measuring the SOC
concentrations of interest.
12.3.4 Experimental Quality Control
Duplicates of the feed and treated water samples shall be collected for at least two of the
sampling events during a Verification Test Run. A process control and trip control sample shall
also be collected as part of Task 6.
The experimental quality control shall be verified by checking the flow rate of the spiked solution
once per day. To ensure the proper feed rate of the spiked SOC solution to the ozone or AOP
system, use a stopwatch to measure the time required to collect a specified volume of the feed
solution from the feed system. This requires that the feed line to the contactor be temporarily
disconnected so that the pumping rate of the stock SOC solution can be measured. Typically, a
graduated cylinder is used to collect the pumped SOC sample and the size of the graduated
cylinder is such that the length of collection time exceeds 10 seconds.
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12.3.5 Treatment of Effluent
Treated water resulting from SOC spiking experiments using ozone or ozone/AOP equipment
shall not be distributed to the public. The treated water might have to be passed through a
granular activated carbon (GAC) filter for removal of residual SOCs during the 200 hours of
Verification testing. The size of the GAC filter and the type of carbon would need to be
determined by the Manufacturer and FTO and approved by the State's pollution control
authority. Since some SOCs are more readily adsorbed than others, and there may be
competition between SOCs for adsorption sites on the carbon, GAC filters would have to be
designed on a case-by-case basis. The discharge of treated water shall be directed to a
location that is approved by the State.
12.4 Analytical Schedule
Feed water and treated water SOC samples shall be collected once per 25 hours of operation.
Duplicate sampling is required for two of the samples of Verification Testing.
12.5 Evaluation Criteria
The difference in concentration of the SOC(s) of interest in the feed and treated waters will be
compared to the Manufacturer's statement of performance objectives for the equipment being tested.
The ozone production and power usage may also be used to evaluate the performance of the
equipment.
13.0 TASK 5: DATA MANAGEMENT
13.1 Introduction
The data management system used in the Verification Testing program shall involve the use of computer
spreadsheet software and manual recording of the operational parameters for the water treatment
equipment on a daily basis.
13.2 Experimental Objectives
The objectives of this task are: 1) to establish a viable structure for the recording and transmission of
field testing data so the FTO will provide sufficient and reliable operational data for verification
purposes, and 2) to provide the information needed for a statistical analysis of the data, as described in
the "EPA/NSF ETV Protocol For Equipment Verification Testing For The Removal Of Synthetic
Organic Chemical Contaminants: Requirements For All Studies."
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13.3 Work Plan
The following protocol has been developed for data handling and data verification by the FTO. Where
possible, a Supervisory Control and Data Acquisition (SCADA) system should be used for automatic
entry of testing data into computer databases. Specific parcels of computer databases for operational
and water quality parameters should then be downloaded by manual importation into Excel (or similar
spreadsheet software) as a comma delimited file. These specific database parcels will be identified
based upon discrete time spans and monitoring parameters. In spreadsheet form the data will be
manipulated into a convenient framework to allow analysis of water treatment equipment operation.
Backup of the computer databases to diskette should be performed on a monthly basis at a minimum.
When SCADA systems are not available, direct instrument feed to data loggers and laptop computers
shall be used when appropriate.
For parameters for which electronic data acquisition is not possible, field testing operators will record
data and calculations by hand in laboratory notebooks (daily measurements will be recorded on
specially-prepared data log sheets as appropriate). Each notebook must be permanently bound with
consecutively numbered pages. Each notebook must indicate the starting and ending dates that apply to
entries in the logbook. All pages will have appropriate headings to avoid entry omissions. All logbook
entries must be made in black water insoluble ink. All corrections in any notebook shall be made by
placing one line through the erroneous information. Products such as "correction fluids" are never to be
utilized for making corrections to notebook entries. Operating logs shall include a description of the
water treatment equipment (description of test runs, names of visitors, description of any problems or
issues, etc.); such descriptions shall be provided in addition to experimental calculations and other
items. The original notebooks will be stored on-site; photocopies will be forwarded to the project
engineer of the FTO at an agreed upon schedule. This protocol will not only ease referencing the
original data, but will also offer protection of the original record of results.
The database for the project will be set up in custom-designed spreadsheets. The spreadsheets will be
capable of storing and manipulating each of the monitored water quality and operational parameters
from each task, each sampling location, and each sampling time. All data from the laboratory
notebooks and data log sheets will be entered into the appropriate spreadsheets. Data entry will be
conducted on-site by the designated field testing operators. All recorded calculations will also be
checked at this time. Following data entry, the spreadsheet will be printed out and the print-out will be
checked against the handwritten data sheet. Any corrections will be noted on the hard-copies and
corrected on the screen, and then a corrected version of the spreadsheet will be printed out. Each step
of the verification process will by initialed by the field testing operator or engineer performing the entry
or verification step.
Each experiment (e.g. verification run) will be assigned a run number that will then by tied to the data
from that experiment through each step of data entry and analysis. As samples are collected and sent to
state-certified or third party- or EPA-accredited laboratories, the data will be tracked by use of the
same system of run numbers. Data from the outside laboratories will be received and reviewed by the
field testing operator. These data will be entered into the data spreadsheets, corrected, and verified in
the same manner as the field data.
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13.4 Statistical Analysis
Water quality developed from grab samples collected during test runs according to the Analytical
Schedule in Task 2 of this Test Plan shall be analyzed for statistical uncertainty. The FTO shall calculate
95% confidence intervals for grab sample data obtained during Verification Testing as described in
"EPA/NSF ETV Protocol For Equipment Verification Testing For The Removal Of Synthetic Organic
Chemical Contaminants: Requirements For All Studies." Statistical analysis could be carried out for a
large variety of testing conditions.
The statistics developed will be helpful in demonstrating the degree of reliability with which water
treatment equipment can attain quality goals. Information on the differences in feed water quality
variations for entire test runs versus the quality produced during the optimized portions of the runs would
be useful in evaluating appropriate operating procedures.
14.0 TASK 6: QUALITY ASSURANCE/QUALITY CONTROL (QA/QC)
14.1 Introduction
Quality assurance and quality control of the operation of the water treatment equipment and the
measured water quality parameters shall be maintained during the Verification Testing program.
14.2 Experimental Objectives
The objective of this task is to maintain strict QA/QC methods and procedures during the ETV
Program. Maintenance of strict QA/QC procedures is important in that if a question arises when
analyzing or interpreting data collected for a given experiment, this information will be possible to verily
exact conditions at the time of testing.
14.3 Work Plan
Equipment flow rates and associated signals should be verified and verification recorded on a routine
basis. Daily routine walk-throughs during the testing program will be used to verily that each piece of
equipment or instrumentation is operating properly. Particular care shall be taken to verily that
chemicals are being fed at the defined flow rate, and into a flow stream that is operating at the expected
flow rate. In addition, the operation of the air preparation equipment or the liquid oxygen supply for the
ozone generator, and the ozone generator, shall be checked in each walkthrough and relevant operating
data shall be recorded and checked to verify that operating conditions are within the acceptable
operating range for the equipment or processes involved. In-line monitoring equipment such as flow
meters, etc. will be checked as indicated below to verily that the readout matches with the actual
measurement (i.e., flow rate) and that the signal being recorded is correct. The items listed are in
addition to any specified checks outlined in the analytical methods.
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When collecting water quantity data, all system flow meters will be calibrated using the classic bucket
and stopwatch method where appropriate. Hydraulic data collection will include the measurement of
the finished water flow rate by the "bucket test" method. This would consist of filling a calibrated vessel
to a known volume and measuring the time to fill the vessel with a stopwatch. This will allow for a direct
check of the system flow measuring devices.
14.3.1 Daily QA/QC Verifications
On-line turbidimeter: Clean out reservoirs and recalibrate, check the flow rate (verified
volumetrically over a specific time period).
On-line pH meters (standardize and recalibrate).
Chemical feed pump flow rates (check and verify components).
On-line turbidimeter readings checked against a properly calibrated bench model.
14.3.2 QA/QC Verifications Performed Every Two Weeks
On-line flow meters/rotameters: Clean equipment to remove any debris or biological
buildup and verify flow volumetrically to avoid erroneous readings.
Chemical feed pump flow rates (verify volumetrically over a specific period of time).
14.3.3 QA/QC Verifications Performed Every Testing Period
Tubing: Verify that all tubing and connections are in good condition and replace if
necessary. For surface water systems, microbial growth could occur between seasonal
verification test runs, so replacement of tubing prior to each verification test may be
necessary.
Differential pressure transmitters (verify gauge readings and electrical signals using a
pressure meter).
14.4 On-Site Analytical Methods
The analytical method utilized in this study for on-site monitoring of raw water and treated water quality
are described in the following section. Use of either bench-top or in-line field analytical equipment will
be acceptable for the verification testing; however, in-line equipment is recommended for ease of
operation.
14.4.1 pH
Analysis for pH shall be performed according to Standard Method 4500-If B or EPA Method
150.1/150.2. A three-point calibration of any pH meter used in this study will be performed
once per day when the instrument is in use. Certified pH buffers in the expected range shall be
used. The pH probe shall be stored in the appropriate solution defined in the instrument manual.
Transport of carbon dioxide across the air-water interface can confound pH measurement in
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poorly buffered waters. If this is a problem, measurement of pH in a confined vessel is
recommended to minimize the effects of carbon dioxide loss with the atmosphere.
14.4.2 Turbidity Analysis
Turbidity analyses shall be performed according to Standard Method 2130 or EPA Method
180.1 with either a bench-top or in-line turbidimeter. Grab samples shall be analyzed using a
bench-top turbidimeter; readings from this instrument will serve as reference measurements
throughout the study. The bench-top turbidimeter shall be calibrated within the expected range
of sample measurements at the beginning of Verification Testing and on a weekly basis using
primary turbidity standards of 0.1, 0.5 and 3.0 NTU. Secondary turbidity standards shall be
used on a daily basis to verify calibration of the turbidimeter and to recalibrate when more than
one turbidity range is used.
During each verification testing period, the bench-top and in-line turbidimeters will be left on
continuously. Once each turbidity measurement is complete, the unit will be switched back to
its lowest setting. All glassware used for turbidity measurements will be cleaned and handled
using lint-free tissues to prevent scratching. Sample vials will be stored inverted to prevent
deposits from forming on the bottom surface of the cell.
The Field Testing Organization shall be required to document any problems experienced with
the monitoring turbidity instruments, and shall also be required to document any subsequent
modifications or enhancements made to monitoring instruments.
14.4.2.1 Bench-top Turbidimeters. The method for collecting grab samples will consist of
running a slow, steady stream from the sample tap, triple-rinsing a dedicated sample beaker in
this stream, allowing the sample to flow down the side of the beaker to minimize bubble
entrainment, double-rinsing the sample vial with the sample, carefully pouring from the beaker
down the side of the sample vial, wiping the sample vial clean, inserting the sample vial into the
turbidimeter, and recording the measured turbidity.
When cold water samples cause the vial to fog and prevent accurate readings, allow the vial to
warm up by submersing partially into a warm water bath for approximately 30 seconds.
14.4.2.2 In-line Turbidimeters. In-line turbidimeters may be used during verification testing
and must be calibrated as specified in the manufacturer's operation and maintenance manual. It
will be necessary to periodically verify the in-line readings using a bench-top turbidimeter;
although the mechanism of analysis is not identical between the two instruments the readings
should be comparable. Should these readings suggest inaccurate readings then all in-line
turbidimeters should be recalibrated. In addition to calibration, periodic cleaning of the lens
should be conducted using lint-free paper, to prevent any particle or microbiological build-up
that could produce inaccurate readings. Periodic verification of the sample flow should also be
performed using a volumetric measurement. Instrument bulbs should be replaced on an as-
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needed basis. It should also be verified that the LED readout matches the data recorded on the
data acquisition system, if the latter is employed.
14.4.3 Dissolved Ozone
The dissolved ozone concentration can be measured using an indigo bleaching technique, such
as Standard Method 4500-03 B or the HACH Indigo AccuVac method. When sampling for
dissolved ozone, it is important to minimize sample agitation and transfer from one container to
another. One good sampling technique is to collect the sample directly from the sample tap. If
HACH AccuVac vials are used, the tip of the AccuVac can be placed directly into the tap
opening where the water is flowing. Apply pressure and snap the tip while it is inside the sample
tap opening. The vacuum in the AccuVac vial will draw the water sample into the AccuVac.
Once the AccuVac is filled, remove the AccuVac from the sample tap and analyze according
the HACH instructions. If necessary, a short piece (i.e., less than 2 feet) of Tygon tubing can
be attached to the sample tap for dissolved ozone sampling. If HACH AccuVac vials are not
used, use of tubing attached to the sample port for sample collection is recommended to
minimize sample agitation and mixing. This tubing should be Tygon and should be no longer
than 2 feet in length.
Another method for measuring dissolved ozone is a dissolved ozone probe. These probes can
be placed in the process stream to provide continuous measurements of ozone residuals.
Check the probe tip daily to ensure that the membrane has been installed properly and that
there are no air bubbles underneath the membrane. Also, check that the pressure and flow rate
within the contactor are within the appropriate range for the probe being used. The
performance of the probe shall be verified on a daily basis by measuring the dissolved ozone
concentration with one of the indigo bleaching methods to ensure that the probe is functioning
properly.
A third method for measuring dissolved ozone concentrations is an on-line analyzer which uses
UV spectrophotometry to measure the gas-phase concentration of ozone which has been
stripped from a liquid sample. These analyzers then correlate the gas-phase ozone
concentration to the dissolved ozone concentration. These analyzers are calibrated at the
factory.
14.4.4 Gas Phase Ozone
Gas phase ozone concentrations can be measured using either UV absorbance ozone monitors
or a wet-chemistry test. Ozone monitors are calibrated at the factory and provide a continuous
measure of the ozone concentration in gas phase. The wet-chemistry test method of measuring
the ozone concentration of a gas stream involves bubbling ozone through a potassium iodide
solution, acidification with sulfuric acid, and titration with sodium thiosulfate. This method is
described in detail in Gordon et al. (1992). During each Verification Test, a wet-chemistry
measurement of the ozone feed gas shall be conducted to independently check that the ozone
monitor is functioning properly. If ozone monitors are not available, wet-chemistry tests shall be
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performed three times per day or three times per shift to measure the ozone concentration in the
feed gas and off gas.
14.4.5 Hydrogen Peroxide
The concentration of hydrogen peroxide can be measured using one of two spectrophotometric
methods: 1) cobalt-bicarbonate and 2) peroxidase. The cobalt-bicarbonate method, described
in Masschelein el al. (1977), can be used to measure up to 2 mg/L hydrogen peroxide at 260
nm, whereas the peroxidase method, described in Bader el al. (1988), can be used to measure
up to 1.7 mg/L hydrogen peroxide at 551 nm.
At low pH, ozone and peroxide can be in solution at the same time, because the reaction rate is
slow. The presence of ozone interferes with any hydrogen peroxide analysis; therefore, to
measure the amount of hydrogen peroxide in the AOP system, ozone production shall be
temporarily terminated while hydrogen peroxide samples are being collected and analyzed.
To ensure the proper feed rate of hydrogen peroxide to the ozone/AOP system, use a
stopwatch to measure the time required to collect a specified volume of hydrogen peroxide
stock solution from the feed system. This requires that the hydrogen peroxide feed line to the
contactor be temporarily disconnected so that the pumping rate of the stock hydrogen peroxide
solution can be measured. Typically, a graduated cylinder is used to collect the pumped
hydrogen peroxide sample and the size of the graduated cylinder is such that the length of
collection time exceeds 10 seconds.
The strength of the peroxide feed solution can also be determined from the peroxide supplier's
shipping information, as long as the peroxide being used for testing has not been: 1) diluted by
the user; 2) exposed to contamination (which would affect its strength); 3) stored for longer than
one year; or, 4) stored at temperatures greater than 77ฐF.
14.4.6 Temperature
Readings for temperature shall be conducted in accordance with Standard Method 2550.
Raw water temperatures shall be obtained at least once daily. The thermometer shall have a
scale marked for every 0.1 ฐC, as a minimum, and should be calibrated weekly against a
precision thermometer certified by the National Institute of Standards and Technology (NIST),
(A thermometer having a range of -1ฐC to +51ฐC, subdivided in 0.1ฐ increments, would be
appropriate for this work.)
14.4.7 Color
True color shall be measured with a spectrophotometer at 455 nm, using an adaptation of the
Standard Methods 2120 procedure. Samples shall be collected in clean plastic or glass bottles
and analyzed as soon after collection as possible. If samples can not be analyzed immediately
they shall be stored at 4ฐC for up to 24 hours, and then warmed to room temperature before
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analysis. The filtration system described in Standard Methods 2120 C shall be used, and
results should be expressed in terms of PtCo color units.
14.4.8 Dissolved Oxygen
Analysis for dissolved oxygen shall be performed according to Standard Method 4500-0 using
an iodometric method or the membrane electrode method. The techniques described for
sample collection must be followed very carefully to avoid causing changes in dissolved oxygen
during the sampling event. Sampling for dissolved oxygen does not need to be coordinated with
sampling for other water quality parameters, so dissolved oxygen samples should be taken at
times when immediate analysis is going to be possible. This will eliminate problems that may be
associated with holding samples for a period of time before the determination is made.
If the sampling probe is not mounted such that the probe is continuously exposed to the process
stream, then care must be taken when measuring the dissolved oxygen concentration. For best
results, collect the dissolved oxygen sample with minimal agitation and measure the dissolved
oxygen concentration immediately. If possible, measure the dissolved oxygen under a
continuous stream of sample by placing the tip of the probe in the sample container, allowing the
sample to overflow the container while the probe reaches equilibrium (usually less than 5
minutes).
14.5 Chemical and Biological Samples Shipped Off-Site for Analysis
The analytical methods that shall be used during testing for chemical and biological samples that are
shipped off-site for analyses are described in the section below.
14.5.1 Organic Samples
Samples for analysis of total organic carbon (TOC), UV254 absorbance, and dissolved organic
carbon (DOC) shall be collected in glass bottles supplied by the state-certified or third party- or
EPA-accredited laboratory and shipped at 4 ฐC to the analytical laboratory within 24 hours of
sampling. These samples shall be preserved in accordance with Standard Method 5010 B.
Storage time before analysis shall be minimized, according to Standard Methods.
14.5.2 Algae
Algae samples shall be preserved with Lugol's solution after collection, stored and shipped in a
cooler at a temperature of approximately 2 to 8 ฐC, and held at that temperature range until
counted.
14.5.3 Inorganic Samples
Inorganic chemical samples, including alkalinity, shall be collected and preserved in accordance
with Standard Method 2320 B. The samples shall be refrigerated at approximately 2 to 8 ฐC.
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Samples shall be processed for analysis by a state-certified or third party- or EPA-accredited
laboratory within 24 hours of collection. The laboratory shall keep the samples at
approximately 2 to 8 ฐC until initiation of analysis.
Bromate samples shall be collected in sampling containers supplied by the state-certified or third
party- or EPA-accredited laboratory. Sample collection and storage requirements are outlined
in EPA Method 300.1 or shall be provided by the laboratory conducting the analysis.
14.5.4 SOC Analysis
Analysis of SOCs requires a trained analyst using sophisticated instrumentation. Only state-
certified or third party- or EPA-accredited laboratories shall analyze SOC samples that are
collected during Initial Operations and Verification Testing. As stated in the "EPA/NSF ETV
Protocol For Equipment Verification Testing For The Removal Of Synthetic Organic Chemical
Contaminants: Requirements For All Studies," approved methods for some SOCs may not be
available, and for these SOCs, a proposed, peer-reviewed method may be used.
There are many approved methods for analyzing Phase II and Phase V SOCs. Depending on
the laboratory, gas chromatography (GC) or high performance liquid chromatography (HPLC)
methods can be used to analyze SOCs. For both methods, the equipment is highly specialized
and proper operation of these instruments requires a skilled laboratory technician.
Mass spectrometry is not required for all SOCs, however it is recommended for SOC
identification. Retention times relative to the internal standard can also be used to identify
SOCs. Either peak height or peak area can be used to determine the SOC concentrations.
SOCs shall be analyzed with an internal standard similar in analytical behavior and not affected
by the matrix for QA/QC. An appropriate surrogate standard shall also be used during SOC
analysis. Data pertaining to the internal and surrogate standards shall be reported with the SOC
concentrations of the samples being analyzed. A method blank shall also be prepared and
analyzed by the state-certified or third party- or EPA-accredited laboratory to verify minimal
contamination in the laboratory.
At least three standards shall be used to develop the standard curve for SOC quantification and
these three standards shall be extracted and analyzed (by GC or HPLC) on the same day as the
samples.
During each Verification Test period, one treated water sample shall be analyzed by scanning
for the presence and concentration of potential by-products of SOC oxidation by ozone. Gas
chromatography followed by mass spectrometry can be used to identify many of the organic by-
products formed by ozonation. The spectra obtained by this analysis can be matched to a
compound library in a computer database to identify the various byproducts. This analysis shall
be performed by a state-certified or third party- or EPA-accredited analytical laboratory. The
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scan should be targeted toward the SOC of interest, and the potential by-products associated
with ozonation of that SOC.
Spiked samples shall be analyzed once, at the beginning of each Verification Test Run. The
laboratory shall spike a feed water sample with a known quantity of the SOC(s) of interest and
analyze this spiked sample. SOC analysis of the spiked sample will indicate if there are any
interferences present in the feed water. The broad scan can be a performance-based scan (i.e.,
the scan is not used for compliance, and therefore undergoes less rigorous QA/QC and is less
expensive than a compliance based scan analysis.)
14.6 Experimental QA/QC Samples
14.6.1 Process Control
A second round of testing shall be carried out using procedures identical to the steps outlined
above, but without operating the ozone or ozone/AOP equipment. The purpose of this testing is
to evaluate any cumulative effects produced by the equipment, the spiking and sampling
procedures, and the sample handling procedures on SOCs. The process control samples
should show minimal loss of SOC(s) relative to the trip control sample. Significant loss of SOC
concentrations in the process control sample indicates that some aspect of the process other
than ozone oxidation contributes to SOC removal. Re-testing is required when this is shown to
occur.
14.6.2 Trip Control
For tests utilizing spiked SOCs, a replicate or subsample of the spiking solution shall
accompany the actual spiking solution from the analytical laboratory. This replicate sample shall
undergo all of the processes used on the actual solution including dose preparation, shipping,
preparation for spiking, and return to the laboratory for analysis. The trip control samples
should show minimal loss of SOC(s). Significant decreases in the SOC concentration of the trip
control sample indicates that some step in handling the solution contributed to the reduction in
the SOC concentration. The seeding tests must be repeated when significant loss of SOCs in
the trip control sample is observed.
15.0 OPERATION AND MAINTENANCE
The FTO shall obtain the Manufacturer-supplied Operation and Maintenance (O&M) Manual to
evaluate the instructions and procedures for their applicability during the verification testing period. The
following are recommendations for criteria for O&M Manuals for drinking water treatment equipment
employing ozone treatment.
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15.1 Maintenance
The Manufacturer shall provide readily understood information on the recommended or required
maintenance schedule for each piece of operating equipment including, but not limited to, the following,
where applicable:
ozone generator (dielectric replacement)
ozone diffusers or injection port, control valves
ozone destruct unit (catalyst replacement)
gas phase ozone monitors (for feed gas and off gas)
dissolved ozone monitoring equipment
cooling water equipment
air preparation unit or oxygen feed system for ozone generation
gas and liquid rotameters
UV lamps and other relevant equipment
peroxide feed equipment
other equipment such as pumps and valves
The Manufacturer shall also provide readily understood information on the recommended or required
maintenance for non-mechanical or non-electrical equipment, including but not limited to, the following,
where applicable:
piping
contactor chamber
15.2 Operation
The Manufacturer shall provide readily understood recommendations for procedures related to proper
operation of all equipment. Among the operating aspects that should be addressed in the O&M manual
are:
Ozone Generator
air preparation or oxygen feed requirements (moisture content, filtration requirements, flow rate)
cooling water requirements (flow)
range of variable voltage for adjusting ozone output
proper sequence of operation for start-up and shut-down
proper sequence of operation for initial start-up or for re-start after maintenance
Ozone Monitors (Gas Phase)
temperature and pressure compensation
zeroing and calibration procedures
proper sequence of operation for start-up and shut-down
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Ozone Destruct Units
heater and/or blower requirements
catalyst requirements
proper sequence of operation for start-up and shut-down
Air Preparation or Oxygen Feed Systems
desiccant requirements and replacement procedures
filters (maintenance and replacement schedule)
proper sequence of operation for start-up and shut-down
supplemental gas (air or nitrogen) flow rate, pressure, and temperature.
Cooling Water System
maintenance of proper temperature
monitoring cooling water flow
pump maintenance
proper sequence of operation for start-up and shut-down
maintenance of recirculation equipment, if cooling water is recirculated
Ozone Contactor Systems
maintenance schedule and procedures
replacement procedures
UV lamps
hours of operation (verification procedures)
UV irradiance (calibration and verification procedures)
maintenance schedule and procedures
replacement procedures
proper sequence of operation for start-up and shut-down
Hydrogen Peroxide Feed System
procedures for variable speed adjustments to pump
information about proper tubing type and size
anticipated schedule for tubing replacement
storage information (i.e., safety, container type, container material, temperature, length of storage
time) for stock hydrogen peroxide solutions
proper sequence of operation for start-up and shut-down
Control Valves
open/close indication
sequence of operations
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The Manufacturer shall provide a troubleshooting guide; a simple checklist of what to do for a variety of
problems, including but not limited to:
no flow to unit
sudden change in flow to unit
no electric power
automatic operation (if provided) not functioning
valve stuck or will not operate
16.0 REFERENCES
APHA, AWWA, and WEF (1999). Standard Methods for he Examination of Water And
Wastewater, 20th Ed., APHA, Washington, DC.
American Water Works Association Research Foundation and Compagnie Generate des Eaux (1991).
Ozone in Water Treatment Application and Engineering, Cooperative Research Report, Langlais,
B., Reckhow, D. A., and Brink, D. R, eds., Lewis Publishers, Boca Raton, FL.
Bader, FL, Sturzenegger, V., and Hoigne, J. (1988). "Photometric Method for the Determination of
Low Concentrations of Hydrogen Peroxide by the Peroxidase Catalyzed Oxidation of N,N-Diethyl-/>
Phenylenediamine (DPD)," Water Research, 22(9): 1109.
Gordon, G., Rakness, K., and Robson, C. M. (1992). "Ozone Concentration Measurement in a
Process Gas," Proceedings of the International Ozone Association Conference Ozonation for
Drinking Water Treatment, Pasadena, CA, March 10-13.
Masschelein, W., Denis, M., and Ledent, R. (1977). "Spectrophotometric Determination of Residual
Hydrogen Peroxide," Water and Sewerage Works, 124(8):69.
Pontius, F. W. (1998). "New Horizons in Federal Regulation," Journal of the American Water
Works Association, 90(3):38.
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Table 1. Water Quality Sampling and Measurement Schedule
Parameter
Sampling Location
Mandatory
(M) or
Optional
(O)
Frequency*
Surface Water
Systems
Groundwater
Systems
Temperature (ฐC)
Feed Water, Treated
water
M
3/d or 3/shift
3/d or 3/shift
Dissolved Ozone Residual (mgL)
Treated!
0
3/d or 3/shift
3/d or 3/shift
pH
Feed Water
M
3/d or 3/shift
3/d or 3/shift
Total Alkalinity (mg/L as CaC03)
Feed Water
0
1/d
1/d
Total Organic Carbon (mg/L)
Feed Water
0
1/25 hours of
ozone production
1/50 hours of
ozone production
Dissolved Organic Carbon (mg/L)
Feed Water
0
1/25 hours of
ozone production
1/50 hours of
ozone production
UV absorbance at 254 nm (1/m)
Feed Water, Treated
water
0
1/d
1/50 hours of
ozone production
Color (Pt-Co)
Feed Water, Treated
water
0
1/d
1/50 hours of
ozone production
Turbidity (NTU)
Feed Water, treated water
0
3/d or 3/shift
1/d
Bromide (mg/L)
Feed Water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
April 2002
This TSTP has not been validated in the field or reviewed for editorial clarity.
Page 3-35
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Table 1. Water Quality Sampling and Measurement Schedule (continued)
Parameter
Sampling Location
Mandatory
(M) or
Optional (O)
Frequency*
Surface Water
Systems
Groundwater
Systems
Bromate (|J.g/L)
Treated Water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
SOCs (ng/L)
Feed Water, Treated
water
M
1 per 25 hours of
ozone production
lper25houreof
ozone production
SOC scan
Feed Water, Treated
water
M
1 per Verification
test period, after
100th hour of
operation
1 per Verification
test period, after
100th hour of
operation
Total THM (|~ig/L) (chloroform,
bromoform, bromodichloromethane,
dibromochloromethane)
Treated Water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
HAA5 (ng/L) (monochloroacetic acid,
monobromoacetic acid, dichloroacetic
acid, dibromoacetic acid,
trichloroacetic acid)
Treated Water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
Iron(jjg/L)
Feed Water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
Dissolved Manganese (|_ig/L)
(Manganese concentration passing
through 0.2 |j,m filter)
Feed Water, Treated
water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
Total Manganese (|_ig/L)
Feed Water, Treated
water
0
1/50 hours of
ozone production
1/50 hours of
ozone production
April 2002
This TSTP has not been validated in the field or reviewed for editorial clarity.
Page 3-36
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Table 1. Water Quality Sampling and Measurement Schedule (continued)
Parameter
Sampling Location
Mandatory
(M) or
Optional (O)
Frequency*
Surface Water
Systems
Groundwater
Systems
Total Sulfides
Feed Water
O
1/d
1/d
Dissolved Oxygen
Feed Water, Treated
water
O
1/50 hours of
ozone production
1/50 hours of
ozone production
Hydrogen Peroxide (mg/L)
Stock Solution,
Treated Water
Mff
1/50 hours of
ozone production
1/Verification Test
Period
1/50 hours of
ozone production
1/Verification Test
Period
Quenching Solution (mg/L) (e.g.,
hydrogen peroxide)
Feed Water
M
1/d
1/d
Algal enumeration and species
Feed Water
O
1 per Verification
Test Period
Not Required
Calcium (mg/L as CaC03)
Feed Water
O
1/50 hours of
ozone production
1/50 hours of
ozone production
Total Hardness (mg/L as CaC03)
Feed Water
O
1/50 hours of
ozone production
1/50 hours of
ozone production
* 3/d or 3/shift means that the water quality parameter shall be measured either 3 times per day if ozone production is continuous over the 200 hours of
Verification Testing, or 3 times per staffed shift if ozone production is periodically terminated or interrupted, and the length of time of ozone production is less than
24 hours. 1/50 hours of ozone production means that the water quality parameter shall be measured once per each 50 hours of ozone production, regardless of
interruptions in ozone production, f The dissolved ozone concentration should be measured at sampling ports within the ozone contactor or immediately at the
outlet of the ozone contactor. If the ozone decay coefficient is being determined, at least two sampling ports will need to be sampled, ff The peroxide
concentration of the stock solution shall be checked at the prescribed frequency. The peroxide concentration within the contactor shall be checked once during or
immediately prior to the verification testing period, while the ozone equipment is not operating. Peroxide monitoring within the contactor will require that samples
be withdrawn at appropriate sampling ports at the end or outlet of the contactor.
April 2002
This TSTP has not been validated in the field or reviewed for editorial clarity.
Page 3-37
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Table 2. Analytical Methods
Parameter
Facility
Standard Methods number
or Alternative Reference1
EPA Method2
Temperature (ฐC)
On-site
2550 B
Dissolved Ozone
Residual (mg/L)
On-site
4500 03 B; HACH Indigo
Blue Method*
pH
On-site
4500 IT
150.1/150.2
Total Alkalinity (mg/L
as CaC03)
Lab
2320 B
Phase II and Phase V
SOCs
Lab
6252, 6410, 6420, 6431,
6440, 6610, 6630, 6640,
6651
525.2, 505, 515.1,
531.1, 547, 548.1,
549.1, 1613
Total Organic Carbon
(mg/L)
Lab
5310 C
Dissolved Organic
Carbon (mg/L)
Lab
5310 C
UV absorbance at 254
nm (1/m)
Lab
5910 B
Color (Pt-Co)
Lab
2120 C
110.2
Turbidity (NTU)
On-site
2130 B
180.1
Bromide (mg/L)
Lab
4500-Br
300.0
Bromate (|_ig/L)
Lab
300.1
Total THM (|~ig/L)
Lab
6232 B
502.2, 524.2, 551
HAA5 (ng/L)
Lab
6251 B
552.1
Iron (ng/L)
Lab
3111 B, 3113 B, 3120 B
200.7,200.8, 200.9
Total Manganese
(Hg/L)
Lab
3111 B, 3113 B, 3120 B
200.7, 200.8, 200.9
Dissolved Manganese
(|j,g/L) (Manganese
concentration passing
through 0.2 |j,m filter)
Lab
3500-Mn
3111B, 3113 B, 3120 B
Total Sulfides
Lab or
On-Site
4500-S2" D, E
Dissolved Oxygen
Lab or
On-Site
4500-0
April 2002
This TSTP has not been validated in the field or reviewed for editorial clarity.
Page 3-38
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Table 2. Analytical Methods (continued)
Parameter
Facility
Standard Methods number
or Alternative Reference1
EPA Method2
Algal enumeration and
speciation
Lab
Part 10000, Biological
Examination"!'
Parameter
Facility
Standard Methods number or
Alternative Reference1
EPA Method2
Calcium (mg/L as
CaC03)
Lab
3500-CaD, 3111 B, 3120 B
200.7
Total Hardness (mg/L
as CaC03)
Lab
2340 C
SOC scan
Lab
6410B, 6420C, 6440C
525.2 - Extended for
Broad Spectrum
1 Standard Method Source: 20th Edition of Standard Methods for the Examination of Water and Wastewater, 1999,
American Water Works Association.
2 EPA Methods Source: EPA Office of Ground Water and Drinking Water. EPA Methods are available from the
National Technical Information Service (NTIS).
* Dissolved ozone residual measurements can also be from a properly calibrated and installed dissolved ozone
monitor or properly calibrated and installed dissolved ozone monitor.
f Standard Methods does not contain a method for enumeration and speciation of algae. It does, however, contain
methods for laboratory techniques that may need to be performed for proper enumeration and speciation of the algae.
Only an experienced and qualified laboratory analyst shall conduct algal enumeration and speciation.
April 2002
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Page 3-39
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Table 3. System Operating Data
Operational Parameter
Frequency
Water Flow (gpm)
Feed Water
3/d or 3/shift
Side Stream (if applicable)
3/d or 3/shift
Cooling Water
3/d or 3/shift
Water Pressure (psig)
Inlet to Ozone System
3/d or 3/shift
Outlet of Ozone System
3/d or 3/shift
Side Stream (if applicable)
3/d or 3/shift
Cooling Water
3/d or 3/shift
Water Temperature (ฐC)
Inlet to Ozone System
3/d or 3/shift
Outlet te of Ozone System
3/d or 3/shift
Side Stream (if applicable)
3/d or 3/shift
Gas Phase Ozone
Concentration
(% wt)
Feed Gas
3/d or 3/shift
Off Gas
3/d or 3/shift
Power Usage (kw/hr)
Ozone Generator
3/d or 3/shift
Air Preparation System or Oxygen System
3/d or 3/shift
Gas Phase Ozone Feed and Off Gas Monitors
3/d or 3/shift
Cooling Water System
3/d or 3/shift
Destruct Units
3/d or 3/shift
Other pumps or motors
3/d or 3/shift
Ozone Feed Gas Temperature (ฐC)
3/d or 3/shift
Ozone Feed Gas Pressure (psig)
3/d or 3/shift
Ozone Feed Gas Flow (scfm)
3/d or 3/shift
Atmospheric Pressure (psia)
1/d
Dew Point (if using air feed system)
1/d
Ozone Production (lb/d)
Ozone Decay Rate (1/minute) (optional)
1/d
1/d
If applicable:
Peroxide feed concentration (mg/L)
Peroxide feed rate (mL/min)
Peroxide to Ozone ratio (by weight)
3/d or 3/shift
If applicable:
Purity of oxygen supply (%)
Supplemental nitrogen flow rate (scfm), pressure (psig), and temperature (ฐC)
Supplemental air flow rate (scfm), pressure (psig), and temperature (ฐC)
1/d or 1/shift
1/d or 1/shift
1/d or 1/shift
If applicable:
Operating parameters for UV-light systems (see ETV Equipment Verification
Testing Plan for Microorganism Contaminant Inactivation by Ultraviolet Based
Technology)
3/d or 3/shift
April 2002
This TSTP has not been validated in the field or reviewed for editorial clarity.
Page 3-40
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CHAPTER 4
EPA/NSF ETV EQUIPMENT VERIFICATION TESTING PLAN
FOR THE REMOVAL OF SYNTHETIC ORGANIC CHEMICAL CONTAMINANTS
BY ADSORPTIVE MEDIA PROCESSES
Prepared by:
NSF International
789 Dixboro Rd.
Ann Arbor, MI 48105
Copyright 2004 NSF International 40CFR35.6450.
Permission is hereby granted to reproduce all or part of this work,
subject to the limitation that users may not sell all or any part of the
work and may not create any derivative work therefrom. Contact ETV
Drinking Water Systems Center Manager at (800) NSF-MARK with
any questions regarding authorized or unauthorized uses of this work.
-------
TABLE OF CONTENTS
Page
1.0 APPLICATION OF THIS EQUIPMENT VERIFICATION TESTING PLAN 4-5
2.0 INTRODUCTION 4-6
3.0 GENERAL APPROACH 4-7
4.0 BACKGROUND 4-10
4.1 SOC Health Effects and Regulations 4-11
4.2 SOC Removal by Adsorption Processes 4-11
4.3 Application ofAdsorptive Media 4-12
4.4 Adsorption System Design Considerations 4-14
4.4.1 Contactor Configuration and Operation 4-14
4.4.2 Types of Adsorbents 4-15
4.5 In-Place Regeneration 4-16
5.0 DEFINITION OF OPERATIONAL PARAMETERS AND ABBREVIATIONS. 4-16
6.0 OVERVIEW OF TASKS 4-19
6.1 Taskl: Characterization of Source Water Quality 4-19
6.2 Task 2: System Design and Operation 4-19
6.3 Task 3: System Integrity Verification Testing (SIVT) 4-19
6.4 Task 4: Adsorption Capacity Verification Testing (ACVT) 4-20
6.5 Task 5: In-Place Regeneration 4-20
6.6 Task 6: Operation and Maintenance Manual 4-20
6.7 Task 7: Data Management 4-20
6.8 Task 8: Quality Assurance/Quality Control 4-20
7.0 TESTING PERIOD 4-20
8.0 TASK 1: CHARACTERIZATION OF SOURCE WATER QUALITY 4-22
8.1 Introduction 4-22
8.2 Objectives 4-23
8.3 Work Plan 4-23
8.4 Analytical Schedule 4-24
8.5 Evaluation Criteria 4-25
9.0 TASK 2: SYSTEM DESIGN AND OPERATION 4-25
9.1 Introduction 4-25
9.2 Objectives 4-25
9.3 Work Plan 4-26
9.4 Analytical Schedule 4-32
9.5 Evaluation Criteria 4-33
January 2004 This TSTP has not been validated in the field. Page 4-2
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TABLE OF CONTENTS (continued)
Page
10.0 TASK 3: SYSTEM INTEGRITY VERIFICATION TESTING 4-34
10.1 Introduction 4-34
10.2 Objectives 4-34
10.3 Work Plan 4-34
10.4 Analytical Schedule 4-37
10.4.1 Operational Data Collection 4-37
10.4.2 Water Quality Data Collection 4-37
10.5 Evaluation Criteria 4-39
11.0 TASK 4: ADSORPTION CAPACITY VERIFICATION TESTING 4-40
11.1 Introduction 4-40
11.2 Objectives 4-41
11.3 Work Plan 4-41
11.4 Analytical Schedule 4-42
11.4.1 Influent Sampling Requirements 4-42
11.4.2 Effluent Sampling Requirements 4-46
11.5 Evaluation Criteria 4-49
12.0 TASK 5: IN-PLACE REGENERATION 4-53
12.1 Introduction 4-53
12.2 Objectives 4-53
12.3 Work Plan 4-53
12.4 Analytical Schedule 4-54
12.5 Evaluation Criteria 4-54
13.0 TASK 6: OPERATION AND MAINTENANCE MANUAL 4-55
13.1 Objectives 4-55
13.2 Operation 4-55
13.3 Maintenance 4-56
14.0 TASK 7: DATA MANAGEMENT 4-57
14.1 Introduction 4-57
14.2 Objectives 4-57
14.3 Work Plan 4-57
15.0 TASK 8: QUALITY ASSURANCE/QUALITY CONTROL 4-58
15.1 Introduction 4-58
15.2 Objectives 4-58
15.3 Work Plan 4-58
15.3.1 Daily QA/QC Checks 4-59
15.3.2 Weekly QA/QC Checks 4-59
15.3.3 Monthly QA/QC Checks 4-59
15.4 Analytical Methods 4-59
January 2004 This TSTP has not been validated in the field. Page 4-3
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TABLE OF CONTENTS (continued)
Page
16.0 REFERENCES 4-61
APPENDIX A: REGULATED SOCS 4-63
APPENDIX B: DRINKING WATER STANDARDS AND HEALTH ADVISORIES.... 4-66
LIST OF TABLES
Table 3.1 Examples of Statements of Performance Capabilities 4-8
Table 8.1 Source Water Sampling Requirements 4-24
Table 9.1 Maintenance and Operability Information for Adsorptive Media Package
Plants 4-26
Table 9.2 Adsorption System Design Parameters 4-28
Table 9.3 Schedule for Observing and Recording Package Plant Operating and
Performance Data 4-33
Table 10.1 Required Water Quality Analyses and Minimum Sampling Frequencies for
SIVT 4-36
Table 10.2 Analytical Methods for Phase II and V Rule SOCs 4-38
Table 11.1 Influent Concentration Variability Requirements for Standard Testing During
ACVT 4-44
Table 11.2 Minimum Influent Sampling Frequency Requirements for Water Quality
Parameters 4-46
Table 11.3 Minimum Effluent Sampling Frequency Requirements for Other Water Quality
Parameters 4-48
LIST OF FIGURES
Figure 4.1 Multiple Adsorbent Contactors Operated in Parallel-Staggered Mode {Adapted
from USEPA 1999) 4-15
Figure 9.1 Example of an Adsorption Treatment System Schematic 4-29
Figure 11.1 Examples of Good and Basic Quality Breakthrough Curves 4-52
January 2004
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1.0 APPLICATION OF THIS EQUIPMENT VERIFICATION TESTING PLAN
This document is the Environmental Technology Verification (ETV) Technology Specific Test
Plan (TSTP) for evaluation of drinking water treatment equipment utilizing adsorptive media for
synthetic organic chemical (SOC) removal. This TSTP is to be used within the structure
provided by Protocol for Equipment Verification Testing for Removal of Synthetic Organic
Chemical Contaminants: Chapter 1 General Requirements. This TSTP is to be used as a guide
in the development of the Product-Specific Test Plan (PSTP) for testing of adsorptive media and
related equipment to achieve removal of SOCs.
This document is applicable only to fixed-bed adsorption processes in which adsorption occurs
as water flows through a stationary bed of adsorptive media. It is anticipated that most such
systems will use granular activated carbon (GAC) as the adsorptive media, but other media types
are also acceptable for verification testing. This document is NOT applicable to slurry
systems, such as those using powdered activated carbon (PAC) or other diffuse adsorption
processes in which the adsorptive media are added directly to water.
To participate in the equipment verification process for adsorption processes, the equipment
manufacturer and its designated Field Testing Organization (FTO) shall employ the procedures
and methods described in this TSTP and in the referenced ETV protocol document as guidelines
for the development of the PSTP. The FTO shall clearly specify in the PSTP, the SOCs targeted
for removal and the sampling program that shall be followed during verification testing. The
PSTP should generally follow those tasks outlined herein, with changes and modifications made
for adaptations to specific equipment. At a minimum, the format of the procedures written in the
PSTP for each task should consist of the following sections:
Introduction;
Objectives;
Work Plan;
Analytical Schedule; and
Evaluation Criteria.
The primary goal of equipment employed in this verification testing program is to remove SOCs
present in water supplies, treating water to compliance with Phase II and V Rules of the Safe
Drinking Water Act (SDWA). The organic contaminants listed in Phase II (Appendix A, Table
A.l) and Phase V (Appendix A, Table A.2) Rules include compounds classified as both SOCs
(including pesticides and herbicides) and volatile organic chemicals (VOCs). This document
focuses on verification testing of systems for the removal of SOCs (including pesticides and
herbicides) as classified in Phase II and V Rules of the SDWA. For verification testing of
systems for the removal of VOCs listed in Phase I, II, and V Rules of the SDWA, a companion
document should be used: EPA/NSF ETV Equipment Verification Testing Plan for the Removal
of Volatile Organic Chemical Contaminants by Adsorptive Media (EPA/NSF, 2002). These
documents may also be used for verification testing of adsorptive media for the removal of
chemicals listed in Drinking Water Standards and Health Advisories (USEPA 2000), which are
included as Appendix B in this document.
January 2004
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Page 4-5
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Experimental design of the PSTP shall be developed so that relevant performance specifications
for adsorptive media related to SOC removal are addressed. The manufacturer may wish to
establish a statement of performance capabilities (see Section 3.0, General Approach) that is
based upon removal of target SOCs from influent water sources, or alternatively, one based upon
compliance with drinking water standards. For example, the manufacturer could include in the
PSTP a statement of performance capabilities that would achieve compliance with maximum
contaminant levels (MCLs) stipulated in the National Primary Drinking Water Standards or the
EPA National Secondary Drinking Water Regulations for a specific water quality parameter.
The experimental design of the PSTP shall be developed to address the specific statement of
performance capabilities established by the manufacturer. Each PSTP shall include all of the
tasks described in this document, Tasks 1 to 8. An overview of the tasks is given in Section 6.0,
Overview of Tasks.
2.0 INTRODUCTION
Fixed-bed adsorptive media processes are currently used for a number of water treatment
applications, including removal of color, taste and odor, disinfection byproduct precursors
(DBPs), SOCs, VOCs, and inorganic compounds (Snoeyink and Summers 1999). Performance
of adsorptive media for SOC removal is highly dependent on a number of fictors, including
influent SOC concentration; influent water quality, including other SOCs or VOCs, background
organic matter (BOM), pH, temperature; and system design, including empty-bed contact time
(EBCT) and adsorbent type. Adsorption is not a steady-state process; this TSTP is designed
based on a statement of performance capabilities that specifies a run time achievable for a given
fixed-bed adsorptive media process under specified influent conditions. The run time is the
operation time of the system during which time the removal of SOC(s) meets or exceeds that
stated in the manufacturer's statement of performance capabilities. Alternatively, the statement
of performance capabilities may specify a maximum adsorbent usage rate (AUR) to be verified.
Standard pretreatment, such as cartridge filtration, included as part of the packaged/modular
adsorption treatment equipment is considered an integral part of the treatment system. In such
cases, the system shall be considered as a single unit and the pretreatment process shall not be
separated for evaluation purposes.
Additional pretreatment processes may be required to reduce particle loading to the adsorption
process for surface water applications (and ground waters in which iron and manganese
precipitation is an issue). These are considered to constitute a separate treatment module whose
performance and operation are outside the scope of this document. Where such pretreatment is
required to reduce the fouling potential of the adsorption process feed water, consult the ETV
document, EPA/NSF ETV Protocol for Physical Removal of Microbiological and Particulate
Contaminants (EPA/NSF 2002), for evaluation testing procedures.
Two or more parallel contactors, whose effluents are blended prior to further treatment or
distribution, are considered one system for the purposes of verification testing.
January 2004
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Page 4-6
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3.0 GENERAL APPROACH
Testing of equipment covered by this TSTP shall be conducted by an FTO that is qualified by
NSF International (NSF) and selected by the equipment manufacturer. Testing of analytical
water quality performed in conjunction with this TSTP shall be contracted with a laboratory that
is certified, accredited or approved by a state, a third-party organization (i.e., NSF), or the EPA.
For verification testing, the manufacturer shall identify in a statement of performance
capabilities, the specific performance criteria to be verified and the specific operational
conditions under which the verification testing shall be performed. The statement of
performance capabilities must be specific and verifiable. Statements should also be made
regarding the applications of the equipment, the known limitations of the equipment and under
what conditions the equipment is likely to under perform or fail. There are different types of
statements of performance capabilities that may be verified. Examples are provided in Table 3.1.
Verification testing shall consist of an evaluation of the fixed-bed adsorptive media treatment
system using an influent water containing one SOC at target influent concentrations equal to that
stated in the statement of performance capabilities, for a minimum period of 13 days and one 8-
hour shift. Statistical analyses of the data results shall include averages, minimum, and
maximum for each analyte. For sample sets of eight or more, the results shall also include the
standard deviation and confidence interval for each analyte. A pilot plant representing the
package plant shall not be substituted for the actual package treatment system. The 13.3-day
minimum testing period is designed to allow for an evaluation of the system's mechanical and
hydraulic integrity and operability under field conditions, as well as to assess SOC removal
performance for 13.3 days of operation. However, breakthrough of the SOC will often not occur
within the first 13.3 days of operation. Consequently, verification testing of the system for
longer than 13.3 days may be desirable to achieve breakthrough and will be necessary to verify a
manufacturer's statement of performance capabilities of run time greater than 13.3 days. For
adsorption systems incorporating in-place media regeneration, the effectiveness of regeneration
shall also be assessed.
January 2004
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Page 4-7
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Table 3.1 Examples of Statements of Performance Capabilities
Testing
Mode
Single or
Multiple
Compounds
Example Statement of Performance Capabilities
Constant
influent, low
variability
Single
Multiple
Constant
influent, high
variability
Single
Multiple
This single-contactor package plant, when operated at a GAC EBCT of
15 minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 60 days (AUR < 0.086 g/L or 0.72
lb/1,000 gal) in GAC influent waters containing mean endrin
concentrations at or below 20 |_ig/L with low variability (RSD < 10%);
TOC concentrations at or below 3.0 mg/L; turbidity levels at or below
1.0 Nephlometric Turbidity Units (NTU); and temperature between 20
and 25ฐC, containing no other SOCs at levels above 1 |_ig/L.
This single-contactor package plant, when operated at a GAC EBCT of
15 minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 120 days (AUR < 0.043 g/L or
0.36 lb/1,000 gal) in GAC influent waters containing mean endrin
concentrations at or below 20 |_ig/L with low variability (RSD < 10%);
TOC concentrations at or below 3.0 mg/L; turbidity levels at or below
1.0 NTU; temperature between 20 and 25ฐC; containing the following
SOCs: dinoseb at 12 (ig/L, simazine at 5 |_ig/L. 2,4-D at 10 |_ig/L. A
performance statement could also be made for these other compounds.
This single-contactor package plant, when operated at a GAC EBCT of
15 minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 60 days (AUR < 0.086 g/L or 0.72
lb/1,000 gal) in GAC influent waters containing mean endrin
concentrations at or below 25 |_ig/L with high variability (ranging from 5
to 40 |_ig/L. RSD > 30 and < 60% ); TOC concentrations at or below 3.0
mg/L; turbidity levels at or below 1.0 NTU; and temperature between 20
and 25ฐC, containing no other SOCs at levels above 1 |_ig/L.
This single-contactor package plant, when operated at a GAC EBCT of
15 minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 90 days (AUR < 0.058 g/L or 0.49
lb/1,000 gal) in GAC influent waters containing endrin concentrations at
or below 25 |_ig/L with high variability (ranging from 5 to 40 |_ig/L, RSD
> 30 and < 60%); TOC concentrations at or below 3.0 mg/L; turbidity
levels at or below 1.0 NTU; temperature between 20 and 25ฐC;
containing the following SOCs: dinoseb at 12 |_ig/L. simazine at 5 |_ig/L,
2,4-D at 10 |_ig/L. A performance statement could also be made for these
other compounds.
January 2004
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Page 4-8
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Table 3.1 Examples of Statements of Performance Capabilities (cont.)
This single-contactor package plant, when operated at a GAC EBCT of 15
minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 60 days (AUR < 0.086 g/L or 0.72
lb/1,000 gal) after the GAC influent water begins receiving a spike of
endrin at a mean concentration of 25 |_ig/L (with low variability, RSD <
10%) for 48 hours; after treating the following water quality with no
SOCs present for 120 days or less; TOC concentrations at or below 3.0
mg/L; turbidity levels at or below 1.0 NTU; and temperature between 20
and 25ฐC, containing no other SOCs at levels above 1 |_ig/L.
This single-contactor package plant, when operated at a GAC EBCT of 15
minutes or more, is capable of maintaining a treated water endrin
concentration below 2 |_ig/L for up to 90 days (AUR < 0.058 g/L or 0.49
lb/1,000 gal) after the GAC influent water begins receiving a spike of
endrin at a mean concentration of 25 |_ig/L (with low variability, RSD <
10%) for 48 hours; after treating the following water quality with no
SOCs present for 120 days or less; TOC concentrations at or below 3.0
mg/L; turbidity levels at or below 1.0 NTU; temperature between 20 and
25ฐC; with the following SOCs also contained in the 48-hour spiked
influent: dinoseb at 12 |_ig/L. simazine at 5 |_ig/L. 2,4-D at 10 |_ig/L. A
performance statement could also be made for these other compounds.
The design and duration of the equipment verification testing is based on the overall equipment
performance demonstration goal of the test. At a minimum, verification testing must accomplish
a demonstration of system integrity and initial performance by operating the system for a
minimum of 13.3 days [System Integrity Verification Testing (SIVT)]. Equipment verification
testing for a time period exceeding 13.3 days may have two objectives. Objective A includes
completing the requirements of SIVT, and then evaluating adsorption capacity by testing until
breakthrough of the SOC. Objective B also includes completing the requirements of SIVT, and
then evaluating adsorption capacity to a run time greater than 13.3 days, but prior to
breakthrough of the SOC. Testing under Objective B will result in termination of testing prior to
breakthrough, yielding an AUR higher than that potentially achievable by the system. However,
due to long run times to breakthrough for highly adsorbable SOCs, it may be preferable to
terminate the test prior to breakthrough, still showing that run times substantially greater than
13.3 days are achievable by the system for the SOC tested. For both SIVT and both optional
objectives, the AUR shall be determined by the run time of the last effluent sample taken during
testing (if testing is terminated prior to breakthrough), or the run time to breakthrough,
whichever occurs first.
During verification testing, the target SOC may already be present in the source water used.
However, the manufacturer may wish to perform verification testing at an influent concentration
higher than that of the SOC normally present in the source water, or the manufacturer may wish
to test for a compound not detected in the source water to be tested. In these cases, the
adsorption influent water may be spiked to the target concentration with the SOC to be tested.
Attenuation Single
of spiked
influent
Multiple
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If a manufacturer's statement of performance capabilities bases performance on simultaneous
treatment of multiple SOCs, verification testing shall be performed with an equivalent mixture of
multiple SOCs (specific SOCs and influent concentrations targeted based on the statement of
performance capabilities). Although testing with multiple influent SOCs is allowable, this TSTP
is designed to verify performance of a single SOC influent. However, standard verification
testing cf a multiple-compound manufacturer's statement of performance capabilities can be
conducted using this TSTP. For verification testing of an AUR by testing until breakthrough of
the SOC (Objective A), this document provides guidance for estimating the usage rate. This
guidance, however, is based on a single compound influent, and is not directly applicable to
multiple-compound influents, due to the impact of competitive adsorption. The manufacturer's
statement of performance capabilities may be based on a run time for a single compound within
the mixture of compounds, or it may be based on multiple run times for each of multiple
compounds. For regulated SOCs, the AUR will be based on the first compound to exceed the
MCL in the system effluent.
Verification testing of three modes of operation are possible under this TSTP: (1) constant
influent with low variability, (2) constant influent with high variability about a target mean
concentration, and (3) attenuation of a spiked influent. Most statements of performance
capabilities will be based on the presence of a single influent SOC at a constant concentration
with low variability, and this TSTP has been designed to verify these types of manufacturer's
statements of performance capabilities. However, this TSTP may also be used to perform
verification testing under conditions of highly variable influent SOC concentrations about a
target mean concentration and attenuation of a spiked influent. For verification testing of
attenuation of a spiked influent, the statement of performance capabilities must state the amount
of time the system was in operation receiving influent water without the SOC to be spiked before
spiking begins, as in the example given in Table 3.1.
Package plants that operate by blending the effluents of more than one contactor in parallel prior
to further treatment and distribution shall be evaluated by assessing the water quality of the
blended effluent from all contactors. If contactors are operated in staggered operation cycles to
improve the overall efficiency of the process, then effluent testing will still be performed on the
blended effluent of all contactors. The statement of performance capabilities shall clearly state
the number of contactors operated and clearly describe the mode of operation (parallel or
parallel-staggered) so that package plant performance can be evaluated in terms of the mode of
operation employed.
For verification testing of Objective A (testing until breakthrough is reached), breakthrough is
defined as reaching an effluent concentration of the SOC tested. This concentration can be
chosen by the manufacturer or it can be a level equal to a regulated or proposed MCL, in which
case the statement of performance capabilities should designate it as such. Depending on the
quality and amount of data gathered to characterize the breakthrough curve, the AUR can be
calculated by different methods, as described in Section 11.5.
4.0 BACKGROUND
This section provides a brief overview of SOC regulations, SOC health effects, SOC removal by
fixed-bed adsorptive systems, and adsorption system design. This information should assist in
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providing a background on SOC removal by adsorption processes and on the applicability of
fixed-bed adsorption processes to treatment of SOCs. Due to the predominance of the use of
GAC media for adsorption, the information presented in this section will focus on adsorption
using GAC. The term SOC as used in this section includes volatile, semi volatile, and
nonvolatile compounds.
4.1 SOC Health Effects and Regulations
Three general types of organic compounds found in water are (1) compounds resulting from the
breakdown of naturally-occurring organic material, such as humic materials from plants and
algae, microorganisms and their metabolites, and high molecular weight aliphatic and aromatic
hydrocarbons; (2) compounds formed due to domestic and commercial activities (SOCs); and (3)
compounds formed by chemical reactions during water treatment and transmission (Cohn, Cox,
and Berger 1999). SOCs include pesticides, solvents, metal degreasers, and poly chlorinated
biphenyls.
The 1974 SDWA specified the process by which EPA adopted national drinking water
regulations, including the establishment and publication of recommended maximum contaminant
levels (RMCLs), set at levels at which no known or anticipated health effects would occur
(Pontius and Clark 1999). RMCLs were followed by the establishment of MCLs, set as close to
the RMCL as economically and technically feasible. Currently, 56 organic contaminants are
regulated under Phase I Rule Volatile Organic Contaminants, Phase II Rule Contaminants, and
Phase V Rule Contaminants. Appendix A lists currently regulated organic contaminants,
including MCL goal (MCLG), MCL, potential health effects and sources of drinking water
contamination. Appendix B contains the most recent Drinking Water Standards and Health
Advisories tables available (USEPA 2000), listing 172 SOCs, and describing the status of their
legislation, MCLGs, MCLs, health advisory document status, and available health effects data.
These tables are revised periodically by EPA and can be accessed on the Internet at
www.epa.gov/ost/drinking/standards/summary.html or a copy may be ordered by calling the Safe
Drinking Water Hotline (1-800-426-4791).
The SDWA also requires that EPA establish a list of contaminants that serves as the primary
source for priority contaminants considered for regulation. The list is divided into contaminants
that are priorities for future research, those that need additional occurrence data, and those that
are priorities for future rulemaking. The final Drinking Water Contaminant Candidate List
(CCL) was published in 1998. The CCL can be accessed on the Internet at
www.epa.gov/safewater/ccl/cclfs.html.
4.2 SOC Removal by Adsorption Processes
Removal of organic compounds by adsorption occurs through several steps: external diffusion,
internal diffusion, and adsorption. First, organic compounds are transported from the bulk
solution to the boundary layer of water surrounding the adsorbent particle. Second, organic
compounds are transported by molecular diffusion through the external boundary layer (film
diffusion). Third, organic compounds are transported through the adsorbent's pores to an
available internal adsorption site. The transport mechanism for internal diffusion can be pore
diffusion, molecular diffusion through the solution within the pores, or surface diffusion
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(diffusion along the adsorbent surface after adsorption has occurred). The final step is physical
adsorption of the organic compound to the adsorbent. The slowest step of these four is the rate-
limiting step, and it will control the rate of organic compound removal. In adsorption by GAC,
the rate-limiting step is usually film diffusion or pore diffusion (Snoeyink and Summers 1999).
4.3 Application of Adsorptive Media
In a GAC fixed-bed adsorption system, the mass transfer zone (MTZ) is the region in which
adsorption is taking place. The activated carbon behind the MTZ is completely saturated with
the adsorbate, while that ahead of the MTZ has not been exposed. Within the MTZ, the degree
of saturation varies from zero to complete saturation. The length of the MTZ can vary (see
Snoeyink and Summers 1999 for more information on factors affecting the MTZ length) and in
some cases, the MTZ is very short and an ideal plug-flow behavior can be assumed. This
assumption simplifies analysis and prediction of run time to breakthrough for adsorption of a
single compound. Breakthrough is defined as the point when the contactor effluent
concentration reaches the maximum acceptable effluent concentration, which is also referred to
as the treatment objective. The breakthrough curve is a plot of column effluent concentration as
a function of operation time or throughput in bed volumes (BV) treated. Throughput is related to
operation time by EBCT, as presented in Equation 1:
, _ xr. Operation time (days) 1,440 min/day
Throughput (BV) = ^ \\ J (1)
EBCT (min)
EBCT is the hydraulic retention time of an empty contactor. The EBCT parameter normalizes
bed depths at different loading rates and it is calculated as the volume of the contactor occupied
by the adsorbent divided by the flow rate.
The performance of adsorptive media for removal of SOCs varies widely. In large part,
performance is dependent on the influent concentration and adsorbability of the compound
studied. For a 6-minute EBCT adsorber with bituminous coal-based GAC, breakthrough of
trichloroethene to 50% of its influent concentration (310 |ig/L) occurred after 25,000 BV (104
days). Breakthrough of cis-1,2 dichloroethene to 50% of its influent concentration (70 |ig/L)
occurred after 17,000 BV (59 days) in a 5-minute EBCT contactor, also using bituminous coal-
based GAC (Sontheimer, Crittenden, and Summers 1988).
The equilibrium relationship between the solid phase concentration (quantity of adsorbate per
unit adsorbent), qs, and the equilibrium solution concentration, Ce, is the adsorption isotherm.
This relationship can be described by the Freundlich equation, as presented in Equation 2:
IE = (2)
where K and 1 hi are constants. The constant K is related to the capacity of the adsorbent for the
adsorbate, and 1 In is a function of the strength of adsorption (Snoeyink and Summers 1999).
Values for K and 1 hi have been tabulated for many SOCs in the literature (Snoeyink and
Summers 1999; Sontheimer, Crittenden, and Summers 1988; Faust and Aly 1998; Speth and
Miltner 1990, 1998). The value and units of K are dependent on the units of Ce and qs.
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Many researchers have shown that the presence of BOM can have a negative impact on the
adsorption capacity of an adsorbent for SOCs. Relative to the SOC targeted for removal by
adsorption, BOM will move more rapidly through the contactor and adsorb onto adsorbent sites.
As more adsorption sites are taken by preloading with BOM, the capacity of the adsorbent for
the SOC is reduced (Crittenden et al. 1985; Sontheimer, Crittenden, and Summers, 1988; Speth
and Adams 1993; Snoeyink and Summers 1999). In one study, the capacity of activated carbon
for trichloroethene (TCE) was reduced by 50% when the carbon was preloaded with BOM, as
compared to adsorption in distilled water (Summers et al. 1989).
Competitive adsorption can also impact performance. In many cases, other SOCs will be in
solution in the source water to be treated for removal of a specific SOC. The amount of
adsorbent required for the same removal of a specific SOC within a mixture of SOCs will be
greater than that for adsorption of the SOC in a single solute system. SOCs will compete for
adsorption sites on the adsorbent surface (Snoeyink and Summers 1999). In addition,
displacement of adsorbed compounds from the surface of the adsorbent can result in an effluent
concentration greater than the influent concentration. More information on competitive effects
can be found in the literature (Sontheimer, Crittenden, and Summers 1988; Speth and Adams
1993; Snoeyink and Summers 1999).
Adsorptive media designed for the removal of SOCs can be used to remove a SOC present in the
source water at a constant concentration, yielding an effluent concentration below the treatment
objective; when the treatment objective is reached, the media is replaced or regenerated in-place.
The influent SOC concentration may be fairly constant, or highly variable. In another
application, adsorptive media can attenuate a SOC spike event, such as a spill, lowering the
effluent concentration of the SOC to a level that is below the treatment objective. This TSTP can
be used to evaluate adsorptive media as treatment to constant SOC influent concentration (low or
high variability) and to attenuate a short-duration spike of an SOC.
During operation of an adsorbent contactor subjected to a constant influent SOC concentration,
the concentration of the SOC in the influent and effluent can be monitored and plotted. A plot of
the effluent concentration as a function of operation time or throughput in BV treated is a
breakthrough curve. Breakthrough curves are often generated by pilot-scale contactors to
develop design criteria for full-scale systems. As defined in this document, breakthrough is
reached when the concentration of the target compound in the adsorbent contactor effluent
reaches the treatment objective, often the MCL. Immediate breakthrough is the level of
adsorbate present in the adsorbent contactor effluent at the start of operation. For many highly-
adsorbable SOCs, this level will not be detectable. Initial breakthrough is the point at which
effluent concentrations begin to rise above immediate breakthrough levels.
The breakthrough curve is often used to determine the AUR. The AUR is the mass of adsorbent
required to treat a specific volume of water to a predetermined quality. High AUR values result
in increased operation and maintenance (O&M) costs caused by more frequent adsorbent
replacement. The AUR can be calculated by the formula presented as Equation 3:
AUR = * (3)
BVbt
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where p is the apparent density of the adsorbent and BVbt is the BV to breakthrough. The AUR
commonly has units of lbs/1,000 gal or g/L. The AUR can be converted from g/L to lbs/1,000
gal by multiplying the value in g/L by 8.35 lb-L/g-1,000 gal.
At an influent concentration, Co, assuming a symmetrical breakthrough curve, the adsorbent
capacity q can be estimated for a specific compound from the breakthrough curve by the formula
presented as Equation 4:
q = (4)
AURbt=50%
where AURbt=5o% is the AUR calculated at 50% breakthrough of the compound. This
approximation of adsorbent capacity is only valid at the influent concentration (Jo) of the
compound. It is not valid at other influent concentrations; capacity is highly dependent on
influent concentration.
4.4 Adsorption System Design Considerations
4.4.1 Contactor Configuration and Operation
An important contactor design parameter is the EBCT. The EBCT has a large impact on
cost and performance of an adsorbent system. In general, systems with shorter EBCTs
have lower capital costs, but higher O&M costs due to more frequent adsorbent
replacement. Large EBCTs will result in lower O&M costs, but higher capital costs.
Most GAC system EBCTs range from 5 to 20 minutes. The EBCT can be calculated by
the following equations, presented as Equation 5:
EBCT = = = (5)
Q Q/Ac HLR
where V is the volume of bed occupied by the adsorbent, Q is the flow rate, L is the
adsorbent bed length, Ac is the cross-sectional adsorbent bed area, and HLR is the
hydraulic loading rate.
In some cases, it is advantageous to operate two contactors in series, where half of the
required adsorbent media (and therefore EBCT) is contained in each. A sampling port
between the two contactors allows for monitoring of breakthrough of the compound
being treated. The spent adsorbent in the upper half of the system can be replaced or
regenerated, and the flow of water rerouted so the contactor containing fresh adsorbent is
downstream. See Sontheimer, Crittenden, and Summers (1988) and Snoeyink and
Summers (1999) for more information on contactor configuration.
Package plants that contain more than one adsorbent contactor in parallel operation can
achieve more efficient AURs by staggering the operation of parallel contactors (at the
expense of higher capital costs). When multiple contactors are operated in parallel and
staggered with respect to their operation cycles (Figure 4.1), the blended effluent of all
contactors constitutes the water quality treated by the system. Under this mode of
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operation, poorer water quality of older contactors is blended with high quality water
from contactors containing fresh adsorbent. The water quality of each contactor may
exceed the treatment objective, but the blended water quality is maintained below the
treatment objective. Thus, each contactor can be operated for a longer period of time as
compared to single contactor operation (USEPA 1999).
For small package plants, this mode of operation may not always be feasible since the
logistics of staggering the operation of a very small number of contactors (e.g., two), due
to the characteristics of the breakthrough curve of the SOC being treated could lead to an
increase in capital costs. A very sharp breakthrough curve could lead to difficulties in
scheduling contactors for replacement. However, O&M costs may be lowered
substantially when contactors are operated in parallel-staggered mode, especially if the
package plant is comprised of several contactors, or if several package plants are operated
in parallel. Based on a modeling analysis of multiple contactor operation presented by
the USEPA (1999), operation times for two contactors operated in parallel-staggered
mode are estimated as 29 to 50% longer than that for a single contactor, assuming a
treatment objective of 40 to 60% breakthrough. For the same treatment objective, the
gain in individual contactor operation time is estimated as 43 to 67% for three contactors,
and 55 to 83% for four contactors. The range in estimates is a function of the shape of
the breakthrough curve and the relative treatment objective. These estimates may not be
applicable to extremely sharp breakthrough curves.
Influent water
Disinfectant
Finished
water
Blended effluent
Figure 4.1 Multiple Adsorbent Contactors Operated in Parallel-Staggered Mode
(Adaptedfrom USEPA 1999)
4.4.2 Types of Adsorbents
The most widely used adsorbent is activated carbon. The most commonly used raw
materials for producing activated carbon used in water treatment are bituminous coal,
peat, lignite, petrol coke, wood, and coconut shells. The pore structure and adsorbent
properties of activated carbon are a function of the raw material used and the activation
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processactivating agent, length of activation and temperature of activation. The
surface area of activated carbon used for water treatment ranges from 600 to 1,500 nf/g
(Sontheimer, Crittenden, and Summers 1988).
Many types of synthetic resins have been used for adsorption of organic compounds from
water. Synthetic resins vary in both the functional groups and the matrices that support
functional groups (Snoeyink and Summers 1999). More information on types of ion
exchange resins can be found in Clifford (1999) and Snoeyink and Summers (1999).
4.5 In-Place Regeneration
Once the effluent concentration of the SOC treated exceeds the treatment objective, the
adsorbent is taken off-line and regenerated or replaced with fresh adsorbent. Some adsorption
systems, especially resins, are designed for in-place regeneration. Normally, in-place reactivation
is produced by addition of a strong base solution or a solvent such as acetone or isopropanol to
the adsorbent bed. The ability of the regeneration step to restore the resin's capacity is important
and is included as part of the verification testing.
5.0 DEFINITION OF OPERATIONAL PARAMETERS AND ABBREVIATIONS
Definitions and abbreviations that may apply to adsorptive media processes for SOC include:
1/n: Freundlich exponent constant.
Adsorbate: the molecule adsorbed on to the surface of the adsorbent.
Adsorbent: the solid material onto which molecules adsorb, such as GAC or synthetic resins.
Adsorbent capacity: mass of solute adsorbed per unit mass of adsorbent at a given point of
operation, commonly equilibrium.
Ac: cross-section area of adsorbent bed.
Adsorption capacity: see adsorbent capacity.
Adsorbent usage rate (AUR): the mass of adsorbent required to treat a specific volume of
water to a predetermined quality, in units of g/L or lb/1,000 gal (1 g/L = 8.35 lb/1,000 gal).
AURbt =5o%* AUR calculated at 50/o breakthrough of the compound.
AURdw : AUR for a compound in distilled water.
AURnw: AUR for a compound in natural water (in the presence of BOM).
Bed volumes (BV): a normalized unit of throughput, defined as operation time divided by
EBCT.
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BOM: background organic matter. Measurement of the source water total organic carbon (TOC)
concentration will provide an indicator of the level of BOM present.
Breakthrough: the point when the concentration of a target compound in the adsorbent
contactor effluent reaches the treatment objective.
Breakthrough curve: a plot of effluent adsorbate concentration as a function of operation time
or throughput in BV, usually extending past the breakthrough point to exhaustion. The curve is
characteristic of the adsorbent, adsorbate, system parameters, and influent water quality.
BVbt: BV to breakthrough.
CCL: Drinking Water Contaminant Candidate List.
Ce'> equilibrium solution concentration.
Ce: concentration in the adsorbent contactor effluent.
Co: concentration in the adsorbent contactor influent.
Ce : average contactor effluent concentration for a GAC breakthrough curve operated until
exhaustion.
dio: effective size, defined as the sieve opening size (mm) at which 10% of the sample passes.
d5o: mean particle diameter, defined as the sieve opening size (mm) at which 50% of the sample
passes.
Empty-bed contact time (EBCT): the hydraulic retention time of an empty contactor, defined
as volume of the contactor occupied by the adsorbent divided by the flow rate, Q.
Er: the regeneration efficiency (percent).
Exhaustion or saturation: the point in the breakthrough curve when the effluent concentration
reaches its influent concentration, indicating that no adsorption is occurring. In practice, effluent
concentrations may reach a plateau below the influent concentration because the adsorbate is
removed by other mechanisms, such as biodegradation or slow adsorption kinetics.
GAC: granular activated carbon.
gpm: gallons per minute.
HLR: hydraulic loading rate.
Hydraulic loading rate: the velocity or flow rate per area at which water is loaded to the
contactor (OIAc or Z/EBCT), usually in units of gpm/ft or m/hr.
K. Freundlich constant.
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L: length of contactor, usually in units of meters.
Loading rate: see hydraulic loading rate,
m: meters.
iha: mass of adsorbent.
MCL: maximum contaminant level.
MCLG: maximum contaminant level goal.
niR: mass SOC recovered in the regeneration stream.
MRL: minimum reporting level.
min: minutes.
Ns: minimum number of paired influent and effluent samples required to be taken.
Q: volumetric flow rate.
q: adsorbent capacity, in units of mass of adsorbate/mass of adsorbent (also moles of
adsorbate/mass of adsorbent).
-------
TOC: total organic carbon.
UV-254: ultraviolet absorbance at 254 nm.
V: contactor volume.
VOC: volatile organic chemical.
y: mean.
Ybt: adsorbent throughput to breakthrough, in units of BV.
6.0 OVERVIEW OF TASKS
6.1 Task 1: Characterization of Source Water Quality
This task includes an analysis of available historic data for the source water to be treated,
including the concentrations of SOCs and water quality parameters, as well as seasonal
variability in concentrations. SOCs (including VOCs) already present in the source water can
impact the performance of the adsorptive media for SOC removal depending on the
concentration of the background SOCs and their adsorbability relative to the SOC to be tested.
Furthermore, BOM can also reduce the capacity of the adsorbent for SOCs, and this "fouling"
tends to be greater at higher BOM concentrations. Finally, an assessment of the need for
pretreatment or the appropriateness of currently planned pretreatment must be made based on
source water quality.
If sufficient historic data is not available to properly evaluate the source water quality, additional
monitoring of the source water shall be performed to adequately assess source water quality.
6.2 Task 2: System Design and Operation
This task involves procedures for determining the design and operating parameters of the
adsorptive media treatment system. The following tasks shall be performed or documented: the
experimental mode of operation, treatment system design parameters, start-up and O&M
procedures, an operations monitoring plan, and an estimate of the run time to SOC breakthrough
(for verification testing beyond the minimal 13.3-day period).
6.3 Task 3: System Integrity Verification Testing (SIVT)
The objectives of this task are to demonstrate that the equipment is (1) able to initially produce a
finished water as described in the manufacturer's statement of performance capabilities and (2)
able to reliably operate under field conditions. The equipment is operated, monitored, and
sampled for approximately two weeks. This task evaluates the short-term ability of the
equipment to produce water of acceptable quality. SIVT is not designed to evaluate the long-
term ability of the equipment to treat water containing SOCs. SIVT must be performed at least
once for each system evaluated under this TSTP.
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6.4 Task 4: Adsorption Capacity Verification Testing (ACVT)
After Task 3 has been performed, the long-term effectiveness of the treatment system to remove
SOCs shall be evaluated by Task 4. The main purpose of Adsorption Capacity Verification
Testing (ACVT) is to evaluate the capability of the adsorptive media treatment system for
removal of SOCs. Specifically, the AUR will be determined for the SOC tested. The AUR will
be assessed under the design and operation conditions of the treatment system, as well as influent
water quality conditions of the source water after pretreatment, if any. Influent and effluent
sampling guidelines are described based on the experimental design (constant influent with low
variability, constant influent with high variability, or attenuation of a spiked influent).
6.5 Task 5: In-Place Regeneration
Some treatment systems may use adsorptive resins that can be regenerated in-place, and may
incorporate regeneration capability as an integral part of the equipment. In such cases, the
objective of this task is to evaluate regeneration effectiveness and the impact of regeneration of
performance.
6.6 Task 6: Operation and Maintenance Manual
The FTO shall obtain the manufacturer-supplied O&M manual(s) to evaluate the instructions and
procedures for their applicability during the verification testing period. Recommendations for
criteria for the evaluation of O&M manuals for package plants employing adsorptive media for
SOC removal are given in this section.
6.7 Task 7: Data Management
The objective of this task is to establish an effective field procedure for data management at the
field operations site and for transmission of data obtained during the verification testing from the
FTO to NSF.
6.8 Task 8: Quality Assurance/Quality Control
The objective of this task is to develop a Quality Assurance/Quality Control (QA/QC) plan for
verification testing. This important item will assist in obtaining an accurate measurement of
operational and water quality parameters during adsorptive media system verification testing.
7.0 TESTING PERIOD
Guidelines for adsorptive media equipment verification testing frequency and duration are given
in this section. To some extent, the number and length of test runs conducted will depend on
how rigorous a demonstration the equipment manufacturer wishes to perform, and how strong a
statement of performance capabilities the manufacturer would like to be able to make about
equipment performance.
During initial operations, a manufacturer shall evaluate equipment operation and determine the
appropriate conditions that result in effective treatment of the feed water. After an initial
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operations step, a test run shall consist of operating the treatment equipment for 13 days and one
8-hour shift of actual run time, the minimum required testing duration to satisfy the requirements
of this TSTP. Although 13.3 days of operation are adequate to verify system integrity (e.g.,
mechanical and hydraulic functioning, excessive headloss, channeling, etc.), SOCs at levels
typically found in natural source waters will not achieve breakthrough within 13.3 days of
operation. Equipment manufacturers should recognize that a statement of performance
capabilities that their adsorption system could treat a natural source water effectively for 13.3
days without exhibiting SOC breakthrough would not be impressive. For this reason, it is
expected that the test will be made more rigorous (strengthening the statement of performance
capabilities a manufacturer could make) by operating the test equipment for a longer period or
until breakthrough of SOCs is achieved. Task 3 shall consist of 13.3 days of testing for
verification of system integrity. Task 4, adsorption capacity verification testing, shall verify the
long-term effectiveness of the treatment system to remove SOCs.
For tests not running until breakthrough, the AUR reported can be based on no greater a run time
than the total operation time during which the equipment was operated as of the last pair of SOC
influent and effluent samples taken. To verify a minimum AUR, or longest possible run time
while maintaining the target SOC concentration below the treatment objective as stipulated in the
manufacturer's statement of performance capabilities, the system must be operated until
breakthrough is achieved. Once breakthrough occurs, and the effluent SOC concentration is
greater than the treatment objective stated in the manufacturer's statement of performance
capabilities, it is no longer necessary to continue operation of the system, unless a complete
breakthrough curve is desired. It may be desirable to capture the complete breakthrough curve,
however, as the AUR can be calculated based on the last effluent sample with concentration
lower than the treatment objective, or by an interpolation of a best-fit curve approach to a
complete breakthrough curve data set. These options are described in Section 11.5.
Definition of target treatment objective exceeded. Due to analytical and experimental
variability, the concentration of the SOC in the contactor may increase above the treatment
objective, only to fall below it on a subsequent sampling. Therefore, it is recommended that
verification testing be designed to produce the best possible quality data set, one that clearly
shows the breakthrough curve trend and minimizes scatter in the data caused by analytical and
experimental variability. If the data set clearly shows a breakthrough trend, with some
variability, a best-fit curve may be used to fit the data, and the point at which the effluent SOC
concentration exceeds the treatment objective can be interpolated. Otherwise, the last sample
taken (with concentration below the treatment objective) prior to the first point at which the
effluent equals or exceeds the treatment objective shall designate the run time for purposes of
calculation of the AUR. It is worthwhile to develop a very good quality data set that can be fit to
a curve. Utilizing the run time of the last data point prior to the first data point with a
concentration above the treatment objective will yield a conservative estimate of the run time to
breakthrough.
The duration of verification testing to determine the AUR based on operation until the SOC
tested reaches breakthrough for many SOCs will be longer than 13.3 days. The length of the
testing period will depend on the adsorbability and concentration of the compound tested.
Highly adsorbable compounds may yield operation times greater than one year in length prior to
breakthrough. The run termination criteria can be based on achieving breakthrough (as defined
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by an effluent SOC concentration exceeding the MCL or other treatment objective). In this case,
the testing period would be the shortest time necessary to verify the AUR. The AUR will be
determined for a test regardless of the operation time; when the test is terminated prior to
breakthrough, the AUR will be calculated based on the total run time for which the SOC was
treated while effluent levels were maintained below treatment objective. For verification testing
operating until breakthrough or beyond, a best-fit curve of the data set can be used to interpolate
the run time used for the AUR calculation. In addition, a full breakthrough curve is information
that may be of benefit to the manufacturer. Determining the AUR is explained in more detail in
Task 2, System Design and Operation.
For ACVT of attenuation of a spiked SOC compound, the testing period shall begin when the
application of the spike ends (see examples in Table 3.1). The amount of time the system is
operated prior to, during, and after the application of the spike shall be specified by the
manufacturer. Ideally, the time period during which the system is operated after the application
of the spike shall be long enough to demonstrate effective attenuation of the influent pulse.
8.0 TASK 1: CHARACTERIZATION OF SOURCE WATER QUALITY
8.1 Introduction
A characterization of the source water quality is necessary to identify SOCs present in the source
water and to evaluate the impact of other water quality parameters or contaminants on adsorption
of SOCs. The presence of other SOCs at detectable concentrations (e.g., > 1 |ig/L) can
negatively impact the adsorption of the SOC being tested due to competitive adsorption. The
significance of the effect will depend on the concentration of background SOCs and their
adsorbability relative to the SOC being tested. For studies evaluating AURs at breakthrough,
estimates of run times to breakthrough must be examined together with existing water quality to
determine the potential reliability of the estimates.
BOM in water can reduce the adsorption capacity of SOCs. Since all source waters contain
organic matter, some impact is expected. Higher levels of BOM will typically have an increased
impact on adsorption of SOCs, but characteristics of the organic matter are important and the
adsorbability of the SOC is also a factor. Measurement of the source water TOC concentration
will provide an indicator of the level of BOM present. Pretreatment prior to the adsorption
process may reduce TOC levels. Other water quality indicators such as pH, temperature, and
conductivity may impact adsorption and should be quantified.
Seasonal variability in water quality may impact the results of equipment verification testing
since testing duration often spans several months. Assessment of seasonal variability in water
quality prior to equipment verification testing will help in evaluating whether the proposed water
source is appropriate, what type of pretreatment might be necessary, or the appropriateness of
pretreatment that is already in place. Source water variability should be evaluated in relation to
the expected length of the testing period
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8.2 Objectives
The objectives of this task are to:
Identify SOCs known to occur in the proposed source water;
Determine typical values for concentrations of other water quality parameters;
Identify any characteristic seasonal trends in concentrations of SOCs and other
water quality parameters;
Determine the level of BOM present in the source water; and
Assess the need for pretreatment prior to adsorption, or assess the appropriateness
of designed pretreatment.
If historic water quality data is not available for one or more parameters, an analysis of the
proposed source water shall be performed for these parameters.
8.3 Work Plan
A combination of laboratory analysis and review of historic data should provide the needed data
to evaluate source water quality. Sources for historic data include municipalities, laboratories,
United States Geographical Survey (USGS), EPA, and local regulatory agencies. Analysis of the
proposed source water prior to verification testing shall be performed for those parameters for
which no historic data can be located. Ideally, 2 to 5 years of historic water quality data for each
parameter will be available for the proposed source water. At a minimum, 1 year of data
sampled at no greater than 3-month intervals, may constitute historic data.
The FTO shall prepare a Source Water Quality Evaluation Report containing the historic and
monitored data obtained, a statistical evaluation of the data, and graphical summaries for all
parameters. This report shall be shared with NSF so that NSF and the FTO can determine the
significance of the data for use in developing a PSTP. If the source water quality data is not
obtained or analyzed properly, the verification test may fail or the results of the test may not be
considered acceptable.
The report shall list all SOCs previously identified in the source water, emphasizing those
encountered most recently and those that show a seasonal reoccurrence that might impact
equipment verification testing.
A description of the source water should also be included in the Source Water Quality
Evaluation Report including, but not limited to, the following items:
Nature of water source (i.e., ground water or surface water);
Location of water source;
Size of watershed;
Brief description of land use; and
Potential sources of pollution.
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If the SOC concentrations in the source water are below that described by the manufacturer's
statement of performance capabilities, higher SOC concentrations can be obtained during
verification testing by spiking.
8.4 Analytical Schedule
When historic data are not available, it is recommended that at least 12 months of monthly (or
more frequent) monitoring be performed prior to verification testing. At a minimum, 2 samples,
spaced by a minimum of 4 weeks and a maximum of 12 months, shall be obtained for the
parameters listed in Table 8.1.
Table 8.1 Source Water Sampling Requirements*
Parameter Notes
Alkalinity
Ammonia
Calcium hardness
Conductivity
Dissolved oxygen
Hydrogen sulfide
pH
SOC scan
Temperature
Total chlorine
Total dissolved solids (TDS)
Total hardness
TOC
Total suspended solids (TSS)
Turbidity
UV-254
*See Table 10.1 for analytical methods.
All data collected, whether from historic records or sampled directly and analyzed, shall be
summarized in conjunction with the sampling date. Results shall include the average, minimum,
maximum, and number of data points in the data set. For sample sets of eight or more, the results
shall also include the standard deviation and confidence interval for each analyte. When
summarizing SOC data of sample sets of eight or more, the 10th, 25th, 50th, 75th, and 90th
percentiles shall also be reported.
For each water quality parameter, a graph of concentration vs. sampling date shall be
constructed. This type of graph aids in the interpretation of seasonal trends that may impact
Optional
Optional
Required for groundwater sources only.
Required for groundwater sources only.
Standard Methods 6410B, 6420C, 6431C, 6440C, 6630D.
EPA Method 525.2 (extended for broad spectrum)
Total chlorine residual must be < 0.1 mg/L during verification
testing.
Optional
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equipment verification testing. Where convenient (e.g., calcium and total hardness) more than
one parameter may be combined in one graph. The concentration of each parameter shall be
plotted against actual sampling date. A box-and-whisker style plot to demonstrate the
distribution of each parameter is also recommended.
8.5 Evaluation Criteria
The source water quality shall be evaluated in the context of the manufacturer's statement of
performance capabilities for the removal of SOCs. The source water quality shall also be
evaluated with regards to the appropriateness of pretreatment in place prior to adsorption or the
need for pretreatment. The source water quality should challenge the capabilities of the
equipment, but should not be beyond the range of water quality suitable for treatment by the
equipment. Other evaluation criteria are given below:
Pretreatment for particle removal may be required if the source water turbidity is
greater than 5 to 10 NTU or if the source water TSS exceeds 5 mg/L.
Manufacturer specifications regarding pretreatment for particle removal should be
followed.
Pretreatment for hardness may be required if the source water hardness is greater
than the manufacturer's recommendations or if the pH, alkalinity, and hardness
analyses indicate that the water is unstable.
Adjustment of source water pH may be required if the source water pH is outside
the manufacturer's specifications. Water pH can impact adsorption efficiency
and, at extremes, may pose a corrosion hazard to the equipment.
9.0 TASK 2: SYSTEM DESIGN AND OPERATION
9.1 Introduction
This task involves procedures for determining the design and operating parameters of the
adsorptive media treatment system.
9.2 Objectives
The objectives of this task are to:
Establish the experimental design (mode of operation: constant, spike, or variable
influent; SOC spiking);
Document treatment system design parameters;
Describe system start-up and O&M procedures;
Develop an operations monitoring plan; and
Estimate the run time to SOC breakthrough (for verification testing beyond the minimal
13.3-day period).
Documentation of the treatment system design parameters shall be provided to EPA, NSF, and
peer reviewers for evaluation.
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Each PSTP will include a list of criteria for evaluating O&M information This shall be
compiled and submitted for evaluation by EPA, NSF and technical peer reviewers. An example
is provided in Table 9.1. The purpose of this O&M information is to allow utilities to effectively
choose a technology that their operators are capable of operating, and to provide information on
how many hours the operators can be expected to work on the system. Information about
obtaining replacement parts and ease of operation of the system would also be valuable.
Table 9.1 Maintenance and Operability Information for Adsorptive Media Package Plants
Maintenance Information
Equipment Maintenance freque ncy Replacement frequency
Pumps
Valves
Motors
Mixers
Chemical mixers
Water meters
Pressure gauges
Cartridge filters
Seals
Piping
Operability Information: Rank 1 (easy) to 3 (difficult) or N/A (not applicable)
Operation aspect Rank
Chemical feed pumps calibration
Flow meters calibration
Pressure gauges calibration
pH meters calibration
TDS or conductivity meters calibration
9.3 Work Plan
The PSTP shall specify information on the design and operation of the adsorption system being
evaluated. The work activities of this task are described below.
Experimental design. Three types of experimental designs are allowable under this TSTP: (1)
constant influent with low variability, (2) constant influent with high variability, and (3)
attenuation of a spiked influent. In general, this TSTP is designed for verification testing of a
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system treating a single SOC at a constant influent concentration with low variability. In some
cases, the manufacturer's statement of performance capabilities may be based on a system
treating a water with high variability in SOC concentration, or it may be based on attenuation of
a spiked influent. In these cases, the experimental design will be based on testing under the
influent conditions to be verified.
If the SOC to be tested for removal by adsorptive media is not present in the influent to the
adsorptive media, it shall be spiked into the influent water so that the resulting concentration is
equal to the targeted concentration. A sampling point shall be located downstream of the spike
location, but prior to the adsorption media, to confirm the influent concentration during testing.
All influent samples shall be taken from this sampling point. For testing of highly variable
influent conditions or attenuation of a spike influent, spiking shall simulate the conditions of
high variability or a spiked influent. For example, a spike concentration of 50 |ig/L diquat for a
duration of 3 days could simulate a spike influent for an attenuation study. In all cases, spiking
of the SOC shall match as closely as possible the influent conditions described in the
manufacturer's statement of performance capabilities.
This TSTP is designed to assess the removal of only one SOC in the adsorptive system influent.
If a manufacturer's statement of performance capabilities is based on simultaneous treatment of
multiple compounds, this should be simulated in the adsorption influent by spiking additional
compounds as necessary. Some sections in this document, such as the estimation of run time to
breakthrough, are designed based on a single compound influent and are not directly applicable
to simultaneous treatment of multiple compounds. In general, run times will be lower (AURs
will be higher) for systems subjected to multiple influent compounds as compared to those
treating an influent water with a single compound, due to the effects of competitive adsorption.
System design parameters. The FTO shall document the adsorption system design parameters
listed in Table 9.2. The PSTP shall contain a simple schematic of the entire treatment system,
including any pretreatment processes, showing sampling points, spike location, valves, pumps,
etc. An example of this schematic is shown in Figure 9.1.
Start-up and O&M procedures. System start-up and O&M procedures based on manufacturer
specifications shall be described by the FTO in the PSTP. Specific procedures for backwashing
and regeneration shall be included. Start-up procedures may include bed preparation such as
pre-wetting, degassing, and fines removal. Start-up itself will involve setting valves to the
correct run status, starting the feed pump to deliver test water to the system, adjusting the flow
rate to the target value, and other procedures as required by the manufacturer. Assuming
continuous operation, the system shall be operated for 24 hours before sampling commences.
For purposes of calculating run times, the start of operation shall constitute the beginning of the
run.
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Table 9.2 Adsorption System Design Parameters
Parameter Units Notes
General
Test type
Test location
Utility name
Water source
Water source name
Water source type (surface water only)
Feed mode (semi-batch or continuous)
Spiked SOC compound(s), if any
T arget spike concentration(s)
Spiking method
Pretreatment processes
Adsorptive Media
Media manufacturer
Media type
Media trade name
Mesh size
Effective size, dio
Mean particle diameter, dso
Apparent bed density, Pgac
Hg/L
Constant influent with low variability, constant influent
with high variability, or attenuation of spiked influent
Surface or ground water
Reservoir, lake, river, etc.
Describe
Describe
Describe
Bituminous, lignite, etc.
US std Upper x lower
mesh sizes
mm Indicate whether measured in field or as reported by
manufacturer
mm Indicate whether measured in field or as reported by
manufacturer
g/L, kg/rr?, Indicate whether measured in field or as reported by
lb/ft
manufacturer
Adsorption System
Contactor configuration
Number of adsorbers in series
Adsorber dimensions
BV per adsorber
Bed depth for each adsorber
Volumetric flow rate
EBCT
m
L
m
mL/min
min
Hydraulic loading rate (or superficial velocity) m/hr
Mass of dry media per adsorber kg
Regeneration system, regenerant fluid, and
regeneration procedure
Describe
Diameter, depth and any other appropriate dimensions
Clearly report total EBCT if more than one contactor in
series
Describe, if system has in-place regeneration capacity
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Source
Water
IT"1
ฆET
Feed
Pump
Backwash Water
Supply
Backwash
Wastewater
1
Effluent
A.
Sampling
Point
= Pressure
Gauge
Pretreatment Adsorber No. 1 Adsorber No. 2
Figure 9.1 Example of an Adsorption Treatment System Schematic
Operation with a continuous flow of test water from the source is preferable, but continuous
feeding from a batch-filled feed tank is acceptable. If a batch feed tank is used, the residence
time in the feed tank should be minimized to avoid volatilization losses of SOCs. (Although the
SOC to be tested may be considered nonvolatile, other SOCs present in the source water that
may impact adsorption performance may be semi-volatile or volatile.) The system flow rate
should be adjusted as necessary during operation to maintain the system flow rate within 5% of
the target flow. The system should be operated continuously to the extent possible, and only shut
down for backwashing, necessary maintenance, or regeneration (for in-place regenerable media).
Any down time shall be recorded and not included in the cumulative run time or throughput
volume calculations. The reason for each shutdown shall be documented. Adsorbers using non-
disposable media should be backwashed at least once during the test period. The manufacturer
shall specify backwash parameters including, but not limited to, flow rate, percent bed
expansion, and duration of expansion.
If the system is designed for continuous operation, then the system should be evaluated under
continuous operation for verification testing. If the system is designed for intermittent or
continuous operation, than either mode of operation during verification testing is acceptable. It
is preferable that the system be operated continuously. As with down time, total operation time
under intermittent operation constitutes the sum of the amount of time the system is in operation
providing treated water.
Operations monitoring plan The FTO shall provide an operations monitoring plan in the
PSTP, including operational parameters to be monitored, monitoring points, and monitoring
frequencies. At a minimum, flow rate, pressure before and after each adsorption or filtration bed
and headloss (differential pressure) across each bed, influent temperature, and influent pH should
be monitored routinely. Other parameters recommended by the equipment manufacturer should
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also be included. Influent and effluent sampling times should also be specified in the monitoring
plan.
Estimation of throughput to breakthrough. For systems evaluating single SOC adsorption
under constant influent conditions with low variability, the following section provides a
methodology for estimating the run time to breakthrough. This step should still be followed if
verification testing is planned for the minimum 13.3-day period, to confirm that breakthrough
will most likely not occur within the 13.3-day run time. If the objective of verification testing is
to achieve breakthrough of the compound treated, an estimation of throughput to breakthrough is
critical for purposes of estimating the duration of the operation cycle, and for purposes of
designing a sampling plan to effectively capture the breakthrough curve and/or the breakthrough
point (point at which the effluent concentration exceeds the treatment objective).
If the run time estimate to breakthrough is lower than 13.3 days, then effluent sampling during
verification testing should be designed assuming that the AUR will be based on operation of the
system to breakthrough. This should be done even if verification testing is planned for only 13.3
days: breakthrough may occur earlier than 13.3 days, and sampling guidelines should be
followed to best capture the point of breakthrough for use in the AUR calculation. The system
must be operated for a minimum 13.3-day period regardless of when the treatment objective is
exceeded. If it is very likely that the treatment objective will be exceeded during the 13.3-day
minimum verification period, then it is recommended that the manufacturer evaluate
modifications to the system design, such as an increase in the adsorber EBCT.
This method of estimating adsorbent bed life to breakthrough is based on a methodology
described in Snoeyink and Summers (1999). It is assumed that all the adsorbent in the adsorber
will reach equilibrium with the influent concentration, that isotherm data can be successfully
extrapolated to the influent concentration to estimate the capacity, and that the length of the mass
transfer zone is negligible (a very sharp breakthrough curve is assumed).
This method is based on isotherm data using the Freundlich equation, presented as Equation 6:
where (q)o is the mass adsorbed (mg/g) when the effluent concentration, Ce, is equal to the
influent concentration, Co; and K and 1 hi are constants. Literature sources should be consulted
for appropriate values of K and 1 In (Snoeyink and Summers 1999; Sontheimer, Crittenden, and
Summers 1988; Faust and Aly 1998; Speth and Miltner 1990, 1998).
The AUR (mass of adsorbent in the column divided by the volume treated to breakthrough) is
then estimated from isotherm data in the formula presented as Equation 7:
(q)0=KC0lln
(6)
AUR(g/L)
(C0-Ce) m^L
(q)0(m^g)
(7)
where Ce is the average effluent concentration during the entire run.
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Using this estimate of the AUR, the volume of water that can be treated per unit volume of
carbon is estimated by Equation 8:
Ybt (8)
AUR
where Ybt is the throughput in BV and Pgac is the apparent density of the adsorbent.
Finally, the operation time to breakthrough, tbt, in days can be calculated from the throughput by
Equation 9:
^=rw-EBCT(min) (?)
l,440(min/ day)
The value of tbt estimated by Equation 9 is a rough estimate of the time to breakthrough, based
on several assumptions noted above. It should be used with care, and a generous safety factor
should be included, as breakthrough may occur much earlier or later than this run time estimate
due to several factors described previously.
Several limitations of this method exist and should be noted. First, it is only valid for a single
long contactor, or for columns in series in which all of the adsorbent in the column is in
equilibrium with the compound at the influent concentration. Second, this method does not
account for the potential impact of biodegradation of the compound during treatment or slow
adsorption kinetics. Finally, the impact of competition for adsorption sites on adsorption
equilibrium in a batch is not necessarily the same as that on adsorption in a column. Competitive
effects may have a larger impact on adsorption in a column than in a batch study (Snoeyink and
Summers 1999).
Another limitation of the AUR estimated by this method is that adsorption capacity is based on
experiments performed in distilled water, in the absence of BOM that may have a significant
impact on adsorption capacity in the field. A natural water correction factor has been proposed,
whereby the distilled water AUR (AURdw) is adjusted, yielding a better estimate of the natural
water AUR, AURnw (Ford et al., 1989; USEPA 1990). For this relationship, the units of AUR
are lb/1,000 gal. The correlation described by Equation 10a is valid for values of AURdw =
0.564 lbs/1,000 gal. For values of AURdw > 0.564 lbs/1,000 gal, the value for AURnw used is
equal to AURdw, as described in Equation 10b.
AUR NW = 0.7443- (AURDW)04835 AURdw = 0.564 lbs/1,000 gal (10a)
AURnw = AURDW AURdw > 0.564 lbs/1,000 gal (10b)
Example. To estimate the adsorbent bed life of a 10 minute EBCT GAC (Pgac = 500 g/L)
contactor treating dalapon at a constant influent concentration of 300 |ig/L, first look up the
Freundlich K and 1 In values for dalapon, as shown in Equations 11 and 12:
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K = 23 (mg/g)(L/mg)1/n
(11)
1 In = 0.224 (12)
Use Equation 6 to calculate (qe)o = 17.6 mg/g. Assuming Ce = 0, use Equation 7 to estimate the
AURdw, 0.0171 g/L (0.142 lb/1,000 gal). Correcting this value using Equation 10a, gives
AURnw = 0.290 lb/1,000 gal or 0.0348 g/L. The throughput, F/,,, is 14,400 BV, calculated by
Equation 8. Finally, the estimate of operation time to breakthrough, tbt, is calculated by Equation
9 , which is 99.8 days.
Although Equation 10a includes a correction factor for the impact of BOM on adsorption, it does
not account for the impacts of biodegradation or competitive effects due to the possible presence
of other SOCs. The BOM correction is only an estimate; the actual impact of BOM on
performance will vary, depending on the characteristics of BOM, concentration, and the amount
of time the adsorbent has been preloaded with BOM prior to verification testing of SOC
adsorption.
The above analysis is applicable to single contactor operation. For package plants that operate
two or more contactors in parallel, with staggered operation cycles, longer run times are expected
for a given treatment objective maintained in the blended effluent of all contactors. Depending
on the shape of the breakthrough curve, and the operation time to initial breakthrough for a
single contactor, the run time of each of two to four contactors operated in parallel-staggered
mode may be increased by 30 to 80%. For extremely sharp breakthrough curves, this mode of
operation may not yield any significant benefit, depending on the ratio of the treatment objective
to the influent concentration, in relation to the number of parallel contactors. It is recommended
that parallel operation of adsorbent contactors be modeled to yield the best estimate of operation
times based on maintaining a treatment objective in the blended effluent. See USEPA (1999) for
an analysis of multiple contactor effluent blending for GAC. Alternatively, the effluents of each
contactor can be monitored, with the experimental results of breakthrough in the first adsorber
used to refine the run time estimate based on the blended effluent.
9.4 Analytical Schedule
System flow rate, pressures and headloss across each contactor, and other operational parameters
should be measured at the frequencies indicated in Table 9.3. Ideally, flow rate and headloss are
measured on a continuous basis. The headloss before and after backwashing should be recorded
as a measure of backwash effectiveness. A record of backwashing frequency and backwash
water volume produced should also be maintained. See Table 9.3 for further details. Stoppage
time should be recorded, including the exact times of stoppage and restart, as well as the reason
for the stoppage. This will allow for an accurate assessment and adjustment for the impact of
stoppage time on the effective operation time. The cumulative amount of stoppage time that
must be taken into account in calculating the total run time of verification testing should be
continuously updated.
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Table 9.3 Schedule for Observing and Recording Package Plant Operating and
Performance Data
Operational Parameter
Action
Feed water and adsorbent contactor
volumetric flow rate
GAC contactor headloss
Filter backwash
Electric power
Chemicals used
Chemical feed volume and dosage
RPM of rapid mix and flocculator (if
applicable)
Hours operated per day
When staffed, check and record every 2 hours; adjust
when >5% above or below target. Record before and
after adjustment.
Record initial clean bed total headloss at start of run and
record total headloss every 2 hours, when staffed.
Record time and duration of each filter washing. Record
volume used to wash filter. Record headloss before and
after backwashing.
Record meter daily.
Record name of chemical, supplier, commercial
strength, and dilution used for stock solution to be fed (if
diluted) for all chemicals fed during treatment.
Refill as needed and
Check and record every 2 hours,
note volumes and times of refill.
Check daily and record.
Record in logbook at end of day or at beginning of first
shift on the following work day. Any stoppage of flow
to the contactors shall be recorded. Flow stoppage that
exceeds 2 hours per a 24-hour period or 7 hours per
week shall be accounted for by not including it in the
cumulative operation time.
9.5 Evaluation Criteria
The oontactor flow rate should be maintained within 5% of the target value. The flow rate
should be adjusted when it is outside of this range. Criteria for backwashing are usually based
on a headloss threshold and should be provided by the equipment manufacturer. The criteria will
likely vary depending on EBCT on adsorbent media size.
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10.0 TASK 3: SYSTEM INTEGRITY VERIFICATION TESTING
10.1 Introduction
This task will evaluate the short-term ability of the equipment to produce water of acceptable
quality. SIVT is not designed to evaluate the long-term ability of the equipment to treat water
containing SOCs. SIVT must be performed at least once for each system evaluated under this
TSTP.
10.2 Objectives
The objectives of this task are to demonstrate that the equipment is (1) able to produce a treated
water within performance objectives, and (2) able to operate reliably under field conditions.
Specific objectives include:
Characterization of the influent SOC concentration and variability and
Evaluation of the concentrations during testing of other water quality parameters
that impact SOC adsorption, including TOC, UV-254, pH, temperature, and other
background SOCs.
10.3 Work Plan
The manufacturer and its designated FTO shall specify in the PSTP the operating conditions to
be evaluated during verification testing and shall supply written procedures on the O&M of the
treatment system. For applications where the treatment system is expected to operate
continuously, the equipment shall be operated continuously for a minimum of 320 hours (13 full
days plus one 8-hour work shift) to complete SIVT. For applications where the treatment system
is expected to operate intermittently, such as for very small systems, the equipment shall be
operated for a minimum of 2 hours continuously each day for a total minimum operation time of
320 hours. For adsorptive media vessels operated as post-filter adsorbers, the media filters on-
line upstream of the adsorptive media vessels shall be operated from start-up until turbidity
breakthrough or terminal headloss is attained, at which time the media filters shall be
backwashed and operation shall resume.
For adsorptive media filters that are not operated as post-filter adsorbers, but that specify a
backwash cycle as part of normal operation, at least one backwashing event, located between day
3 and 10 of SIVT, shall be included in the test. This backwash shall be performed even if the
backwash criteria (e.g., volume treated, headloss, pressure drop) are not experienced or met.
Backwashing the adsorber a few days prior to the end of the SIVT allows for an evaluation of
system performance after backwashing. For systems that are backwashed more often (e.g., every
3 to 4 days), at least one backwashing event shall occur between days 3 and 10 of SIVT.
Interruptions in the treatment system shall be documented and are allowed only for backwashing
events and required equipment maintenance. Since adsorptive media performance is a function
of EBCT, which is dependent on the volumetric flow rate, it is critical that verification testing be
conducted at a set flow rate that is maintained within 5% of the design value.
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Any influent spiking irregularities that occur during the study must be reported by the FTO. This
includes, but is not limited to, events such as a period of time when the contaminant feed pump is
not pumping at the correct flow rate, a period of time when the contaminant stock solution runs
out, or a period of time when volatile losses may have occurred from the stock solution. The
FTO must document the occurrence of these events, including a clear description, corrective
actions taken, the length of time during which the irregularity occurred (this may have to be
estimated), and the approximate dates and times when the event began and ended. The
description should include the FTO's opinion as to the severity of the irregularity, in terms of its
impact on testing results.
Package plants that contain multiple adsorbent contactors to be operated in parallel should follow
manufacturer's guidelines for system start-up. If the contactors are to be operated in a staggered
format, then each contactor should be brought on-line sequentially, as designated by the
manufacturer's instructions. If the SOC to be treated is already present in the influent water,
then the start of verification testing should take place when the first contactor is brought on-line.
Alternatively, each contactor can be brought on-line sequentially until all contactors are in
operation prior to the start of verification testing if the SOC to be tested is not present in the
source water. Spiking of the SOC to be tested would begin when all contactors are operational.
The FTO shall provide the details for spiking in the PSTP, such as materials for preparation of
the spike solution, details about feed pumps, reservoirs and mixers, and sampling to confirm
influent concentrations.
Water Quality Sample Collection. Water quality data shall be collected at regular intervals as
described in the analytical schedule (see Table 10.1). Additional or more frequent analyses may
be stipulated at the discretion of the FTO. Sample collection frequency and procedure shall be
defined by the FTO in the PSTP.
The PSTP shall identify the treated water data quality objectives (DQOs) to be achieved in the
statement of performance capabilities of the equipment to be evaluated in the verification test.
The PSTP shall also identify in the statement of performance capabilities the specific SOCs that
shall be monitored during equipment testing. The statement of performance capabilities
prepared by the FTO shall indicate the range of water qualities and operating conditions under
which the equipment can be challenged while successfully treating the contaminated water
supply.
It should be noted that many of the packaged and/or modular drinking water treatment systems
participating in an SOC removal verification test will be capable of achieving multiple water
treatment objectives. Although the SOC TSTP is designed for the removal of SOCs, the
manufacturer may want to examine the capabilities of the treatment system for removal of
additional water quality parameters. Appropriate EPA/NSF ETV protocol(s) and TSTP(s)
should be consulted.
Many of the water quality parameters described in this task shall be measured on-site by the
NSF-qualified FTO. For the water quality parameters requiring analysis at an off-site laboratory,
water samples shall be collected in appropriate containers (containing necessary preservatives as
applicable) prepared by a laboratory that is certified, accredited or approved by a state, a
third-party organization (i.e., NSF), or the EPA. Representative methods to be used for
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measurement of water quality parameters in the field and lab are identified in Table 10.1. If new
methods are published and approved or current methods updated, the most current methods shall
be used.
Sample collection procedures for intermittent flow systems must ensure that freshly treated water
is collected and not water that was stagnant in the bed. For intermittent flow systems, sample
collection should occur during a continuous flow period, after a minimum of 10 BV has passed
through the system or after 1 hour of continuous flow.
Table 10.1 Required Water Quality Analyses and Minimum Sampling Frequencies for SIVT
Parameter Frequency Sampling Standard Method EPA Analysis
Location1
Method
Location2
SOCs
Daily
INF, EFF
See Table 10.2
See Table
10.2
2
Alkalinity
Weekly
INF
2320 B
3
Ammonia
Weekly
INF
4500-NH3 D, G
350.1
3
Calcium hardness
Weekly
INF
3111 D; 3120 B; 3500-CaD
200.7
3
Chlorine, free
Daily3
INF
4500-C1 D, F, G, H
1
Chlorine, total
Daily3
INF
4500-C1 D, E, F, G, I
1
Conductivity
Weekly
INF
2510 B
120.1
3
Dissolved oxygen
Weekly
INF
4500-0 B, G
1
Hydrogen sulfide
Weekly
INF
4500-S2" D, E, F, G
3
PH
Daily
INF, EFF
4500-H+ B
150.1; 150.2
1
Temperature
Daily
INF
2550 B
1
TDS
Weekly
INF
2540 C
3
Total hardness
Twice
weekly
INF
2340 B, C
3
TOC
Daily
INF, EFF
5310 B, C, D
2
Total suspended
Weekly
INF
2540 D
3
solids (TSS)
Turbidity
See note4
INF, EFF
2130 B
180.1
1
UV -254
Twice
weekly
INF, EFF
5910 B
3
1 INF: Influent; EFF: Effluent. Where both influent and effluent sampling is required, samples should be
paired (taken at approximately the same time).
Analysis location: 1-Must be analyzed on-site; 2-Must be analyzed by a laboratory that is certified,
accredited or approved by a state, a third party organization (i.e., NSF), or the EPA; 3-Can be analyzed either
on-site or by a laboratory that is certified, accredited or approved by a state, a third party organization (i.e.,
NSF), or the EPA.
3 Free and total chlorine should be analyzed daily to ensure the absence of chlorine in the influent water. The
FTO may require less frequent monitoring if there is no reason to expect free or total chlorine in the influent
water. This will depend on the water source.
4 For contactors operated in filter-adsorber mode, a continuous turbidimeter should be used. Daily samples
should be analyzed using a bench-top turbidimeter to confirm the continuous turbidimeter readings. For
contactors operated in post-filter adsorber mode, the minimum sampling frequency for turbidity is weekly.
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In the case of water quality samples to be shipped to the laboratory that is certified, accredited or
approved by a state, a third party organization (i.e., NSF), or the EPA for analysis, the samples
shall be collected in appropriate containers (containing preservatives as applicable) prepared by
the laboratory. These samples shall be preserved, stored, shipped, and analyzed in accordance
with appropriate procedures and holding times, as specified by the analytical laboratory.
Acceptable methods for ihe required analytical procedures are described in Task 8, Quality
Assurance/Quality Control. At a minimum, all PSTPs shall include a table(s) showing all
parameters to be analyzed, the analytical methods, the laboratory reporting limits or quantitation
limits, sample volume, bottle type, preservation method, and holding time.
If the known or expected concentration of the SOC or SOCs to be tested in the influent water is
lower than desired for verification testing, then the influent water should be spiked to achieve the
desired concentration. The FTO shall stipulate in the PSTP procedures to be followed for
influent spiking. These should be based on information reported in the literature and the
experience of the FTO and manufacturer with the compound or compounds to be tested.
In general, three types of experimental designs for ACVT are allowable under this TSTP (as
described in Section 9.3). SIVT should be conducted following the procedures applicable to the
experimental design to be tested during ACVT. Furthermore, once the SIVT phase is complete,
testing may continue under the guidelines and procedures described for ACVT. It is expected
that SIVT will be performed with a constant influent concentration of the SOCs to be tested.
10.4 Analytical Schedule
10.4.1 Operational Data Collection
The FTO shall provide written procedures describing the operational parameters that
should be monitored, the monitoring points, and the frequency of monitoring. At a
minimum, such operational parameters shall include system flow rates and headloss or
pressure. The FTO shall include acceptable values and ranges for all operational
parameters monitored.
10.4.2 Water Quality Data Collection
During SIVT, the GAC influent and effluent water quality shall be characterized by
analysis of the water quality parameters listed in Table 10.1. The first sampling for each
required analyte shall be performed 1 day after plant operation start-up and then by the
given frequency. Although many parameters may be analyzed off site, free and total
chlorine residual, dissolved oxygen, pH, temperature, and turbidity must be analyzed on-
site. It is recommended that UV-254 be also analyzed on-site.
The required water quality parameters listed in Table 10.1 are selected to provide state
drinking water regulatory agencies with background data on the quality of the GAC
influent water being treated and the quality of the treated water. Collection of these data
will enhance the acceptability of the SIVT to a wide range of drinking water regulatory
agencies.
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Acceptable analytical methods for Phase II and V Rule SOCs are listed in Table 10.2.
References to both Standard Method and EPA Method procedures for sample analysis are
given. If new methods are published and approved or current methods updated, the most
current methods shall be used.
For the water quality parameters requiring analysis at an off-site laboratory, water
samples shall be collected in appropriate containers (containing necessary preservatives
as applicable) prepared by a laboratory that is certified, accredited or approved by a state,
a third-party organization (i.e., NSF), or the EPA These samples shall be preserved,
stored, shipped and analyzed in accordance with appropriate procedures and holding
times, including chain of custody requirements, as specified by the analytical lab.
Table 10.2 Analytical Methods for Phase II and V Rule SOCs
Parameter
Standard Method
EPA Method
Alachlor
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Atrazine
Benzo(a)pyrene (PAHs)
Carbofuran
Chlordane
2,4-D
Dalapon
Di (2-ethylhexyl) adipate
Di (2-ethylhexyl) phthalate
Dibromochloropropane (DBCP)
Dinoseb
6610 B
6610 B
6610 B
6410 B; 6440 B
6610 B
6410 B; 6630 B,C
6640 B
6640 B
6200 B, C; 6231 B
6640 B
505; 507; 525.2; 508.1; 551.1
531.1
531.1
531.1
505; 507; 508.1; 525.2; 551.1
525.2; 550; 550.1
531.1
505; 508; 508.1; 525.2
515.1; 515.2; 555
515.1; 515.3; 552.1; 552.2
506; 525.2
506; 525.2
504.1; 551
515.1; 515.2; 515.3; 555
Diquat
549.2
Endothall
548.1
Endrin
6410 B; 6630 B, C
505; 508; 508.1; 525.2; 551.1
Ethylene dibromide (EDB)
6040 B; 6200 B, C; 6231 B
504.1; 551
Glyphosate
6651 B
547
Heptachlor
6410 B; 6630 B, C
505; 508; 508.1; 525.2; 551.1
Heptachlor epoxide
6410 B; 6630 B, C
505; 508; 508.1; 525.2; 551.1
Hexachlorobenzene
6040 B; 6410 B
505; 508; 508.1; 525.2; 551.1
Hexachlorocyclopentadiene
6410 B
505; 508; 508.1; 525.2; 551.1
Lindane
6630 B
505; 508; 508.1; 525.2; 551.1
Methoxychlor
6630 B
505; 508; 508.1; 525.2; 551.1
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Table 10.2 Analytical Methods for Phase II and V Rule SOCs (cont.)
Parameter Standard Method EPA Method
Oxamyl (vydate)
6610
B
531.1
Pentachlorophenol
6410
B;
6420
B; 6640 B
515.1; 515.2; 515.3; 525.2; 555
Picloram
6640
B
515.1; 515.2; 515.3; 555
Polychlorinated biphenyls (PCBs)
6410
B;
6630
C
505; 508; 508A; 508.1; 515.2
Simazine
505; 507; 508.1; 525.2; 551.1
2,3,7,8-TCDD (Dioxin)
1613
Toxaphene
6410
B;
6630
B, C
505; 508; 508.1; 525.2
2,4,5-TP (Silvex)
6640
B
515.1; 515.2; 515.3; 555
10.5 Evaluation Criteria
The results of SIVT shall be evaluated based on removal of SOCs. For filter-adsorbers, turbidity
removal shall also be evaluated. The EPA/NSF Equipment Verification Testing Plan for
Coagulation and Filtration within the EPA/NSF ETV Protocol for Physical Removal of
Microbiological and Particulate Contaminants (EPA/NSF 2002) shall be followed if the filter-
adsorber is to be verified as a filter of particulate matter. Time series plots shall be generated
describing GAC influent and effluent SOC concentration, TOC concentration, UV-254, and
turbidity. The other parameters analyzed should be tabulated. Statistical analyses of the data
results shall include averages, minimum, and maximum for each analyte. For sample sets of
eight or more, the results shall also include the standard deviation and confidence interval for
each analyte. When summarizing SOC data of sample sets of eight or more, the 10th, 25th, 50th,
75th, and 90th percentiles shall also be reported. The length of the study, after taking into account
all stoppage time, must be clearly reported.
The SIVT should yield high percent removals (low immediate breakthrough) of SOCs, TOC, and
UV-254, demonstrating the initial \ery effective ability of GAC to remove natural and synthetic
organic compounds. High levels of immediate breakthrough of SOCs are indicative of failure of
the treatment system to initially adsorb SOCs, possibly due to hydraulic channeling, insufficient
media, very low GAC adsorption capacity, or inappropriate GAC contactor design for the water
quality tested (concentration of SOC combined with concentrations of other water quality
parameters). Long-term SOC control will be evaluated during Task 4, Adsorption Capacity
Verification Testing.
The mean and variability of the influent SOC concentration during testing shall be reported by
the FTO. A target concentration value may be reported as the mean concentration during testing
if it is within 5% of the actual measured mean concentration.
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11.0 TASK 4: ADSORPTION CAPACITY VERIFICATION TESTING
11.1 Introduction
Removal of SOCs by adsorptive media is an unsteady-state process. The ability of an adsorptive
media treatment system to remove SOCs in most cases will initially be excellent, but will
diminish over time as breakthrough of the SOC occurs. The breakthrough of a given SOC is
characteristic of the SOC and of the treatment system: breakthrough is dependent on design,
EBCT, type of adsorptive media used, influent SOC concentration, SOC adsorbability, and
influent water quality. Breakthrough behavior is highly dependent on the concentration and
adsorbability of SOCs.
The main purpose of ACVT is to evaluate the capability of the adsorptive media treatment
system for removal of SOCs. Specifically, the AUR will be determined for the SOC tested. The
AUR will be assessed under the design and operation conditions of the treatment system, as well
as influent water quality conditions of the source water after pretreatment, if any. Accurate
characterization of influent water quality is important because the AUR, as a function of influent
water quality, needs to be evaluated in that context. The "influent" is defined as water entering
the adsorber after all pretreatment steps. The breakthrough of the SOC must be captured by a
sufficient amount of data (number and scheduling of effluent samples) to allow for an accurate
determination of the AUR under the conditions of the verification test.
ACVT shall be performed at least once for a system, but may be performed multiple times on
different water qualities to verify the manufacturer's objectives made on the ability of the
equipment to remove SOCs under various influent water quality conditions. ACVT may also be
performed multiple times to evaluate different levels of influent SOCs (treatment challenge
levels) and different modes of testing (constant influent with low or high variability, and
attenuation of a spike SOC).
For standard testing (single compound at constant target influent concentration with low
variability), it is critical to accurately determine the average influent concentration during testing
of a system. Furthermore, variability of the influent concentration above and below the mean
must be minimized. Excessive variability may impact the AUR and diminish the validity of the
test and, therefore, is not acceptable. The maximum allowable influent concentration variability
is defined in this section. The mean and variability of the influent SOC concentration during
testing shall be reported by the FTO. A target concentration value may be reported as the mean
concentration during testing if it is within 5% of the actual measured mean concentration.
Systems evaluating adsorbent performance under non-standard modes (attenuation of a spiked
influent SOC and treatment of a highly variable influent concentration) will not target a constant
influent concentration with low variability; restrictions on the variability of the influent
concentration do not apply. Separate influent variability guidelines for non-standard modes of
operation are described in this section.
Adsorption will also be affected by the concentrations of other water quality parameters and
SOCs. Characterization of the influent water quality to the adsorption process is needed so that
system performance can be assessed properly and to ensure that influent water quality conditions
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match those targeted for equipment verification testing. The adsorption process influent water
and the source water may or may not be identical, depending on whether the treatment
equipment incorporates pretreatment (such as filtration).
Package plants that contain multiple contactors operated in parallel and staggered with respect to
operation cycles shall be considered a single adsorptive media system: the influent water as
applied in this section relates to the influent to all parallel contactors. The effluent as applied in
this section relates to the blended effluent of all contactors in operation. It is assumed that the
contactors in a multiple contactor package plant each contain the same EBCT. If the EBCT
varies between contactors, then an average EBCT should be reported, as well as the actual
EBCTs of each adsorber and an explanation of the system setup and operation.
11.2 Objectives
The objective of this task is to verify the manufacturer's statement of performance capability
regarding the operation time and AUR of the adsorptive media treatment system for removal of
one or more SOCs to levels below the treatment objective.
Specific objectives include:
Characterization of the influent SOC concentration and variability;
Evaluation of the concentrations during testing of other water quality parameters
that impact SOC adsorption including TOC, UV-254, pH, temperature, and other
background SOCs;
Evaluation of the breakthrough of SOC to determine the AUR; and
Evaluation of the breakthrough of other water quality parameters.
11.3 Work Plan
For ACVT, the FTO shall specify a run time criterion. A run time criterion can be set based on
treated water quality conditions (such as exceeding the MCL for the SOC tested), or set to a
specific maximum run time. A combination of treated water quality and maximum run time
criteria may also be utilized. Since the duration of SIVT is 13 days plus one 8-hour shift, the
minimum duration of ACVT shall also be 13 days plus one 8-hour shift. However, it is expected
that all ACVT runs will be longer than 2 weeks in duration.
The PSTP shall identify the treated water DQOs to be achieved in the statement of performance
capabilities of the equipment to be evaluated in the verification test. The PSTP shall also
identify in the statement of performance capabilities the specific SOCs that shall be monitored
during equipment testing. The statement of performance capabilities prepared by the FTO shall
indicate the range of water qualities and operating conditions under which the equipment can be
challenged while successfully treating the contaminated water supply.
It should be noted that many of the packaged and/or modular drinking water treatment systems
participating in an SOC removal verification test will be capable of achieving multiple water
treatment objectives. Although the SOC TSTP is designed for the removal of SOCs, the
manufacturer may want to examine the capabilities of the treatment system for removal of
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additional water quality parameters. Appropriate EPA/NSF ETV protocol(s) and TSTP(s)
should be consulted.
Some of the water quality parameters described in this task shall be measured on-site by the
NSF-qualified FTO. For the water quality parameters requiring analysis off site, water samples
shall be analyzed by a laboratory that is certified, accredited or approved by a state, a third-party
organization (i.e., NSF), or the EPA. Representative methods to be used for measurement of
water quality parameters in the field and lab are identified in Table 10.2. The analytical methods
utilized for on-site monitoring of raw and finished water qualities are described in Task 8,
Quality Assurance/Quality Control.
For the water quality parameters requiring analysis at an off-site laboratory, water samples shall
be collected in appropriate containers (containing necessary preservatives as applicable) prepared
by a laboratory that is certified, accredited or approved by a state, a third-party organization (i.e.,
NSF), or the EPA. These samples shall be preserved, stored, shipped and analyzed in
accordance with appropriate procedures and holding times, including chain of custody
requirements, as specified by the analytical lab.
Package plants that contain multiple adsorbent contactors to be operated in parallel should follow
manufacturer's guidelines for system start-up. If the contactors are to be operated in a staggered
format, then each contactor should be brought on-line sequentially, as designated by the
manufacturer's instructions. If the SOC to be treated is already present in the influent water,
then the start of verification testing should take place when the first contactor is brought on-line.
Alternatively, each contactor can be brought on-line sequentially until all contactors are in
operation prior to the start of verification testing if the SOC to be tested is not present in the
source water. Spiking of the SOC to be tested would begin when all contactors are operational.
For multiple contactor verification testing of attenuation of a spiked compound, all contactors
should be brought on-line sequentially as designated by the manufacturer prior to spiking the
compound.
Any influent spiking irregularities that occur during the study must be reported by the FTO. This
includes, but is not limited to, events such as a period of time when the contaminant feed pump is
not pumping at the correct flow rate, a period of time when the contaminant stock solution runs
out, or a period of time when volatile losses may have occurred from the stock solution. The
FTO must document the occurrence of these events including a clear description, corrective
actions taken, the length of time during which the irregularity occurred (this may have to be
estimated), and the known or estimated dates and times when the event began and ended. The
description should include the FTO's opinion as to the severity of the irregularity in terms of its
impact on testing results.
11.4 Analytical Schedule
11.4.1 Influent Sampling Requirements
Standard testing. All SOCs named in the manufacturer's statement of performance
capabilities or analyzed in the adsorptive system effluent shall be sampled in the influent
water. Influent SOC samples shall be taken at a sampling port located prior to the
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adsorptive media, after all pretreatment steps. During the first 2 weeks of testing,
systems being tested for the first time should follow the influent sampling guidelines
specified under Task 3, System Integrity Verification Testing. These systems should then
follow the requirements specified in this section for influent sampling after the first 2
weeks. Systems that have already completed SIVT requirements can follow the influent
sampling guidelines specified in this section for the entire study.
"Standard testing" applies to systems expected to be tested with a constant SOC influent
concentration study with a low amount of influent variability. Standard testing also
applies to studies in which the influent SOC is spiked to a constant level into a source
water in which the influent SOC is either not present or is present at a lower, constant
concentration. For standard testing, influent SOC concentration variability should not
exceed the guidelines summarized in Table 10.2.
Since variability of source water SOC concentration may be higher than expected during
any study, about twice as many influent samples are required to be taken as are analyzed.
Equation 13 defines the total number of influent samples that must be taken (this number
will be greater than the number analyzed, as long as variability is shown to be within the
guidelines summarized in Table 11.1).
63.7
N, = - (13)
8.24
where Ns is the required minimum number of samples taken (but not necessarily
analyzed) for low-variable influent studies and tbt is the operation time to breakthrough in
days.
The result of this formula should be rounded to the nearest whole integer. Of the total
number of samples taken (as given by Equation 13), every second sample must be
analyzed, beginning with the first sample taken. By using this formula, the minimum
frequency of influent sampling is gradually reduced: for a 1-year study, a minimum of 26
samples must be analyzed, or 1 sample every 2 weeks. This compares to 8 analyzed
samples required for a 60-day study, or approximately 1 every week. The intent of this
minimum influent sampling schedule is to reduce the sampling burden on more lengthy
studies. The equation is not valid for run times shorter than 60 days. Assuming SIVT is
not applicable to the study, the frequency of sampling between day 1 and 60 should be 3
samples per week. As before, every second sample should be analyzed. When SIVT is
performed for the first 2 weeks of operation, then the sampling guidelines given in Task
3, System Integrity Verification Testing, must be followed for the first 2 weeks. Between
14 and 60 days, 3 samples per week are required, with every second sample analyzed.
If the data resulting from the analysis of every second influent sample confirms that the
variability of the influent SOC concentration is low, then the samples taken but not
analyzed can be discarded. However, if the data shows that the influent variability is
unexpectedly high, then the "skipped" samples must be analyzed for a more accurate
assessment of influent SOC concentration variability. The breakpoint between low and
high variability is defined in Table 11.1.
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For purposes of determining the minimum influent sampling rate, the testing period is
defined as the operation time between start-up and breakthrough. If the SOC being tested
reaches breakthrough (as defined in this document) on day 100, but the system is
operated for an additional 150 days (for a total of 150 days since startup), the minimum
number of influent samples taken between day 1 and day 100 should be 10, as defined by
Equation 13. Influent samples taken after breakthrough occurs should not be used to
determine the mean influent concentration and influent concentration variability statistics.
As stated earlier, breakthrough is defined in this document as the point during the run
when the SOC concentration in the adsorber effluent exceeds the treatment objective.
In addition to the minimum frequency of influent sampling requirement, studies
performed on a source water with low SOC variability (or studies in which the SOC is
spiked to a constant concentration) must maintain an influent SOC concentration
variability below the maximum allowable, as defined by the relative standard deviation
(RSD), Equation 14:
RSD = 1.5-3.0
40.0
>3.0-10.0
30.0
>10.0
20.0
For example, if the method MRL for trichloroethylene is 1.0 |ig/L, and the average
measured influent trichloroethylene concentration of all samples analyzed between day 1
and tbt is 5.0 |ig/L, then the maximum RSD allowable is 30.0%. If the MRL was 2.0
|ig/L for the same average influent SOC concentration, then the maximum RSD
allowable would be 40.0%. Studies that exceed this maximum RSD must be classified as
adsorptive systems treating an influent water with a highly variable SOC concentration:
the "skipped" samples taken, but not analyzed, must now be analyzed. Additional
sampling requirements are stipulated for highly variable influent SOC concentration
studies as detailed below. Since the sampling rate required for studies conducted with
highly variable influent SOC concentration is more stringent than that for studies
conducted on influent SOCs with low variability, steps should be taken to minimize
variability of the influent SOC during low-variability studies. If variability is higher than
anticipated, the number of influent and effluent samples analyzed will be greater.
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Highly variable influent concentration. For studies designed to test adsorptive media
performance at a constant target influent concentration for a water source where a high
amount of variability is expected, a higher number of samples is necessary to capture the
variability of the influent SOC concentration. This higher sampling frequency is also
required for studies in which the influent SOC concentration varies over time, resulting in
an increasing or decreasing concentration over the course of the study, or other long-term
trends that will impact the calculated RSD. The influent SOC concentration in such a
study may not be extremely variable on a day-to-day basis, but the long-term trend must
be characterized with the increased sampling frequency. Such a study is not ideal as the
long-term change in influent concentration hampers data interpretation. This higher
influent sampling frequency is also recommended when the expected SOC influent
concentration variability is unknown.
The minimum number of influent samples for high-variability studies is also determined
by Equation 13. Every sample taken must be analyzed. By using this formula, the
minimum frequency of influent sampling is gradually reduced: for a 1-year study, a
minimum of 52 samples must be taken and analyzed, or 1 sample every week. This
compares to 15 samples required for a 60-day study, or approximately 2 every week. The
intent of this minimum influent sampling schedule is to reduce the sampling burden on
more lengthy studies. The equation is not valid for run times lower than 60 days.
Assuming SIVT is not applicable to the study, the frequency of sampling between day 1
and 60 should be 3 samples per week. Again, every sample should be analyzed. When
SIVT is performed for the first 2 weeks of operation, then the sampling guidelines given
in Task 3, System Integrity Verification Testing, must be followed for the first 2 weeks.
Between 14 and 60 days, 3 samples per week are required, with every second sample
analyzed.
For purposes of determining the minimum influent sampling rate, the testing period is
defined as the operation time between start-up and breakthrough. Therefore, if the SOC
being tested reaches breakthrough (as defined in this document) on day 100, but the
system is operated for an additional 50 days (for a total of 150 days since start-up), the
minimum number of influent samples taken between day 1 and day 100 should be 20, as
defined by Equation 13. Influent samples taken after breakthrough occurs should not be
used to determine the mean influent concentration and influent concentration variability
statistics. As stated earlier, breakthrough is defined in this document as the point during
the run when the adsorber effluent reaches or exceeds the treatment objective.
No maximum measure of variability shall be set for these highly variable influent studies,
but the variability in SOC influent concentration shall be summarized statistically by
calculating the mean, standard deviation, 10th, 25th, 50th, 75th, and 90th percentiles,
minimum, and maximum. In addition, a statement shall be included describing the
variability observed in the influent SOC concentration over the course of the study.
SOC spike attenuation. For spike attenuation studies, the sampling frequency required
for low-variability studies (standard testing) shall be followed. The purpose of sampling
will be mainly to demonstrate the absence of significant levels of the SOC before and
after the spike. During the spike, the influent shall be sampled more often, at a rate
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sufficient to capture the spike and confirm the accuracy of the spike concentration for
purposes of data interpretation. During the spike, at least 2 samples per day are required,
and a minimum total of 6 samples is required. Samples should be taken daily for at least
2 days before the spike and for at least 3 days after the spike.
Multiple SOC testing. Sampling requirements for verification testing of multiple SOCs
should follow the guidelines set forth above. Each SOC tested shall be sampled at the
minimum specified frequency.
Influent sampling requirements for other water quality parameters. Regardless of
the type of study performed (low SOC variability, high SOC variability, or SOC spike
attenuation), the sampling frequency for water quality parameters summarized in Table
11.2 shall be followed.
Table 11.2 Minimum Influent Sampling Frequency Requirements for
Water Quality Parameters
Parameter
Frequency
Alkalinity
Monthly
Ammonia (optional)
Monthly
Calcium hardness
Monthly
pH
Weekly
TDS or conductivity
Monthly
Temperature
Weekly
TOC
Monthly
Total hardness
Monthly
TSS
Monthly
Turbidity
See note1
UV-254
Monthly
For contactors operated
in filter-adsorber mode, a continuous turbidimeter should be
used. Daily samples should be analyzed using a bench-top turbidimeter to confirm the
continuous turbidimeter readings. For contactors operated in post-filter adsorber mode,
the minimum sampling frequency for turbidity is weekly.
Multiple contactor operation influent sampling requirements. Ideally, water quality
parameter samples should be taken from an influent line that is then split to each
contactor. If this is not possible, then the influent to each contactor should be sampled at
the required sampling frequency. For studies in which the SOC is spiked into the influent
water, the spike should be located at an influent line or batch container that is then split to
each contactor in service.
11.4.2 Effluent Sampling Requirements
To verify the manufacturer's run time or AUR statement of performance capability, an
accurate determination of the run time to breakthrough of the SOC must be obtained
during ACVT. Due to the unsteady-state nature of breakthrough, the uncertain impact of
BOM and other SOCs on adsorption capacity, and the potential for lengthy analysis
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turnaround time, it is difficult to design a sampling plan that will always capture the
complete breakthrough curve, especially when it is very sharp. A few strategies for
sampling designed to improve the chances of collecting samples at critical points (during
breakthrough) while minimizing the analytical cost are presented in this section.
The minimum effluent sampling requirements (Ns) are identical to those defined for the
influent, described in Section 11.4.1, Influent Sampling Requirements. Samples should
be paired: influent and effluent samples should always be taken at the same time,
regardless of study design. If the influent SOC concentration variability is higher than
expected, requiring the "skipped" samples to be run, then the paired effluent for each
additional influent sample analyzed must also be analyzed.
For purposes of determining the minimum effluent sampling rate, the testing period is
defined as the operation time between start-up and breakthrough. Thus, if the SOC being
tested reaches breakthrough (as defined in this document) on day 100, but the system is
operated for an additional 150 days (for a total of 150 days since start-up), the minimum
number of effluent samples taken between day 1 and day 100 should be 20, as defined by
Equation 13. As stated earlier, breakthrough is defined in this document as the point
during the run when the adsorber effluent concentration exceeds the treatment objective.
A conservative sampling schedule approach is recommended, since breakthrough could
occur earlier than expected. Care exercised in establishing the sampling plan will
improve the potential of the data generated to verify the AUR for the SOC tested. This
includes, but is not limited to, an increase in the sampling rate when breakthrough is
expected. Guidance follows on developing a conservative sampling plan.
If prior experience with breakthrough of the target SOC under similar BOM conditions is
identified, the results of previous experiments can be used to improve the run time
estimate obtained during Task 2 using Equations 6 through 9. For example, if prior
experience with adsorption of the same compound on the same water source indicates a
run time to breakthrough 50% shorter than that predicted assuming the absence of BOM,
then the run time estimated in Task 2 should be adjusted accordingly. Prior experience
with other SOCs on the same water source can be used in the same manner, assuming
similar adsorption characteristics to the present compound of interest. Differences in
adsorbent type, temperature, EBCT, pH, etc. should be taken into account when applying
the results of previous studies to the current verification testing.
If no prior experience with SOC adsorption on the water source to be used for
verification testing is available, then two approaches can be followed: a) isotherm tests
with the SOC and adsorbent preloaded with the BOM and b) literature isotherm values
for the SOC and adsorbent can be used with, and adjusted for, non-distilled water
conditions. Isotherm testing can be used to determine the Freundlich adsorption constant
values under preloaded conditions. To do so, adsorbent that has been preloaded with
BOM should be used for isotherm testing. Details on performing isotherm tests can be
found in the literature (Randtke and Snoeyink 1983; Sontheimer, Crittenden, and
Summers 1988; Snoeyink and Summers 1999). Literature Freundlich isotherm constant
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values from the literature can be modified by using Equations 6 and 10a to yield an
estimate of the breakthrough time (see example in Section 9.3).
Once the best possible estimate of run time to breakthrough is determined, a sampling
plan that adequately captures the breakthrough curve must be used. It is recommended
that the rate of effluent sampling for the SOC be increased before, during and after the
expected breakthrough point. It is extremely difficult to estimate run time to
breakthrough accurately. Therefore, a safety factor should be placed around the estimate
of run time in case the compound breaks through earlier than expected. This safety factor
should be as large as feasible. This scenario assumes that all samples taken are
subsequently analyzed.
Another method is to collect many more samples than will be analyzed, such as 5 times
as many samples. Only every 10th sample is analyzed, while the rest are stored
appropriately. When the zone in which breakthrough occurs is known, selected reserve
samples that will fill in the breakthrough curve are analyzed. Only samples that capture
the breakthrough curve are analyzed, thus minimizing the number of samples analyzed.
This method requires that results for the initial samples analyzed are received before the
holding times for the stored samples are exceeded. Overall, the sampling frequency
should be equal to or greater than the minimum described in this section.
Special care should be exercised when evaluating the breakthrough of a SOC in the
presence of other SOCs at significant concentrations. Due to competitive adsorption
effects, breakthrough of the SOC tested may occur earlier than expected.
Effluent sample requirements for the water quality parameters summarized in Table 11.3
should be evenly spaced over the course of the run. These requirements should be
followed for all types of studies, including low and high variability, spike attenuation,
and multiple parallel contactors.
Table 11.3 Minimum Effluent Sampling Frequency Requirements for
Other Water Quality Parameters
Parameter
Frequency
TOC
Monthly
UV-254
Monthly
Turbidity
-r~r :: :r--; r
See note1
used. Daily samples should be analyzed using a bench-top turbidimeter to confirm the
continuous turbidimeter readings. For contactors operated in post-filter adsorber mode,
the minimum sampling frequency for turbidity is weekly.
The effluent sampling requirements outlined in this section apply also to package plants
that blend the effluents of multiple parallel adsorbers prior to further treatment and
distribution. For purposes of sampling, the set of multiple parallel contactors constitutes
the adsorption treatment system evaluated.
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11.5 Evaluation Criteria
Data analysis and interpretation for this task includes:
Effluent SOC data collected and analyzed as described in Section 11.4.2, Effluent
Sampling Requirements, shall be evaluated on a continuous basis to determine whether
breakthrough is occurring or has occurred. A fast turnaround time for sample analysis is
preferable.
The effluent SOC data shall be used in conj unction with the run time estimate described
in Section 9.3 to determine when to terminate test runs. Due to the turnaround time
required for SOC analysis, it may take time to establish when breakthrough has occurred
and that the test can be terminated. It is not recommended that the test be terminated on
the basis of the run time estimate alone. The length of the study, after taking into account
all stoppage time, must be clearly reported.
Plots of effluent concentration against operation time or throughput shall be prepared for
all SOCs evaluated. Breakthrough curves should be prepared on a continuous basis, as
data is available, to aid in evaluating the status of SOC breakthrough. Similar plots
should be prepared for all other water quality analyses conducted.
The AUR shall be determined based on data obtained during verification testing that
shows effluent concentrations lower than the effluent criteria specified in the
manufacturer's statement of performance capabilities. The run time will be shorter than
the maximum testing run time if breakthrough of the SOC evaluated occurs prior to the
end of the run.
The mean and variability of the influent VOC concentration during testing shall be
reported by the FTO. Results shall include the average, minimum, maximum, and
number of data points in the data set. For sample sets of eight or more, the results shall
also include the standard deviation and confidence interval for each analyte. When
summarizing VOC data of sample sets of eight or more, the 10th, 25th, 50th, 75th, and 90th
percentiles shall also be reported. A target concentration value may be reported as the
mean concentration during testing if it is within 5% of the actual measured mean
concentration.
Based on tbt, the AUR is calculated using the following equation, Equation 15:
AUR(g/L) =ฃMฑ (15)
rbt
where p is the apparent media density and Yu is the number of BV to breakthrough. The
value for Yh, is calculated from //,, by Equation 16:
tbt (days) l,440min/d ay
*bt ~ (1")
EBCT(min)
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For spike attenuation studies, the influent data should be evaluated to determine if
influent SOC concentration matches that described by the manufacturer's statement of
performance capabilities. Effluent data should be evaluated to determine if effluent SOC
levels exceed the MCL as stated in the manufacturer's statement of performance
capabilities. If effluent data exceed the MCL, the operation time at which it exceeded the
MCL should be determined (relative to when the spike occurred) the same way that the
operation time is determined for constant influent studies. Thus the effective AUR may
also be determined for spike attenuation studies.
Constant influent studies: determination of run time to breakthrough. For manufacturers
wishing to make a stronger performance capabilities statement and operate their adsorptive
media system for run times long enough to observe breakthrough of the SOC(s) tested, an
evaluation of the influent and effluent data on which the AUR is based must be performed. This
section provides some guidance on performing this evaluation, which will help with
experimental design and data analysis.
As stated previously, it is difficult to predict when breakthrough will occur for a given SOC
during removal by adsorptive media. After appropriate influent and effluent sampling that
provides the best possible evaluation of the manufacturer's statement of performance capabilities
(described previously in this section), the data analyzed should be evaluated to determine the run
time to breakthrough. Run time to breakthrough can be determined from the data in two ways,
depending on the quality of the data.
Basic quality data is best described as effluent data that is not evenly spaced, that fails to capture
the shape of the breakthrough curve (i.e., an effluent data point below detection limits is
followed by one that approximates influent concentrations), or that is so variable that a best-fit
breakthrough curve would contain excessive uncertainty. Examples of these are shown in Figure
11.1. One or more of these conditions may result h a data set that is difficult to interpret in
determining when breakthrough occurred. Therefore, a conservative approach to determining
the operation time to breakthrough for basic quality data must be utilized: the operation time of
the last sample taken prior to a sample that exceeds the treatment objective is the run time used
for the AUR calculation. Sub-optimal quality data is a result of a variety of factors, including
insufficient or poorly-spaced sampling, variability in system flow rate, analytical variability,
excessive influent SOC concentration variability, or variability of other water quality parameters,
such as pH, TOC, turbidity, or other SOCs. A poor quality data set may result in an effective
AUR much higher than that actually achievable by the treatment system evaluated. Therefore, it
is in the manufacturer's best interest that the data generated during verification testing be of the
highest quality possible.
The operation time to breakthrough and AUR can be calculated from good quality data using the
same method described for basic quality data. Alternatively, a curve fit of a good quality data set
can be performed to determine the operation time to breakthrough by interpolation. In many
cases, good quality data will allow for a straightforward evaluation of the breakthrough curve,
from the point of initial breakthrough to column exhaustion. Evenly spaced data points will be
located throughout the breakthrough curve. Data will often be collected at operation times well
beyond the pint of breakthrough (the point at which the effluent concentration reaches the
treatment objective). Examples of good quality data are also given in Figure 11.1.
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The FTO shall assess the quality of the data generated by the study. Based on this analysis, the
FTO shall determine which method of calculating the run time to breakthrough should be
employed. In either case, a graph of the data must be included in the report. If a curve fit is
performed to determine the operation time to breakthrough, a graph of the data and the curve fit
should be included, along with the curve fit type or method, and relevant statistical information
on the goodness of fit (e.g., r2), and confidence intervals. A confidence interval on the calculated
AUR should be reported.
Again, since basic quality data will yield a conservative estimate of the run time to breakthrough,
it is advantageous for the study to be designed and performed so that the best possible quality
data is obtained.
The methods for estimating the operation time to breakthrough described in this section apply to
both low variability and high variability constant influent studies.
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A - Good Quality
Run time for AUR
calculation
o
c
0)
o
c
o
o
+*
c
o
3
Treatment objective
LU
MRL
Operation time or throughput
B - Good Quality
Run time for AUR
calculation
c
o
+ป
(V
+ป
c
0)
o
c
o
o
Treatment objective
+ป
c
o
3
LU
MRL
Operation time or throughput
D - Basic Quality
c
O
+ป
(V
Run time for AUR
calculation
+ป
c
0)
o
c
o
o
-4-1
c
o
3
' Treatment oBjedive'
st
LU
MRL
Operation time or throughput
C - Basic Quality
Possible breakthrough
T
curves
c
o
-4-1
(3
Run time for AUR
calculation
-4-1
c
0)
o
c
o
o
T/eatm e nt_ objective
ฆ*i
c
-------
12.0 TASK 5: IN-PLACE REGENERATION
12.1 Introduction
This task is applicable only to adsorption treatment systems that use adsorptive media that can be
regenerated in-place and that incorporate regeneration capability as an integral part of the
equipment being tested. If the manufacturer wishes to make a statement of performance
capabilities about the in-place regeneration capability of the equipment, verification testing must
include, as a minimum, two complete cycles: an initial loading cycle, followed by a regeneration
cycle, and then a second loading cycle, followed by a second regeneration cycle. This additional
requirement allows for a comparison of adsorptive media performance before and after
regeneration. Furthermore, the regeneration efficiency shall be determined based on the second
regeneration cycle.
Verification of in-place regeneration based on two complete loading/regeneration cycles is
limited, and additional cycles are recommended if possible. However, the guidelines for
modified testing to verify an in-place regeneration statement of performance capabilities are
described under this task. The regeneration system, regenerant fluids used, and regeneration
procedure shall be documented as part of Task 2, System Design and Operation.
12.2 Objectives
The objectives of this task are to:
Describe operation and sampling requirements for systems in which in-place regeneration
will be verified;
Evaluate adsorptive media performance before and after in-place regeneration;
Characterize any residuals produced during regeneration; and
Evaluate regeneration efficiency.
12.3 Work Plan
To verify a manufacturer's statement of performance capabilities regarding the in-place
regeneration capability of adsorption equipment, verification testing shall be conducted as
described in Section 10.0 (Task 3, System Integrity Verification Testing) and Section 11.0 (Task
4, Adsorption Capacity Verification Testing), combined with the additional requirements or
modifications as described in this task.
The testing period shall include, as a minimum, two complete cycles: an initial loading cycle,
followed by a regeneration cycle, and then a second loading cycle, followed by a second
regeneration cycle. During each loading period, the adsorptive media system must be operated at
least until breakthrough of the SOC occurs, based on the treatment objective defined in the
manufacturer's statement of performance capabilities.
The SOC influent target concentration shall be the same during both loading cycles. The mode
of testing (low-variability constant influent, high-variability constant influent, or attenuation of a
spiked influent SOC) shall also be identical during both loading cycles. All other experimental
parameters, such as water source, pretreatment, and presence of background SOCs, shall be as
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similar as possible during the two (or more, if necessary) loading cycles. If the four-step cycle is
completed in less than 60 days, additional loading/regeneration cycles shall be performed until
the total run time is at least 60 days.
If possible, incorporation of additional cycles into the verification test would increase the amount
of data on regeneration effectiveness and retention of adsorption capacity over time. Whether or
not additional cycles are completed, the FTO must make a statement about the long-term
efficiency of regeneration for the adsorptive media tested. If the long-term efficiency of
regeneration is not studied as part of this verification test, or available from other studies, a
statement by the FTO is required indicating that the long-term regeneration efficiency is
unknown. For adsorptive media that has been well studied, a statement on the long-term
regeneration efficiency can be based on the results of previous peer-reviewed published studies.
Any residuals produced during in-place regeneration of the adsorptive media shall be fully
characterized and documented with respect to quantity and SOC composition. For example, if an
off-gas stream is produced by a high temperature gas purge of the media, the off-gas flow rate,
duration, and total off-gas volume emitted should be measured, and sampling and analysis
should be conducted to determine SOC concentrations and total SOC mass emissions. Likewise,
if a solvent solution is used for regeneration, the quantity and characteristics of the regenerant
before and after use (including SOC concentrations) should be measured and reported. The
information from this residuals characterization task shall be used to determine the efficiency of
regeneration. A mass balance approach shall be used to determine whether all the SOCs were
removed during the regeneration process. The regeneration efficiency and the AUR for each
cycle shall be reported.
12.4 Analytical Schedule
Influent and effluent sampling requirements described in Section 10.0 and Section 11.4, shall be
applied to each loading cycle to assess SOC breakthrough and other water quality parameters.
For characterization of regeneration residuals, a sampling and analytical plan shall be developed
by the FTO in the PSTP to thoroughly characterize the VOC content of the residual stream.
12.5 Evaluation Criteria
Verification testing of adsorption treatment systems with in-place regeneration includes the same
types of data analysis and interpretation as described previously for standard adsorption systems
in Section 11.5. In addition, a comparative analysis of adsorption characteristics before and after
media regeneration shall be performed. The purpose of the comparative analysis is to assess and
quantify whether any reduction in adsorptive media service life or adsorption capacity occurs as
a result of in-place regeneration. This shall be evaluated by determining the media service life
(operation time, throughput in BV of water treated, and AUR until breakthrough) for the initial
and subsequent loading periods, and by quantitatively comparing the results. Similarly, the
adsorption capacity before and after regeneration can be determined and compared. In addition,
a mass balance should be developed for the SOC tested to evaluate the regeneration efficiency
using Equation 17:
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(17)
mR
where Er is the regeneration efficiency, q is the adsorption capacity estimated using Equation 4
(and subject to the limitations noted earlier), m \ is the mass of adsorbent, and mR is the mass
SOC recovered in the regeneration stream. The regeneration efficiency shall be calculated after
both regeneration cycles.
13.0 TASK 6: OPERATION AND MAINTENANCE MANUAL
13.1 Objectives
The FTO shall obtain the manufacturer-supplied O&M manual(s) to evaluate the instructions and
procedures for their applicability during the verification testing period. Below are
recommendations for criteria to evaluate O&M manuals for package plants employing adsorptive
media for SOC removal.
13.2 Operation
The manufacturer shall provide readily understood information on the required or recommended
procedures related to the proper operation of the package plant equipment including, but not
limited to, the following.
Monitoring of Preconditioning of Adsorptive Media:
Utilize manufacturer's procedure, which may vary depending upon adsorptive media
selected;
Backwash parameters (flow rate, time, backwash water turbidity, etc.);
Pretreatment chemical application (chemical concentration, time, and flow rate);
Volume of wastewater; and
Wastewater disposal requirements (see Regeneration Wastewater Disposal below).
Monitoring Operation:
The feed water is the untreated or pretreated water that serves as influent to the package plant,
prior to any treatment processes preceding adsorption in the package plant. Treated water is the
adsorptive media effluent water and is blended if multiple contactors are operated in parallel.
Feed water SOC concentration;
Feed water pH;
Feed water adjusted pH (if applicable);
Feed water flow rate;
Feed water pressure;
Treated water SOC concentration;
Treated water pH;
Treated water adjusted pH;
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Treated water pressure;
Chemical feed rates;
Chemical consumption;
Maintenance and operator labor requirements; and
Spare parts requirements.
Monitoring Regeneration of Adsorptive Media:
Utilize manufacturer's procedure for regeneration which shall vary depending upon
selected adsorptive media, equipment, and process variables;
Backwash parameters (flow rate, time, backwash water turbidity, etc.);
Regeneration parameters (flow rate, time, regeneration chemical concentration and flow
rate, effluent concentration, effluent pH, etc.);
Neutralization parameters (flow rate, time, neutralization chemical concentration); and
Adsorptive media makeup requirement.
Monitoring Regeneration Wastewater Disposal:
Utilize manufacturer's procedure for processing, reclaiming, and/or disposing of
regeneration wastewater, adsorptive media preconditioning wastewater, and waste solids,
which shall vary depending upon selected adsorptive media, equipment, treatment
chemicals and process variables;
pH adjustment parameters (flow rate, pH, time, pH adjustment chemical consumption,
etc.);
Flocculation/coagulation parameters (flow rate, time, flocculation/coagulation chemical
consumption, etc.);
Liquid/solid separation parameters (flow rate, time, etc.);
Solids dewatering parameters (flow rate, time, sludge conditioning chemical
consumption, dewatered sludge solids, content, toxicity of dewatered solids, etc.);
Solids disposal parameters (volume, toxicity, permits, transportation of solids to disposal
site, cost factors of transportation and disposal, etc.); and
Liquid disposal parameters (volume, toxicity, pH, permits, adjustment requirements, cost
factors of disposal, etc.).
13.3 Maintenance
The manufacturer shall provide readily understood information on the required or recommended
maintenance schedule for each piece of operating equipment including, but not limited to:
Pumps;
Valves;
All chemical feed and storage equipment; and
All instruments.
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The manufacturer shall provide readily understood information on the required or recommended
maintenance schedule for non-mechanical or non-electrical equipment including, but not limited
to:
Adsorptive media vessels;
Feed lines; and
Manual valves.
14.0 TASK 7: DATA MANAGEMENT
14.1 Introduction
The data management system used in the verification test shall involve the use of computer
spreadsheets, manual recording methods, or both, for recording operational parameters for the
adsorptive media treatment equipment on a daily basis.
14.2 Objectives
The objective of this task is to establish a viable structure for the recording and transmission of
field testing data to ensure that the FTO provides sufficient and reliable operational data to NSF
for verification purposes.
14.3 Work Plan
The following procedure has been developed for data handling and data verification to be used
by the FTO. Where possible, a Supervisory Control and Data Acquisition (SCADA) system
should be used for automatic entry of testing data into computer databases. Specific parcels of
the computer databases for operational and water quality parameters should then be downloaded
by manual importation into Microsoft Excel or similar spreadsheet software. These specific
database parcels shall be identified based upon discrete time spans and monitoring parameters.
In spreadsheet form, the data shall be manipulated into a convenient framework to allow analysis
of equipment operation. Backup of the computer databases to diskette should be performed on a
weekly basis at a minimum.
In the case that a SCADA system is not available, field testing operators shall record data and
calculations by hand in laboratory notebooks (daily measurements shall be recorded on specially-
prepared data log sheets as appropriate). The laboratory notebook shall provide carbon copies of
each page. The original notebooks shall be stored on-site; the carbon copy sheets shall be
forwarded to the project engineer of the FTO at least once per week. This procedure shall not
only ease referencing the original data, but offer protection of the original record of results. Pilot
operating logs shall include a description of the adsorptive media treatment equipment
(description of test runs, names of visitors, description of any problems or issues, etc.); such
descriptions shall be provided in addition to experimental calculations and other items.
The database for the project shall be set up in the form of custom-designed spreadsheets. The
spreadsheets shall be capable of storing and manipulating each monitored water quality and
operational parameter from each task, each sampling location, and each sampling time. All data
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from the laboratory notebooks and data log sheets shall be entered into the appropriate
spreadsheet. Data entry shall be conducted on-site by the designated field testing operators. All
recorded calculations shall also be checked at this time. Following data entry, the spreadsheet
shall be printed out and the printout shall be checked against the handwritten data sheet. Any
corrections shall be noted on the hard copies and corrected on the screen, and then a corrected
version of the spreadsheet shall be printed out. Each step of the verification process shall be
initialed by the field testing operator or engineer performing the entry or verification step.
Each sample shall be assigned a unique identification (ID) number that shall then be tied to the
data from that experiment through each step of data entry and analysis. As samples are collected
and sent to NSF-qualified analytical laboratories, the data shall be tracked by use of the same
system ID numbers. Data from the outside laboratories shall be received and reviewed by the
field testing operator. These data shall be entered into the data spreadsheets, corrected, and
checked in the same manner as the field data.
15.0 TASK 8: QUALITY ASSURANCE/QUALITY CONTROL
15.1 Introduction
QA/QC for the operation of the adsorptive media treatment equipment and the measured water
quality parameters shall be maintained during the verification test.
15.2 Objectives
The objective of this task is to maintain strict QA/QC methods and procedures during the
equipment verification test. Maintenance of strict QA/QC procedures is important, in that if a
question arises when analyzing or interpreting data collected for a given experiment, it will be
possible to determine the exact conditions at the time of testing.
15.3 Work Plan
When developing the Quality Assurance Project Plan (QAPP) within the PSTP, the FTO should
refer to Chapter 1, Section 6.0 Quality Assurance Project Plan, in addition to the information
provided herein. All of the requirements and guidelines described in Chapter 1 shall be included
in the development of the PSTP. In addition to the general ETV Program QA/QC described in
Chapter 1, the PSTP shall incorporate the specific adsorptive media QA items detailed in this
section.
Equipment flow rates and associated signals should be checked and must be recorded on a
routine basis. A routine daily visual check during testing shall be established to confirm that
each piece of equipment or instrumentation is operating properly. Particular care shall be taken
to confirm that chemicals are being fed at the defined flow rate into a fow stream that is
operating at the expected flow rate and that the chemical concentrations are correct. In-line
monitoring equipment, such as flow meters, shall be checked to confirm that the readout matches
with the actual measurement (i.e., flow rate) and that the signal being recorded is correct. The
items listed in this task are in addition to any specified checks outlined in the analytical methods.
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It is extremely important that system flow rates be maintained at set values and monitored
frequently. Doing so allows a constant and known EBCT to be maintained in the adsorbent
contactor. Adsorbent performance is directly affected by the EBCT, which in turn is
proportional to the volumetric flow rate through the contactor. Therefore, an important QA/QC
objective shall be the maintenance of a constant volumetric flow rate through the adsorbent
contactor by means of frequent monitoring and documentation. Documentation shall include an
average and standard deviation of recorded flow rates through the adsorbent contactor.
15.3.1 Daily QA/QC Checks
Chemical feed pump flow rates (checked volumetrically; more frequent
monitoring, such as every 8 hours, is recommended);
In-line turbidimeter flow rates (checked volumetrically, if employed);
Adsorbent contactor(s) flow rate(s) (checked volumetrically every 2 hours when
staffed; at least twice daily. The flow rate should be adjusted to maintain its value
within 5% of the design flow rate); and
Recalibration of in-line pH meters (if used).
15.3.2 Weekly QA/QC Checks
Recalibration of conductivity meters, and/or turbidimeters (if used). If less
frequent recalibration of conductivity meters and turbidimeters is recommended
by manufacturer, then follow manufacturer's recommendation;
In-line flow meters/rotameters (confirm flow rate volumetrically over a specific
period of time to confirm instrument reading and, if necessary, clean equipment to
remove any foulant buildup); and
Tubing (check condition of all tubing and connections and replace if necessary).
15.3.3 Monthly QA/QC Checks
In-line turbidimeters (clean out reservoirs and recalibrate, if employed) and
Differential pressure transmitters (confirm gauge readings and electrical signal
using a pressure meter).
15.4 Analytical Methods
On-Site Analyses. The analytical methods utilized in this study for on-site monitoring of feed
and effluent water quality are described below. Use of either bench-top or in-line field analytical
equipment will be acceptable for the verification testing; however, in-line equipment is
recommended for ease cf operation. Use of in-line equipment is also preferable because it
reduces the introduction of error and the variability of analytical results generated by inconsistent
sampling techniques.
pH. Analyses for pH shall be performed according to Standard Method 4500-H+ (APHA,
AWWA, and WEF 1998). A 3-point calibration of the pH meter used in this study shall
be performed once per day when the instrument is in use. Certified pH buffers in the
expected range shall be used. The pH probe shall be stored in the appropriate solution
January 2004
This TSTP has not been validated in the field.
Page 4-59
-------
defined in the instrument manual. Transport of carbon dioxide across the air-water
interface can confound pH measurement in poorly buffered waters. If this is a problem,
measurement of pH in a confined vessel is recommended to minimize the effects of
carbon dioxide loss to the atmosphere.
Temperature. Temperature measurements shall be made in accordance with Standard
Method 2550. The thermometer used should be a high quality, mercury-filled, Celsius
thermometer with a scale marked for every 0.1ฐC that covers the range of expected
temperatures with markings etched in the glass. The thermometer should be checked
periodically against a precision thermometer certified by the National Institute of
Standards and Technology (NIST). An in-line thermometer is acceptable for this work.
Turbidity. Turbidity analyses shall be performed according to Standard Method 2130
with either an in-line or bench-top turbidimeter. During verification testing, the in-line
and bench-top turbidimeters shall be left on continuously. Once each turbidity
measurement is complete, the unit shall be switched back to its lowest setting. All
glassware used for turbidity measurements shall be cleaned and handled using lint-free
tissues to prevent scratching. Sample vials shall be stored inverted to prevent deposits
from forming on the bottom surface of the cell.
The FTO shall document any problems experienced with the monitoring turbidity
instruments during testing, and shall also document any subsequent modifications or
enhancements made to monitoring instruments.
Bench-top Turbidimeters. Grab samples shall be analyzed using a bench-top
turbidimeter. Readings from this instrument shall serve as reference measurements
throughout the study. The bench-top turbidimeter shall be calibrated within the expected
range of sample measurements at the beginning of verification testing and on a weekly
basis using primary turbidity standards of 0.1, 0.5, and 3.0 NTU. Secondary turbidity
standards shall be obtained and checked against the primary standards. Secondary
standards shall be used on a daily basis to check the calibration of the turbidimeter and to
recalibrate when more than one turbidity range is used.
The method for collecting grab samples shall consist of running a slow, steady stream
from the sample tap, triple-rinsing a dedicated sample beaker in this stream, allowing the
sample to flow down the side of the beaker to minimize bubble entrainment, double-
rinsing the sample vial with the sample, carefully pouring from the beaker down the side
of the sample vial, wiping the sample vial clean, inserting the sample vial into the
turbidimeter, and recording the measured turbidity. In the case of cold water samples that
cause the vial to fog preventing accurate readings, the vial shall be allowed to warm up
by partial submersion in a warm water bath for approximately 30 seconds.
In-line Turbidimeters. In-line turbidimeters shall be used for measurement of turbidity
in the filtrate water during verification testing and must be calibrated and maintained as
specified in the manufacturer's O&M manual. It will be necessary to check the in-line
readings using a bench-top turbidimeter at least daily; although the mechanism of
analysis is not identical between the two instruments, the readings should be comparable.
January 2004
This TSTP has not been validated in the field.
Page 4-60
-------
If the comparison suggests inaccurate readings, then all in-line turbidimeters should be
recalibrated. In addition to calibration, periodic cleaning of the lens should be conducted
using lint-free paper to prevent any particle or microbiological build-up that could
produce inaccurate readings. Periodic checks of the sample flow should also be
performed using a volumetric measurement. Instrument bulbs should be replaced on an
as-needed basis. The LED readout should also be checked to ensure that it matches the
data recorded on the data acquisition system, if the latter is employed.
Off-Site Analyses. All off-site analytical work associated with equipment verification testing
shall be performed by a laboratory that is certified, accredited or approved by a state, a third-
party organization (i.e., NSF), or the EPA. Sampling for off-site analyses shall be conducted
using proper sampling techniques and samples shall be collected in appropriate volumes and
containers provided by the laboratory. These samples shall be preserved, stored, shipped, and
analyzed in accordance with appropriate procedures and holding times, as specified by the
analytical lab.
16.0 REFERENCES
APHA, AWWA, and WEF. 1998. Standard Methods for the Examination of Water and
Wastewater, 20th ed. L.S. Clesceri, A.E. Greenberg, and A.D. Eaton, eds. Washington, D.C.:
APHA, AWWA, and WEF.
Clifford, D.A. 1999. Ion Exchange and Inorganic Adsorption. Water Quality & Treatment: A
Handbook of Community Water Supplies. R.D. Letterman, ed. New York: McGraw-Hill, Inc.
Crittenden, J.C., P.J. Luft, D.W. Hand, J.L. Oravitz, S. Loper, and M. Ari. 1985. Prediction of
Multicomponent Adsorption Equilibria Using Ideal Adsorbed Solution Theory. Environ Sci
Technol. 19:11:1537-1548.
Cohn, P.D., M. Cox, and P.S. Berger. 1999. Health and Aesthetic Aspects of Water Quality.
Water Quality & Treatment: A Handbook of Community Water Supplies. R.D. Letterman, ed.
New York: McGraw-Hill, Inc.
EPA/NSF. 2002. EPA/NSF ETV Equipment Verification Testing Plan for the Removal of
Volatile Organic Chemical Contaminants by Adsorptive Media. Ann Arbor: NSF International.
EPA/NSF. 2002. EPA/NSF ETV Protocol for Physical Removal of Microbiological and
Particulate Contaminants. Ann Arbor: NSF International.
Faust, S.D. and O.M. Aly. 1998. Chemistry of Water Treatment, 2nd ed. Chelsea, Michigan:
Ann Arbor Press, Inc.
Ford, R., R. Raczko, S.L. Phillips, H. Arora. 1989. Developing Carbon Usage Rate Estimates
for Synthetic Organic Chemicals. In Proc. of the AWWA Annual Conference, Los Angeles,
Calif.
January 2004
This TSTP has not been validated in the field.
Page 4-61
-------
Pontius, F.W. and S.W. Clark. 1999. Drinking Water Quality Standards, Regulations, and
Goals. Water Quality & Treatment: A Handbook of Community Water Supplies. R.D.
Letterman, ed. New York: McGraw-Hill, Inc.
Randtke, S.J. and V.L. Snoeyink. 1983. Evaluating GAC Adsorptive Capacity. J AWWA,
75:8:406.
Snoeyink, V.L. and R.S. Summers. 1999. Adsorption of Organic Compounds. Water Quality &
Treatment: A Handbook of Community Water Supplies. R.D. Letterman, ed. New York:
McGraw-Hill, Inc.
Sontheimer, H., J.C. Crittenden, and R.S. Summers. 1988. Activated Carbon for Water
Treatment, 2nd ed. DVGW-Forschungstelle am Engler-Bunte-Institut der Universitat Karlsruhe,
Karlsruhe, Germany.
Speth, T.F. and J.Q. Adams. 1993. GAC and Air Stripping Design Support for the Safe
Drinking Water Act. Strategies and Technologies for Meeting SDWA Requirements. R.M. Clark
and R.S. Summers, eds. Technomic Publishing Company, Inc., Lancaster, Pennsylvania.
Speth, T.F. and R.J. Miltner. 1990. Adsorption Capacity of GAC for Synthetic Organics. J
AWWA. 82:2:72-75.
Speth, T.F. and R.J. Miltner. 1998. Technical Note: Adsorption Capacity of GAC for Synthetic
Organics. J AWWA. 90:4:171-174.
Summers, R.S., B. Haist, J. Koehler. 1989. The Influence of Background Organic Matter on
GAC Adsorption. J AWWA. 81:5:66-74.
USEPA. 1990. Technologies and Costs for the Removal of Synthetic Organic Chemicals from
Potable Water Supplies. Drinking Water Technology Branch, Office of Ground Water and
Drinking Water, U.S. Environmental Protection Agency, Washington, D.C.
USEPA. 1999. Analysis of GAC Effluent Blending During the ICR Treatment Studies. EPA
815-C-99-002. Cincinnati, Ohio: U.S. Environmental Protection Agency.
USEPA. 2000. Drinking Water Standards and Health Advisories. EPA 822-B-00-001.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 2002. List of Drinking Water Contaminants & MCLs. EPA 816-F-02-013.
Washington, D.C.: U.S. Environmental Protection Agency. (Viewed on July 21, 2003 at
http://www.epa.gov/safewater/mcl.html)
January 2004
This TSTP has not been validated in the field.
Page 4-62
-------
Table A.l Phase II Rule SOCs
APPENDIX A: REGULATED SOCS
Contaminant
MCLG MCL
(mg/L) (mg/L)
Status Potential health effects from
ingestion of water
Sources of contaminant in drinking water BAT
Acrylamide
Alachlor
Aldicarb
Aldicarb sulfuric
Aldicarb sulfoxide
Atra/inc
Carbofuran
Chlordane
2.4-D
l,2-Dibromo-3-
chloropropane (DBCP)
Kpichlorohydrin
Lthylene dibromide
(EDB)
1 Icplachlor
Heptachlor epoxide
Zero
TT1
Zero 0.002
0.001 0.003 Delayed
0.001 0.002
0.001 0.004
0.003 0.003
0.04 0.04
Zero 0.002
0.07 0.07
Zero 0.0002
Zero IT1
Zero 0.00005
Zero 0.0004
Zero 0.0002
Final Nervous system or blood
problems; increased risk of
cancer
final live, liver, kidney or spleen
problems: anemia: increased risk;
of cancer
Nervous system effects
Delayed Nervous system effects
Delayed Nervous system effects
final Cardiovascular system or
reproductive problems
Final Problems with blood, nervous
system, or reproductive system
Final fixer or nervous system
problems: increased risk of
cancer
Final Kidney, liver, or adrenal gland
problems
Final Reproductive difficulties;
increased risk of cancer
Final Increased cancer risk, and over a
long period of time, stomach
problems
Final Problems w illi liver, stomach,
reproductive system, or kidneys;
increased risk of cancer
Final I ,iver damage: increased risk of
cancer
Final Liver damage; increased risk of
Added to water during sewage/wastewater PAP
treatment
Runoff from herbicide used on row crops GAC
Insecticide on cotton, potatoes, other crops; GAC
widely restricted
Biodegradalion of aldicarb GAC
Biodegradation of aldicarb GAC
Runoff from herbicide used tin row crops GAC
Leaching of soil fumigant used on rice and GAC
alfalfa
Residue of banned termiticide GAC
Runoff from herbicide used on row crops GAC
Runoff/leaching fro m soil fumigant used on GAC, PTA
soybeans, cotton, pineapples, and orchards
Discharge from industrial chemical factories: an PAP
impurity of some w aler treatment chemicals
Discharge from petroleum refineries
Residue of banned termiticide
Breakdown of heptachlor
GAC, PTA
GAC
GAC
January 2004
This TSTP has not been validated in the field.
Page 4-63
-------
Table A.l Phase II Rule SOCs (continued)
Contaminant
MCLG
(mg/L)
MCL
(mg/L)
Status
Potential health effects from
ingestion of water
Sources of contaminant in drinking water
BAT
Lindane
0.0002
0.0002
Final
I ,i ver or kidney problems
Runoff/leaching from insecticide used on cattle,
lumber, gardens
GAC
Methoxychlor
0.04
0.04
Final
Reproductive difficulties
Runoff/leaching from insecticide used on fruits,
vegetables, alfalfa, livestock
GAC
Pentachlorophenol
Zero
0.001
Final
Liver or kidney problems:
increased cancer risk
Discharge from wood preserving factories
GAC
Polychlorinated biphenyls
Zero
0.0005
Final
Skin changes; thymus gland
Runoff from landfills; discharge of waste
GAC
(PCBs)
problems; immune deficiencies;
reproductive or nervous system
difficulties; increased risk of
cancer
chemicals
2.4.5-TP isihevi
0.05
0.05
Final
I ,iver problems
Residue of banned herbicide
GAC
Toxaphene
Zero
0.003
Final
Kidney, liver, or thyroid
problems; increased risk of
cancer
Runoff/leaching from insecticide used on cotton
and cattle
GAC
'Each water system must certify, in writing, to the state (using third-party or manufacturer's certification) that when acrylamide and epichlorohydrin are used in
drinking water systems, the combination (or product) of dose and monomer level does not exceed the levels specified, as follows:
Acrylamide = 0.05% dosed at 1 mg/L (or equivalent)
Epichlorohydrin = 0.01% dosed at 20 mg/L (or equivalent)
Abbreviations: MCL: maximum contaminant level GAC: granular activated carbon
MCLG: maximum contaminant level goal PTA: packed tower aeration
BAT: best available technology PAP: polymer addition practices
Sources: USEPA, 2002; adapted from Pontius and Clark (1999) and Faust and Aly (1998)
January 2004
This TSTP has not been validated in the field.
Page 4-64
-------
Table A.2 Phase V Rule SOCs
Contaminant
MCLG
(mg/L)
MCL
(mg/L)
Status
Potential health effects
Sources of contaminant in drinking water
BAT
Ben/o(a)pyrene (PAI Is)
Zero
0.0002
Final
Reproductive difficulties:
increased risk of cancer
I.caching from linings of w ater storage tanks
and distribution lines
(i AC
Dalapon
0.2
0.2
Final
Minor kidney changes
Runoff from herbicide used on rights of w ay
GAC
I)i (2-elhy'Ihcxyl) adipale
0.4
0.4
Final
Weight loss, liver problems, or
possible reproductive difficulties.
Discharge from chemical lactones
GAC. PTA!
Di (2-elhy'Ihcxyl)
Zero
0.006
Filial
Reproductive difficulties; liver
Discharge from rubber and chemical factories
GAC
phthalate
problems; increased risk of
cancer
Dinoseb
0.007
0.007
Final
Reproductive difficulties
Runoff from herbicide used on soybeans and
vegetables
GAC j
Diquat
0.02
0.02
Final
Cataracts
Runoff from herbicide use
GAC
Kndolhall
0.1
0.1
Final
Stomach and intestinal problems
Runoff from herbicide use
GAC
I indrin
0.002
0.002
Final
Liver problems
Residue of banned insecticide
GAC
Glyphosate
0.7
0.7
Filial
Kidney problems: reproductive
difficulties
Runoff from herbicide use
().\
Hexachlorobenzene
Zero
0.001
Final
Liver or kidney problems;
reproductive difficulties;
increased risk of cancer
Discharge from metal refineries and agricultural
chemical factories
GAC
I Iexachlorocyclo-
0.05
0.05
Final
Kidney or stomach problems
Discharge from chemical factories
>
>
penladiene
Oxamyl (vydate)
0.2
0.2
Final
Slight nervous system effects
Runoff/leaching from insecticide used on
apples, potatoes, and tomatoes
GAC
Pieloram
0.5
0.5
Final
I ,iver problems
I Ierbicide runoff
GAC
Sima/ine
0.004
0.004
Final
Problems w itli blood
I Ierbicide runoff
GAC
2.3.7,X-TCDD (Dioxin)
Zero
3x10"s
Final
Reproductive difficulties:
increased risk of cancer
Emissions from waste incineration and other
combustion: discharge from chemical factories
GAL
Abbreviations: MCL: maximum contaminant level GAC: granular activated carbon
MCLG: maximum contaminant level goal OX: oxidation
BAT: best available technology PTA: packed tower aeration
Sources: USEPA, 2002; adapted from Pontius and Clark (1999) and Faust and Aly (1998)
January 2004
This TSTP has not been validated in the field.
Page 4-65
-------
APPENDIX B: DRINKING WATER STANDARDS AND HEALTH ADVISORIES
January 2004 This TSTP has not been validated in the field. Page 4-66
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
Acenaphthene
AHfh inrfian tenHh livrt
-
-
-
,ปp,#aa
2
o
0.06
n 01
2
R 4.
-
0 1
DO
nvi i.iviui icii |5yuivJi iij
Acrylamide
F
zero
TT1
F '87
1.5
0.3
0.0002
W,*T
0.007
-
0.001
..E|4
B2
Acrylonitrile
-
-
-
-
-
-
-
-
0.006
B1
Alachlor
F
zero
0.002
F '88
0.1
0.1
0.01
0.4
-
0.042
B2
Aldicarb3
F:
0.007
0.007
F '95
0.01
0.01
0.001
0.04
0.007
-
D
Aldicarb sulfone3
F'
0.007
0.007
F '95
0.01
0.01
0.001
0.04
0.007
-
D
Aldicarb sulfoxide3
F:
0.007
0.007
F '95
0.01
0.01
0.001
0.04
0.007
-
D
Aldrin
-
-
-
F '92
0.0003
0.0003
0.00003
0.001
-
0.0002
B2
Ametryn
-
-
-
F '88
9
9
0.009
0.3
0.06
-
D
Ammonium sulfamate
-
-
-
F '88
20
20
0.2
8
2
-
D
Anthracene (PAH)5
-
-
-
-
-
-
0.3
10
-
-
D
Atrazine6
F
0.003
0.003
F '88
-
-
0.035
1
0.2
-
C
Baygon
-
-
-
F '88
0.04
0.04
0.004
0.1
0.003
-
C
Bentazon
-
-
-
F '99
0.3
0.3
0.03
1
0.2
-
E
Benz[a]anthracene (PAH)
-
-
-
-
-
-
-
-
-
-
B2
Benzene
F
zero
0.005
F '87
0.2
0.2
-
-
-
0.1
A
Benzo[a]pyrene (PAH)
F
zero
0.0002
-
-
-
-
-
-
0.002
B2
Benzo[b]fluoranthene (PAH)
-
-
-
-
-
-
-
-
-
-
B2
Benzo[g,h,i]perylene (PAH)
-
-
-
-
-
-
-
-
-
-
D
Benzo[k]fluoranthene (PAH)
-
-
-
-
-
-
-
-
-
-
B2
bis-2-Chloroisopropyl ether
**?ฆ
/ป /
/WPi /
AM
1
-
,P
Bromacil
-
-
-
F '88
5
5
0.1
5
0.09
-
C
Bromobenzene
D '86 /
A
4
-
-
D
1 When acrylamide is used in drinking water systems, the combination (or product) of dose and monomer level shall not exceed that equivalent to a polyacrylamide polymer
containing 0.05% monomer dosed at 1 mg/L.
2 Determined not to be carcinogenic at low doses by OPP.
3 The lifetime HA value or the MCLG/MCL value for any combination of two or more of these three chemicals should remain at 0.007 mg/L because of similar mode of action.
4 Administrative stay of the effective date.
5 PAH = Polycyclic aromatic hydrocarbon
6 Under review
January 2004
This TSTP has not been validated in the field.
Page 4-67
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
Bromochloromethane
.
.
.
F '89
50
1
0.01
0.5
0.09
.
D
,F
.Zf!ป
/
ง
JJK?
0.7
-
Ji,W /
J?
Bromoform (THM)
F
zero
0.081
D '93
5
2
0.02
0.7
-
0.4
B2
Bromomethane
-
-
-
D '89
0.1
0.1
0.001
0.05
0.01
-
D
Butyl benzyl phthalate (PAE)2
-
-
-
-
-
-
0.2
7
-
-
C
Butylate
-
-
-
F '89
2
2
0.05
2
0.4
-
D
Carbaryl
-
-
-
F '88
1
1
0.1
4
0.7
-
D
Carbofuran3
F
0.04
0.04
F '87
0.05
0.05
0.005
0.2
0.04
-
E
Carbon tetrachloride
F
zero
0.005
F '87
4
0.2
0.0007
0.03
-
0.03
B2
Carboxin
-
-
-
F '88
1
1
0.1
4
0.7
-
D
Chloramben
-
-
-
F '88
3
3
0.015
0.5
0.1
-
D
Chlordane
F
zero
0.002
F '87
0.06
0.06
0.0005
0.02
-
0.001
B2
Chloroform (THM)
F
zero
0.081
D '93
4
4
0.01
0.4
-
0.6
B2
Chloromethane
-
-
-
F '89
9
0.4
0.004
0.1
0.003
-
C
Chlorophenol (2-)
-
-
-
D '94
0.5
0.5
0.005
0.2
0.04
-
D
p-Chlorophenyl methyl sulfide/sulfone/sulfoxide
-
-
-
-
-
-
-
-
-
-
D
Chlorothalonil
-
-
-
F '88
0.2
0.2
0.015
0.5
-
0.15
B2
Chlorotoluene o-
-
-
-
F '89
2
2
0.02
0.7
0.1
-
D
Chlorotoluene p-
-
-
-
F '89
2
2
0.02
0.7
0.1
-
D
Chlorpyrifos
-
-
-
F '92
0.03
0.03
0.003
0.1
0.02
-
D
Chrysene (PAH)
-
-
-
-
-
-
-
-
-
-
B2
Cysnftzipe
**?ฆ
/
./b'W''
Jm
J.1
0.002
AS?
0.001
7
/j /
1 1998 Final Rule for Disinfectants and Disinfection By-products: The total for trihalomethanes is 0.08 mg/L.
2 PAE = phthalate acid ester
3 Under review
January 2004
This TSTP has not been validated in the field.
Page 4-68
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Chemicals
Standards
Status
Reg.
MCLG
(mg/L)
MCL
(mg/L)
Status
HA
Document
Health Advisories
10-kg child
One-day
(mg/L)
Ten-day
(mg/L)
RfD
(mg/kg/
DWEL
Lifetime
day)
(mg/L)
(mg/L)
mg/L at
Risk
Cyanogen chloride1
DCPA (Dacthal)
Dalapon (sodium sa
Di(2-ethylhexyl)adipate
Di(2-ethylhexyl)phthalate (PAE)
Diazinon
Dibromochloromomethane (THM)
Dibromochloropropane (DBCP)
Dibutyl phthalate (PAE)
Dicamba
Dichloroacetic acid
Dichlorobenzene o-
Dichlorobenzene m-5
Dichlorobenzene p-
Dichlorodifluoromethane
Dichloroethylene (1,1-)
Dichloroethane (1,2-)
Dichloroethylene (cis-1,2-)
Dichloroethylene (trans-1,2-)
Dichloromethane
Dichlorophenol (2,4-)
Dichloropropane (1,2-)
Dichloropropene (1,3-)
Dieldrin
Diethyl phthalate (PAE)
0.07
0.2
0.4
zero
0.06
zero
zero
0.6
0.075
0.007
zero
0.07
0.1
zero
0.07 i
:
0.4
0.006
0.082
0.0002
0.063
0.6
0.075
0.007
0.005
0.07
0.1
0.005
0.005
F '88
D '93
F '87
F '88
D '93
F '87
F '87
F '87
F '89
F '87
F '87
F '90
F '87
D '93
D '94
F '87
F '88
0.05
1
80
20
0.02
6
0.2
0.3
5
9
9
11
40
2
0.7
4
20
10
0.03
0.03
0.0005
0.05
80
20
0.02
6
0.05
0.3
5
9
9
11
40
1
0.7
1
1
2
0.03
0.09
0.03
0.0005
0.05
0.01
0.01
0.6
0.02
0.00009
0.02
0.1
0.03
0.004
0.09
0.09
0.1
0.2
0.01
0.01
0.02
0.06
0.003
0.03
0.00005
0.8
2
0.4
0.4
20
0.7
0.003
0.7
4
1
0.1
3
3
4
5
0.4
0.4
0.7
2
0.1
1
0.002
30
0.07
0.07
0.2
0.4
0.0006
0.06
0.2
0.6
0.6
0.075
1
0.007
0.07
0.1
0.02
3
0.3
0.04
0.003
0.04
0.5
0.06
0.04
0.0002
Under review
! 1998 Final Rule for Disinfectants and Disinfection By-products: The total for trihalomethanes is 0.08 mg/L.
* 1998 Final Rule for Disinfectants and Disinfection By-products: The total for five haloacetic acids is 0.06 mg/L.
1A quantitative risk estimate has not been determined.
' The values for m-dichlorobenzene are based on data for o-dichlorobenzene.
January 2004
This TSTP has not been validated in the field.
Page 4-69
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
Diisopropyl methylphosphonate
-
-
-
F '89
8
8
0.08
3
0.6
-
D
Dimethrin
**?ฆ
/ป /
10
10
f#
10
2
,7
,P
Dimethyl methylphosphonate
-
-
-
F '92
2
2
0.2
7
0.1
0.7
C
Dimethyl phthalate (PAE)
-
-
-
-
-
-
-
-
-
-
D
Dinitrobenzene (1,3-)
-
-
-
F '91
0.04
0.04
0.0001
0.005
0.001
-
D
Dinitrotoluene (2,4-)
-
-
-
F '92
0.5
0.5
0.002
0.1
-
0.005
B2
Dinitrotoluene (2,6-)
-
-
-
F '92
0.4
0.4
0.001
0.04
-
0.005
B2
Dinitrotoluene (2,6 & 2,4)1
-
-
-
F '92
-
-
-
-
-
0.005
B2
Dinoseb
F
0.007
0.007
F '88
0.3
0.3
0.001
0.04
0.007
-
D
Dioxane p-
-
-
-
F '87
4
0.4
-
-
-
0.3
B2
Diphenamid
-
-
-
F '88
0.3
0.3
0.03
1
0.2
-
D
Diquat
F
0.02
0.02
-
-
-
0.002
0.07
-
-
D
Disulfoton
-
-
-
F '88
0.01
0.01
0.00004
0.001
0.0003
-
E
Dithiane (1,4-)
-
-
-
F '92
0.4
0.4
0.01
0.4
0.08
-
D
Diuron
-
-
-
F '88
1
1
0.0022
0.07
0.01
-
D
Endothall
F
0.1
0.1
F '88
o.s
0.8
0.02
0.7
0.1
-
D
Endrin
F
0.002
0.002
F '87
0.02
0.005
0.0003
0.01
0.002
-
D
Epichlorohydrin
F
zero
TT3
F '87
0.1
0.1
0.002
0.07
-
0.4
B2
Ethylbenzene
F
0.7
0.7
F '87
30
3
0.1
3
0.7
-
D
Ethylene dibromide (EDB)4
F
zero
0.00005
F '87
0.008
0.008
-
-
-
0.00005
B2
Ethylene glycol
-
-
-
F '87
20
6
2
70
14
-
D
Ethylene Thiourea. (ETU)
7
/
if
0.00008
J.P
-
0.02 V
J?
Fenamiphos
-
-
-
F '88
0.009
0.009
0.00025
0.009
0.002
-
D
1 technical grade.
2 New OPP RfD = 0.003 mg/kg/day.
3 When epichlorohydrin is used in drinking water systems, the combination (or product) of dose and monomer level shall not exceed that equivalent to an epichlorohydrin- based
polymer containing 0.01 % monomer dosed at 20 mg/L.
41,2-dibromomethane
January 2004
This TSTP has not been validated in the field.
Page 4-70
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
Fluometuron
-
-
-
F '88
2
2
0.01
0.5
0.09
D
Fluorene (PAH)
-
-
-
-
-
-
0.04
1
-
-
D
Fonofos
-
-
-
F '88
0.02
0.02
0.002
0.07
0.01
-
D
Formaldehyde
-
-
-
D '93
10
5
0.15
5
1
-
B11
Glyphosate
F
0.7
0.7
F '88
20
20
0.12
4
0.7
-
D
Heptachlor
F
zero
0.0004
F '87
0.01
0.01
0.0005
0.02
-
0.0008
B2
Heptachlor epoxide
F
zero
0.0002
F '87
0.01
-
0.00001
0.0004
-
0.0004
B2
Hexachlorobenzene
F
zero
0.001
F '87
0.05
0.05
0.0008
0.03
-
0.002
B2
Hexachlorobutadiene
-
-
-
F '89
0.3
0.3
0.002
0.07
0.001
0.05
C
Hexachlorocyclopentadiene
F
0.05
0.05
-
-
-
0.007
0.2
-
-
D
Hexachloroethane
-
-
-
F '91
5
5
0.001
0.04
0.001
-
C
Hexane (n-)
-
-
-
F '87
10
4
-
-
-
-
D
Hexazinone
-
-
-
F '96
3
2
0.053
2
0.4
-
D
HMX4
-
-
-
F '88
5
5
0.05
2
0.4
-
D
lndeno[1,2,3,-c,d]pyrene (PAH)
-
-
-
-
-
-
-
-
-
-
B2
Isophorone
-
-
-
F '92
15
15
0.2
7
0.1
4
C
Isopropyl methylphosphonate
-
-
-
F '92
30
30
0.1
4
0.7
-
D
Isopropylbenzene (cumene)
-
-
-
D '87
11
11
0.1
4
-
-
D
Lindane5
F
0.0002
0.0002
F '87
1
1
0.0003
0.01
0.0002
-
C
Malathion
-
-
-
F '92
0.2
0.2
0.02
0.8
0.1
-
D
Maleic hydrazide
-
-
-
F '88
10
10
0.5
20
4
-
D
MCPA6
-
-
-
F '88
0.1
0.1
0.00057
0.02
0.004
-
D
Methomyl
-
-
-
F '88
0.3
0.3
0.025
0.9
0.2
-
E
Methoxychlor
F
0.04
0.04
F '87
0.05
0.05
0.005
0.2
0.04
-
D
Methyl ethyl ketone
-
-
-
F '87
75
7.5
0.6
20
-
-
D
Methyl parathion
//M
F '88
JO#
J#
0.00025
0.009
gฃw2,
a i'
,9
1 Carcinogenicity based on inhalation exposure. 5 Lindane = y-hexachiorocydohexane
2 New OPP RfD = 2 mg/kg/day. 6 MCPA = 4(chloro-2-methoxyphenoxy)acetic acid
3 The Health Advisory is based on a new OPP RfD rather than the IRIS RfD. 7 New OPP RfD = 0.0015 mg/kg/day
4 HMX = octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine
January 2004
This TSTP has not been validated in the field.
Page 4-71
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
Metolachlor
.
.
.
F '88
2
2
0.151
0.5
0.1
.
C
Metribuzin
P /*
.##
jQ
0.025'
,P
Monochloroacetic acid
F
-
0.063
-
-
-
-
-
-
-
-
,F
SA /
t
AM
A3
0.1
,P ,ซ
Naphthalene
-
-
-
F '90
0.5
0.5
0.02
0.7
0.1
-
C
Nitrocellulose (non-toxic)
-
-
-
F '88
-
-
-
-
-
-
-
Nitroguanidine
-
-
-
F '90
10
10
0.1
4
0.7
-
D
Nitrophenol p-
-
-
-
F '92
o.s
0.8
0.008
0.3
0.06
-
D
Oxamyl (Vydate)
F
0.2
0.2
F '87
0.2
0.2
0.025
0.9
0.2
-
E
Paraquat
-
-
-
F '88
0.1
0.1
0.0045
0.2
0.03
-
C
Pentachlorophenol
F
zero
0.001
F '87
1
0.3
0.03
1
-
0.03
B2
Phenanthrene (PAH)
-
-
-
-
-
-
-
-
-
-
D
Phenol
-
-
-
D '92
6
6
0.6
20
4
-
D
Picloram
F
0.5
0.5
F '88
20
20
0.074
2
0.5
-
D
Polychlorinated biphenyls (PCBs)
F
zero
0.0005
D '93
-
-
-
-
-
0.01
B2
Prometon5
-
-
-
F '88
0.2
0.2
0.015
0.5
0.1
-
D
Pronamide
-
-
-
F '88
O.S
0.8
0.075
3
0.05
-
C
Propachlor
-
-
-
F '88
0.5
0.5
0.01
0.5
0.09
-
D
Propazine
-
-
-
F '88
1
1
0.02
0.7
0.01
-
C
Propham
-
-
-
F '88
5
5
0.02
0.6
0.1
-
D
Pyrene (PAH)
-
-
-
-
-
-
0.03
-
-
-
D
RDX 6
-
-
-
F '88
0.1
0.1
0.003
0.1
0.002
0.03
C
Simazine
F
0.004
0.004
CO
00
Ll_
0.5
0.5
0.005
0.2
0.004
-
C
Styrene
F
0.1
0.1
F '87
20
2
0.2
7
0.1
-
C
2,4,5-T (Trichlorophenoxyacetic acid)
-
-
-
F'88
0.8
0.8
0.01
0.4
0.07
-
D
1 New OPP RfD = 0.1 mg/kg/day 5 Under review.
2 New OPP RfD = 0.013 mg/kg/day 6 RDX = hexahydro-1,3,5- trinitro-1, 3,5- triazine
3 1998 Final Rule for Disinfectants and Disinfection By-products: the total for five
haloacetic acids is 0.06 mg/L.
4 New OPP RfD = 0.2 mg/kg/day
January 2004
This TSTP has not been validated in the field.
Page 4-72
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
Standards
Health Advisories
Status
10-kg child
RfD
mg/L at
Status
MCLG
MCL
HA
One-day
Ten-day
(mg/kg/
DWEL
Lifetime
10"4 Cance
Cancer
Chemicals
Reg.
(mg/L)
(mg/L)
Document
(mg/L)
(mg/L)
day)
(mg/L)
(mg/L)
Risk
Group
2,3,7,8-TCDD (Dioxin)
F
zero
3E-08
F '87
0.000001
1E-07
1E-09
4E-08
-
2E-08
B2
Tebuthiuron
/j /
/
JW
ฆ2
0.5
-
,-P
Terbacil
-
-
-
F '88
0.3
0.3
0.01
0.4
0.09
-
E
Terbufos
-
-
-
/W$ง /
0.005
0.0009
f
Tetrachloroethane (1,1,1,2-)
-
-
-
F '89
2
2
0.03
1
0.07
0.1
C
Tetrachloroethane (1,1,2,2-)
-
-
-
F '89
0.04
0.04
0.00005
0.002
0.0003
0.02
C
Tetrachloroethylene
F
zero
0.005
F '87
2
2
0.01
0.5
0.01
-
-
Trichlorofluoromethane
-
-
-
F '89
7
7
0.3
10
2
-
D
Toluene
F
1
1
D '93
20
2
0.2
7
1
-
D
Toxaphene
F
zero
0.003
F '96
0.004
0.004
0.0004
0.01
-
0.003
B2
2,4,5-TP (Silvex)
F
0.05
0.05
F '88
0.2
0.2
0.008
0.3
0.05
-
D
Trichloroacetic acid
F
0.3
0.061
D '96
4
4
0.1
4
0.3
-
C
Trichlorobenzene (1,2,4-)
F
0.07
0.07
F '89
0.1
0.1
0.001
0.05
0.01
-
D
Trichlorobenzene (1,3,5-)
-
-
-
F '89
0.6
0.6
0.006
0.2
0.04
-
D
Trichloroethane (1,1,1-)
F
0.2
0.2
F '87
100
40
0.035
1
0.2
-
D
Trichloroethane (1,1,2-)
F
0.003
0.005
F '89
0.6
0.4
0.004
0.1
0.003
0.06
C
Trichloroethylene 2
F
zero
0.005
F '87
-
-
0.007
0.2
-
0.2
B2
Trichlorophenol (2,4,6-)
-
-
-
D '94
0.03
0.03
0.0003
0.01
-
0.3
B2
Trichloropropane (1,2,3-)
-
-
-
F '89
0.6
0.6
0.006
0.2
0.04
-
-
Trifluralin
-
-
-
F '90
0.08
0.08
0.0075
0.3
0.005
0.5
C
Trimethylbenzene (1,2,4-)
-
-
-
D '87
-
-
-
-
-
-
D
Trimethylbenzene (1,3,5-)
-
-
-
D '87
10
-
-
-
-
-
D
Trinitroglycerol
-
-
-
F '87
0.005
0.005
-
-
0.005
0.2
-
Trinitrotoluene (2,4,6-)
-
-
-
F '89
0.02
0.02
0.0005
0.02
0.002
0.1
C
Vinyl chloride2
F
zero
0.002
F '87
3
3
-
-
-
0.002
A
Xylenes
.F
10
If /'
/%Jii /
40
40
*'/2
Ji
fw
-
D /
1 1998 Final Rule for Disinfectants and Disinfection By-products: The total for five haloacetic acids is 0.06 mg/L.
2 Under review
January 2004
This TSTP has not been validated in the field.
Page 4-73
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
DEFINITIONS
The following definitions for terms used in the Tables are not all-encompassing, and should not be construed to be "official" definitions. They are intended to
assist the user in understanding terms found on the following pages.
Action Level: The concentration of a contaminant which, if exceeded, triggers treatment or other requirements which a water system must follow. For lead or
copper it is the level which, if exceeded in over 10% of the homes tested, triggers treatment.
Cancer Group: A qualitative weight-of-evidence judgement as to the likelihood that a chemical may be a carcinogen for humans. Each chemical is placed
into one of the following five categories:
Group Category
A: Human carcinogen
B: Probable human carcinogen:
Bl: indicates limited human evidence;
B2: indicates sufficient evidence in animals and inadequate or no evidence in humans
C: Possible human carcinogen
D: Not classifiable as to human carcinogenicity
E: Evidence of noncarcinogenicity for humans
This categorization is based on EPA's 1986 Guidelines for Carcinogen Risk Assessment. The Proposed Guidelines for Carcinogen Risk Assessment which
were published in 1996, when final, will replace the 1986 cancer guidelines.
10~4 Cancer Risk: The concentration of a chemical in drinking water corresponding to an estimated lifetime cancer risk of 1 in 10,000.
DWEL: Drinking Water Equivalent Level. A lifetime exposure concentration protective of adverse, non-cancer health effects, that assumes all of the
exposure to a contaminant is from drinking water.
HA: Health Advisory. An estimate of acceptable drinking water levels for a chemical substance based on health effects information; a Health Advisory is not
a legally enforceable Federal standard, but serves as technical guidance to assist Federal, state, and local officials.
One-day HA: The concentration of a chemical in drinking water that is not expected to cause any adverse noncarcinogenic effects for up to one day
of exposure.
Ten-day HA: The concentration of a chemical in drinking water that is not expected to cause any adverse noncarcinogenic effects for up to ten days
of exposure.
Lifetime HA: The concentration of a chemical in drinking water that is not expected to cause any adverse noncarcinogenic effects for a lifetime of
exposure.
January 2004
This TSTP has not been validated in the field.
Page 4-74
-------
APPENDIX B
Table B.l Drinking Water Standards and Health Advisories (Cont.)
LED10: Lower Limit on Effective Dose10 . The 95% lower confidence limit of the dose of a chemical needed to produce an adverse effect in 10% of those
exposed to the chemical, relative to the control.
MCLG: Maximum Contaminant Level Goal. A non-enforceable health goal which is set at a level at which no known or anticipated adverse effect on the
health of persons occur and which allows an adequate margin of safety.
MCL: Maximum Contaminant Level. The highest level of a contaminant that is allowed in drinking water. MCLs are set as close to the MCLG as feasible
using the best available treatment technology and taking cost into consideration. MCLs are enforceable standards.
RfD: Reference Dose. An estimate (with uncertainty spanning perhaps an order of magnitude) of a daily oral exposure to the human population (including
sensitive subgroups) that is likely to be without an appreciable risk of deleterious effects during a lifetime.
SDWR: Secondary Drinking Water Regulations. Non-enforceable Federal guidelines regarding cosmetic effects (such as tooth or skin discoloration) or
aesthetic effects (such as taste, odor, or color) of drinking water.
TT: Treatment Technique. A required process intended to reduce the level of a contaminant in drinking water.
ABBREVIATIONS
D: Draft
F: Final
NA: Not Applicable
NOAEL: No-Observed-Adverse-Effect-Level
OPP: Office of Pesticide Programs
P: Proposed
Reg: Regulation
TT: Treatment Technique
Source: U.S. EPA 2000.
January 2004
This TSTP has not been validated in the field.
Page 4-75
-------
THIS PAGE INTENTIONALLY LEFT BLANK
January 2004 This TSTP has not been validated in the field. Page 4-76
------- |