AWT Fall Analyst 2020

the Analyst The Voice of the Water Treatment Industry

Volume 27 Number 4

1300 Piccard Drive, Suite LL 14 • Rockville, MD 20850

Fall 2020

Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management Introduction to Pharmaceutical Waters for U.S. Products Keys to Working With Phosphate Boiler Water Treatment Programs Formulating for a Zero or Low-Phosphorous Environment Tales From the Waterside: How PTSA and Remote Monitoring Protected a Cooling Tower System From Gross Chemical Overfeed T.U.T.O.R.: Why Do Materials of Construction Matter?

Volume 27 Number 4 Fall 2020

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Cover Stainless steel biofilm collection coupon being prepared for swabbing before ATP analysis.

Photo courtesy of the AWT Cooling Water Subcommittee.

Fall 2020

Volume 27

Number 4

8 Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

AWT Cooling Subcommittee Representatives: John Caloritis, CWT (The Metro Group, Inc.); Keith Johnson (Keith M. Johnson Consulting); Richard Rosser, Ph.D. (AMSA, Inc.); Derrick Vandenberg, CWT (Guardian Chemicals Inc.) While the importance of the impact of biofilms on water systems is understood, and water treatment programs increasingly are structured to control biofilm growth, limited information is available to guide water treatment professionals on how to conduct the types of biofilm testing that can be used to assess and optimize biofilm control efforts. This article addresses this lack of information on practical field techniques available to confirm, quantify, and monitor the presence of biofilm, and it describes the methods deemed to be the most technically appropriate.

26 Introduction to Pharmaceutical Waters for U.S. Products

T.C. Soli, Ph.D., Soli Pharma Solutions, Inc. Water is prolifically used in the pharmaceutical industry. Its applications range from preparing compendial grades of water to manufacturing active ingredients, excipients, and a wide variety of sterile and nonsterile finished products (including packaged sterile waters), as well as for testing of all those materials and for equipment and facility cleaning. This article examines treatment methods, pharmaceutical water types, and uses.

40 Keys to Working With Phosphate Boiler Water Treatment Programs

Steven Dunn, Process Performance Management LLC The treatment of water in fossil-fired boilers using phosphate-based materials dates back to the early 1900s. The low feedwater quality at the time caused many boilers to fail because of heavy scale deposition. Calcium and magnesium scales formed on hot heat transfer surfaces, reducing energy transfer and creating conditions for metal failure as increased firing was required to overcome the thermal insulating properties of the scale.

58 Formulating for a Zero or Low-Phosphorus Environment

4

Calendar of Events

5

President’s Message

6

Message From the President-Elect

71 Membership Benefits 72 Association News 73 Industry Notes 76 CWT Spotlight 77 Making a Splash 78 Financial Matters 80 Capital Eyes 82 Tales From the Waterside 85 T.U.T.O.R. 88 Business Notes 90 Advertising Index

Brandon Beyer, BWA–Italmatch USA Corp.

A failure to control scaling and corrosion in industrial water treatment systems can lead to loss of efficiency or equipment failure. Phosphorus has been a primary tool of the water treatment industry, and polymers containing phosphorus either as a terminal group or as part of the backbone are also used in the industry. However, there is a growing push within the United States and abroad to move away from phosphorus to reduce point sources of phosphorus to watersheds. We report here on the current state of zero and low-phosphorous regulations and legislation as well as offer a range of current solutions to challenging water conditions in the absence of phosphorus.

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the Analyst Volume 27 Number 4

1300 Piccard Drive, Suite LL 14 Rockville, MD 20850 (301) 740-1421 • (301) 990-9771 (fax) www.awt.org

2020–2021 AWT Board of Directors President

Michael Bourgeois, CWT

Calendar of Events

Association Events Technical Training Seminars (East)

Secretary

March 17–20, 2021 (Tentative) Graduate Annapolis Annapolis, MD

Treasurer

2021 Business Owners Meeting

President-Elect

Matt Jensen, CWT

Stephen C. Hallier, CWT

September 21, 2021 (Tentative) Providence Convention Center and Omni Hotel Providence, Rhode Island

Noah Baskin

Immediate Past President

Thomas Brandvold, CWT

Directors

John D. Caloritis, CWT Mark Coldren, CWT Stephanie Keck, CWT Fred Shurtz

2021 Annual Convention & Exposition

Ex-Officio Supplier Representative

Garrett S. Garcia

Past Presidents

Jack Altschuler John Baum, CWT R. Trace Blackmore, CWT, LEED AP D.C. “Chuck” Brandvold, CWT Thomas Brandvold, CWT Brent W. Chettle, CWT Dennis Clayton Bernadette Combs, CWT, LEED AP Matt Copthorne, CWT James R. Datesh John E. Davies, CWT Jay Farmerie, CWT Gary Glenna Charles D. Hamrick Jr., CWT Joseph M. Hannigan Jr., CWT Mark R. Juhl

Brian Jutzi, CWT Bruce T. Ketrick Jr., CWT Bruce T. Ketrick Sr., CWT Ron Knestaut Robert D. Lee, CWT Mark T. Lewis, CWT Steven MacCarthy, CWT Anthony J. McNamara, CWT James Mulloy Alfred Nickels Scott W. Olson, CWT William E. Pearson II, CWT William C. Smith Marc Vermeulen, CWT David Wagenfuhr Casey Walton, B.Ch.E, CWT Larry A. Webb

Staff

Executive Director

Heidi J. Zimmerman, CAE

Deputy Executive Director

Sara L. Wood, MBA, CAE

Senior Member Services Manager

Angela Pike

Vice President, Meetings

Grace L. Jan, CMP, CAE

Associate Meeting Planner Kiki DeVane

Exhibits and Sponsorship Manager

Barbara Bienkowski, CEM

Marketing Director

Jennifer Olivares

Marketing Coordinator

Mary Claire Gordon

Managing Editor

Lynne Agoston

Production Manager

Maryia Alenchyk

Director of Accounting Services

Dawn Rosenfeld

The Analyst Staff

Publisher, Heidi J. Zimmerman, CAE Managing Editor, Lynne Agoston Production Manager, Maryia Alenchyk Technical Editor

Michael Henley, mdhenleywater@gmail.com, (303) 324-9507

Advertising Sales

Heather Prichard, advertising@awt.org

The Analyst is published quarterly as the official publication of the Association of Water Technologies. Copyright 2020 by the Association of Water Technologies. Materials may not be reproduced without written permission. Contents of the articles are the sole opinions of the author and do not necessarily express the policies and opinions of the publisher, editor or AWT. Authors are responsible for ensuring that the articles are properly released for classification and proprietary information. All advertising will be subject to publisher’s approval, and advertisers will agree to indemnify and relieve publisher of loss or claims resulting from advertising contents. Editorial material in the Analyst may be reproduced in whole or part with prior written permission. Request permission by writing to: Managing Editor, the Analyst, 1300 Piccard Drive, Suite LL 14, Rockville, MD 20850, USA. Annual subscription rate is $100 per year in the U.S. (4 issues).

Please add $25 for Canada and Mexico. International subscriptions are $200 in U.S. funds.

September 22–25, 2021 Providence Convention Center and Omni Hotel Providence, Rhode Island

2022 Annual Convention & Exposition September 21–24, 2022 Vancouver Convention Centre Vancouver, Canada

2023 Annual Convention & Exposition

October 4–7, 2023 Amway Grand Hotel and Grand Rapids Convention Center Grand Rapids, Michigan

Also, please note that the following AWT committees meet on a monthly basis. All times shown are Eastern Time. To become active in one of these committees, please contact us at (301) 740-1421.

Second Tuesday of each month, 11:00 am – Legislative/Regulatory Committee Second Tuesday of each month, 2:30 pm – Convention Committee Second Wednesday of each month, 11:00 am – Business Resources Committee Second Friday of each month, 10:00 am – Special Projects Subcommittee Second Friday of each month, 11:00 am – Cooling Subcommittee Second Friday of each month, 2:00 pm – Pretreatment Subcommittee Third Monday of each month, 9:00 am – Certification Committee Third Monday of each month, 3:30 pm – Young Professionals Task Force Third Tuesday of each month, 3:00 pm – Education Committee Third Friday of each month, 9:00 am – Boiler Subcommittee Third Friday of each month, 10:00 am – Technical Committee Quarterly (call for meeting dates), 10:00 am – Wastewater Subcommittee

Other Industry Events

BOMA, Winter Business Meeting, January 25–27, 2021, Virtual AWWA, AWWA-WEF Utility Management, February 23–26, 2021, Atlanta, GA CTI, Annual Conference , February 7–11, 2021, New Orleans, LA ASHRAE, AHR Expo, March 15–17, 2021, Chicago, IL ACS, Spring National Meeting & Expo, March 21–25, 2021, San Antonio, TX AWWA, Membrane Technology Conference, March 22–25, 2021, West Palm Beach, FL NACE, Corrosion Risk Management Conference, April 18–22, 2021, Salt Lake City, UT WQA, Convention and Expo, April 27–29, 2021, Las Vegas, NV AWWA, Annual Conference & Expo, June 13–16, 2021, San Diego, CA ASHRAE, Annual Conference, June 26–30, 2021, Phoenix, AZ BOMA, International Conference and Expo, July 18–21, 2021, Boston, MA ASHE, Annual Convention & Expo., August 2–5, 2021, Chicago, IL ACS, Fall Meeting & Expo, August 22–26, 2021, Atlanta, GA USGBC, GreenBuild, September 21–22, 2021, San Diego, CA WEFTEC, Annual Technical Exhibition and Conference, October 16–21, 2021, Chicago, IL IWC, Annual Conference, November 7–11, 2021, Scottsdale, AZ RETA, Annual Convention, November 8–11, 2021, Schaumburg, IL

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the Analyst Volume 27 Number 4

President’s Message

By Michael Bourgeois, CWT

Wow! What a fun Interactive Convention and Exposition. I found the Learning Sessions and Lounges to be quite informative, possibly more than in-person.

The virtual Exhibit Hall was also great, and I enjoyed the chat feature with the vendor representatives. We have heard similar feedback from many attendees, and we will be looking for ways to incorporate their suggestions as part of the 2021 Convention and Exposition in Providence, Rhode Island, September 22–25, 2021.

Strategic Direction As you probably know, AWT has four strategic outcomes we are working toward, but for 2021, we will be focusing primarily on two outcomes: Outcome 1—Training and Education: AWT’s membership heavily utilizes the premier business & technical resources for the water treatment industry through technologically advanced delivery mechanisms.

If you didn’t get to see the video from the Cooling Subcommittee, be sure to check it out. The group is working on an important project on source water. They are inviting AWT members to test for Legionella and related parameters in water at the point of entry into buildings where they are providing water treatment. The purpose of the study is to gain a better understanding of the prevalence and nature of Legionella pneumophila entering premise water systems from public drinking water distribution systems. The goal is to collect over 500 samples. We are looking for members to participate in this study. If you are interested, please contact Angela Pike at apike@awt.org or (240) 404-6477.

Connection During these times, it has been more important than ever to stay connected to our AWT community. Some of the best resources I have found have been from my colleagues at AWT. A great way to stay connected is to volunteer. Sign up for a committee or help with a project. You can lend your expertise and grow your professional network at the same time.

Outcome 3—An Engaged Membership: AWT has increased its membership and addressed membership model options and is known for enhanced communication that encourages a diverse, engaged membership to continuously design a relevant association.

Thank you for the opportunity to serve. I can be reached at mbourgeois@chemcoprod.com.

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the Analyst Volume 27 Number 4

Message From the President-Elect What a great convention!

Although we weren’t able to see each other in person and interact the way that we have always enjoyed in the past, this was the best case scenario, given the times. My hat goes off to AWT and our staff for pulling off a successful, informative, and “above expectation” virtual event. It truly amazes me that, despite all the obstacles we faced, we were still able to enjoy the excellent talks, informative commercial corners, and fantastic interaction right from our homes and offices. With that said, we are working hard to provide a truly amazing in-person event next year in Providence, Rhode Island, September 22–25, 2021. Please join us!

By Matt Jensen, CWT

Visit the Roger Williams Park Zoo, one of the oldest in the country, where you’ll see everything from bison and snow leopards to red pandas, river otters, and Masai giraffe.

Because New England is known for its quaint lighthouses, take a tour of some of the local lights, like the Pomham Rocks Lighthouse in East Providence or the Conimicut Lighthouse in nearby Warwick.

Or, hop on the ferry to visit Newport, Rhode Island.

Only an hour away by water, the area is home to white sand beaches, Gilded Age mansions, vineyards, an old military fort, cultural festivals, and several museums on topics like art, tennis, history, and literature.

Hotel For those in search of the spirit of the city, the Omni Providence Hotel places you within reach of all the best that Providence has to offer. With a premier downtown location, you will find yourself within walking distance of the city's historic attractions, gourmet restaurants, upscale shopping, entertainment, and more. The hotel is connected to the Rhode Island Convention Center, Dunkin’ Donuts Center, and Providence Place Mall, making it the ideal destination.

Location Providence may be the capital of the smallest state, but there is nothing tiny about the cultural punch this city packs. Whether you’re winding along the river’s edge or enjoying Little Italy, this is one urban area that is most enjoyable by foot. And don’t forget the impressive architectural, historical, and artistic components that make Providence great. Here are just a few things Providence has to offer:

Educational Sessions The highlight of every convention is the educational sessions. The abstract submission process is open until January 9, 2021, so be sure to submit a presentation on new technology in the industry or a case study on a successful solution for your customer. We’re looking forward to another quality program.

A short distance away from the hotel is the State House, the active seat of Rhode Island’s government and a must-visit attraction for architectural and history buffs.

Are you a history buff? Visit the Stephen Hopkins House, a National Historic Landmark and the former home of a Rhode Island governor (and signer of the Declaration of Independence) that has been converted into a museum.

Awards Dinner One of the great events that takes place in Providence on select weekends is WaterFire. This fire-filled sculpture installation by Barnaby Evans takes place on three rivers throughout downtown, creating a marvelous spectacle to enjoy the city. While it’s not finalized yet, we are working to see if we can bring WaterFire to our Awards Dinner on Thursday evening. Stay tuned for more information!

A few blocks south, you'll find the John Brown House Museum, an 18th century mansion that once belonged to a merchant and politician.

The Rhode Island School of Design Museum is a world-renowned art museum comprising five different buildings displaying ancient and contemporary art, including everything from photographs and textiles to sculptures and drawings.

As we continue to plan the 2021 Annual Convention, I welcome your feedback. I can be reached at mjensen@ gwt-inc.com. Thank you for the opportunity to serve.

6

the Analyst Volume 27 Number 4

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Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management AWT Cooling Subcommittee Representatives: John Caloritis, CWT (The Metro Group, Inc.); Keith Johnson (Keith M. Johnson Consulting); Richard Rosser, Ph.D. (AMSA, Inc.); Derrick Vandenberg, CWT (Guardian Chemicals Inc.)

8

the Analyst Volume 27 Number 4

(Editor’s note: This report on biofilm monitoring is based on a research project conducted by AWT’s Cooling Water Subcommittee. The listed authors are all members of the subcommittee.)

visits to the locations for biofilm testing. Efforts were made to avoid sampling immediately after system biocide treatments, but no other modifications to the chemical treatment programs applied in these systems were made.

Introduction

Two testing methods—ATP and an enzyme-based biofilm presence/activity method called “HMB®”—were shown to reproducibly detect biofilm in the field. The ATP and HMB® methods for biofilm detection are described in this article. Experience with a biofilm stain method that was included in the study is also discussed.

These detection methods focused on the use of portable strategies that could readily be carried out in the field, and whose methods were already somewhat familiar to AWT members.

Biofilm is a disruptive force that accelerates corrosion, deposition, and fouling in open cooling water systems. It contributes directly and indirectly to waterside corrosion through the various mechanisms of MIC (microbiologically influenced corrosion). Mineral and suspended solid deposition become more likely and more tenacious in the presence of biofilm, as heat transfer rates suffer. Finally, biofilm presence affects overall microbial control and encourages the proliferation of waterborne pathogens, such as Legionella.

To summarize, the article will show that a standard corrosion coupon rack can be used to adequately collect biofilm in a bypass arrangement and that stainless-steel coupons provide a suitable and technically appropriate biofilm collection surface that supports analysis by the ATP and HMB® methods. These allow for sample collection to occur conveniently, consistently, and reproducibly.

While the importance of the impact of biofilms on water systems is understood, and water treatment programs increasingly are structured to control biofilm growth, limited information is available to guide water treatment professionals on how to conduct the types of biofilm testing that can be used to assess and optimize biofilm control efforts.

Background

This article, which is based on a six-month program of biofilm monitoring method evaluation at four industrial facilities, addresses this lack of information on practical field techniques available to confirm, quantify, and monitor the presence of biofilm. It describes the methods deemed to be the most technically appropriate, with relevant focus on these areas: Biofilm collection Field testing Data interpretation

In 2018, AWT’s Cooling Water Subcommittee launched a workgroup project to study various field-based biofilm monitoring techniques. The work focused on studying passive biofilm collection strategies coupled with the use of available biofilm field-testing techniques.

The study used three biofilm analysis methods to quantify the presence/activity of biofilms that developed on four different test surface types exposed in two passive monitoring devices. The analyses were conducted on 30-day biofilms collected in six monthly sampling events at four testing locations. 30-day intervals are considered a minimum timeframe necessary to develop a mature biofilm.

A primary objective was to study methods that could be completed on a typical cooling water service visit, and without reliance on an external laboratory for testing. The study included a six-month testing program conducted in four very different water systems to evaluate the selected biofilm collection equipment and analysis methods. The water systems included two building heating, ventilation, air conditioning (HVAC) systems on city water makeup, one facility HVAC system on high suspended particulate solids river water makeup, and one industrial process water system with high suspended particulate solids.

Adenosine triphosphate (ATP) (total and free) and dipslides were used to monitor planktonic microbial populations in the waters of the industrial water systems during

A detailed summary report on the findings of the study was issued in September 2019 and is available to AWT members in the members-only section of the AWT 9

the Analyst Volume 27 Number 4

Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

website (“Practical Field Use of Biofilm Collection and Analysis Tools,” available at https://www.awt.org/ members-only/cooling-resources/). The report provides insights and observations in a comparative format on equipment and supplies needed to collect and analyze biofilm growth, explains the steps required to set up and conduct a biofilm testing program, and details the costs (equipment, consumables, hours) to conduct the testing.

It allows the reader to draw conclusions about both the availability of field techniques, as well as the reproducibility and success rates of the methods selected for study.

Tools of the Biofilm Monitoring Trade

Biofilm monitoring tools are used to assess the presence and/or activity of microbial biofilms in any water system. These can include “active” monitoring devices that measure and report in real time some physical or activity-related characteristic of the biofilm microbial population, and “passive” monitoring devices, which use retrievable surface samples to collect biofilm for quantitative analysis. The cost and complexity of active monitoring devices makes them suitable for use mainly in large industrial systems. For this reason, we have focused on passive biofilm monitoring devices and analysis methods that are suitable for medium and small industrial or HVAC water systems.

continued

“The cost and complexity of active monitoring devices makes them suitable for use mainly in large industrial systems.” in AWT corrosion monitoring guidelines (“AWT Recommendations and Guidelines for Corrosion Coupons in Cooling Systems”) were followed.

Figure 1: Passive biofouling monitoring devices and retrievable coupons and studs: (a) Corrosion coupon rack (lower) and MRD (upper); (b) Stainless-steel coupon; (c) Stainless-steel mesh coupon; (d) Perforated polycarbonate coupon; and (e) MRD and MRD stainless-steel studs.

MRD

Coupon Rack

Biofilm Collection Devices Two “passive” biofilm monitoring devices were evaluated in the study: 1. A standard off-the-shelf corrosion coupon rack; and 2. A six-port Modified Robbins Device (MRD) from Tyler Advanced Corrosion Technologies (Figure 1a). The MRD, model MPMR-CB06PVC, is a medium pressure (100 pounds per square inch [psi]) device made of polyvinyl chloride (PVC) and homopolymer acetal thermoplastic that accommodates six metal studs as removable biofilm growth surfaces (Figure 1e). When installed in the device, the stud surfaces are approximately flush with the pipe wall and therefore experience the same flow conditions as biofilms on an inner pipe surface. The studs used in this study were 316 stainless steel, with exposed surface area of 0.147 square inches (in 2).

(a)

(b)

(c)

(d)

The coupon rack and MRD were installed with the coupon rack immediately upstream of the MRD. Standard conditions and precautions for installation and operation of corrosion coupon racks as outlined

(e)

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Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

The coupon rack was fitted with three types of coupons: standard stainless-steel strip type coupon, stainless-steel mesh “biofilm” coupon, and perforated polycarbonate coupons (supplied with the HMB® test kit), all with dimensions similar to standard corrosion coupons (Figures 1b, 1c, 1d, respectively). Some coupons were installed with two coupons on one holder. The MRD was fitted with six identical stainless-steel studs.

continued

was found by all users to be challenging and a potential source of sample contamination and error.

Figure 2: Stainless-steel strip type corrosion coupons (top) and stainless-steel MRD studs (bottom) provide suitable surfaces for monitoring biofilm growth.

Evaluation of the Biofilm Collection Tools

The biofilm collection tools were evaluated at the four locations by four water treatment professionals in a program of six monthly biofilm growth-sampling-analysis cycles, with all coupons and studs retrieved and analyzed after an exposure period of approximately one month. Based on these experiences, the following conclusions were drawn by participants in the study.

Both the corrosion coupon rack and the MRD performed reliably under the installation and operating conditions chosen for the program. Both devices allowed for the growth of biofilms on the test surfaces installed in the devices. However, based on six months of experience operating both devices, corrosion coupon racks were preferred over the MRD device for exposing samples for biofilm growth/monitoring. This preference was based on familiarity with operation of corrosion coupon racks, the ability to use an existing rack to conduct biofilm monitoring, and the lower cost of the coupon rack compared to the MRD device, as well as the additional care required when working with the small, cylindrical MRD studs.

Stainless-steel coupons and stainless-steel MRD studs (Figure 2) allowed for the growth of biofilms at all locations. Despite their much smaller surface area, MRD studs provided enough biofilm for analysis by all biofilm methods employed in this study at all testing locations.

However, the physical manipulation of the stud holders and studs during removal, sampling, and reinstallation

“Both the corrosion coupon rack and the MRD performed reliably under the installation and operating conditions chosen for the program.”

11

The perforated polycarbonate and stainless-steel mesh coupons allowed for the growth of biofilms at all locations, but also allowed accumulation of biomass-contaminated debris in systems with high suspended particulate solids, resulting in artificially elevated indications of biofilm presence (Figure 3). The perforated polycarbonate coupon is suitable for systems with low suspended solids. The mesh coupon is best used as a visual, nonquantitative indicator of biofilm presence.

Figure 3: Stainless steel mesh coupon.

Why might you choose to use a relatively expensive MRD? The value of analyzing replicate biofilm samples the Analyst Volume 27 Number 4

Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

(multiple MRD studs versus single coupons) was apparent in the data collected. The natural “growth – detachment – regrowth” cycle of biofilms, compounded by the application of biocides and/or dispersants in industrial water systems, produces a level of variability in biofilm samples that makes testing of replicate samples at each testing event valuable for identifying high or low outlier results.

Without analyses of replicate samples, there is significant risk that important treatment decisions will be made based on a single outlier biofilm test result.

By consensus, a standard strip-type stainless-steel coupon, exposed in a standard corrosion coupon rack, is the preferred biofilm collection device. Biofilm from a defined surface area of these coupons can be easily collected and analyzed for biofilm presence or activity as part of a routine site visit by the water technologist.

Biofilm Assessment Methods

Several commercially available biofilm assessment methods were considered for evaluation in this study.

Criteria for selection of the assessment methods were as follows: 1. Suitable for onsite analysis to minimize changes during sample transport/storage.

2. Limited sample processing prior to analysis to minimize operator influence/error.

3. Quantitative results by direct instrument readout preferred.

4. Reasonable analysis time to minimize service visit time.

5. No specialized microbiology techniques or skills required.

6. Reasonable quality equipment and supplies required to be brought to the site.

7.

Reasonable cost (instrument and per test).

8. Minimal waste generated from testing.

Based on these criteria, the three biofilm assessment methods chosen for evaluation were ATP, the HMB® 12

continued

test, and the HydroBio® biofilm stain. A summary of each method is provided here.

ATP. ATP is a key energy-carrying molecule in all living cells and has been widely used for many years as an indicator of the presence of microorganisms in liquids and on surfaces. ATP is measured by an enzymatic method that generates light in proportion to the amount of ATP present in the sample. The light is measured in a hand-held “luminometer” (Figure 4), with results reported as RLU (relative light units) per sample (e.g., per milliliter for liquid samples, per coupon/ stud or per square centimeter for surface samples). For biofilm samples, a cotton swab sampler is used to collect biofilm from a defined surface area. The sampling swab and reagents used in biofilm ATP analyses in this study are supplied as a single device (“UltraSnap™ pen”) by the luminometer manufacturer, Hygiena, LLC. ATP analyses of water samples conducted in this study used Hygiena AquaSnap™ Total ATP and Free ATP pens.

HMB®. The HMB® test, developed and manufactured

by BioTech International Inc. (Figure 5), is based on measurement of peroxidase enzyme activity in a liquid or surface (biofilm) sample. Peroxidases are enzymes found in all aerobic organisms and organisms exposed to oxygen.

Microbial peroxidase activity is described in the HMB® test manufacturer’s literature as an indicator of the overall level of metabolic activity in a biofilm or liquid sample.

The presence of peroxidases (e.g., catalase) can be detected by the breakdown of hydrogen peroxide with the evolution of oxygen. The HMB® biofilm test measures an increase in oxygen partial pressure in the test vessel headspace resulting from the decomposition of hydrogen peroxide by peroxidases associated with biofilm-based organisms.

A perforated polycarbonate coupon (Figure 1(d)) supplied with the HMB® test materials is recommended for use in biofilm testing. The test involves transferring a coupon with biofilm (or a surface swab biofilm sample) to a tube containing a small amount of hydrogen peroxide, which is then sealed. After 15 minutes the sealed tube is connected to the HMB® instrument which measures the increase in oxygen partial pressure in the headspace, providing results in “BMR” (BioMass Readout) units. Literature provided with the HMB® testing system states that readings less than 0.27 BMR units are considered insignificant, whereas readings greater than 4.0 BMR units indicate the sample is heavily contaminated. the Analyst Volume 27 Number 4

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HydroBio® Test. The HydroBio® biofilm detection test kit from Kurita (Figure 6) is based on a biofilm staining method. Biofilm is allowed to develop on a stainless-steel coupon in a corrosion coupon rack. The coupon is removed from the coupon rack and exposed to rinse and biofilm stain solutions. Stain is retained in proportion to the amount of biofilm present, and the intensity of the stain color is compared to a color comparator chart which provides results as grams of biofilm per square meter of surface area (5 to 45 gram per square meter [g/m 2] in 5 g/m 2 increments). The method differs from the ATP and HMB® assessment methods in that it provides a measure of the mass of biofilm present on the coupon, rather than the activity of the microbial community present in the biofilm on the coupon.

These three biofilm assessment methods are applied to whole biofilms and will detect the presence of nearly all biofilm organisms. Biofilm assessment by viable count of dispersed biofilm microorganisms was not included in the study due to well-known difficulties achieving complete and reproducible biofilm dispersion in the field, and the selectivity of viable count growth media that results in detection of a small fraction of the total microbial population present in environmental samples.

The three selected biofilm analysis methods were used in the study as follows: ATP swab pens were used to quantify biofilm ATP on stainless-steel strip-type coupons from the coupon rack, and on MRD studs from the MRD. The HMB® method was used to assess biofilm peroxidase (enzyme) activity on perforated polycarbonate and stainless-steel mesh coupons from the coupon rack, and on swabs of MRD studs or whole MRD studs from the MRD. Finally, the HydroBio® biofilm stain was used to quantify biofilm biomass associated with stainless-steel strip type coupons from the coupon rack, and on MRD studs from the MRD.

14

continued

Figure 4: Hygiena System Sure ATP Illuminator (top) and (bottom) an example of an ATP pen.

Figure 5: HMBX instrument and vials with rubber septum (left). Septum is pierced by needle (right) with connection to an oxygen sensor in the HMB® instrument.

Figure 6: The HydroBio® Test Kit includes stainless-steel coupons, vials containing stain and rinse solutions, a timer, and a color comparator relating color intensity to biofilm mass.

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Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

Figure 7: An example of the HydroBio® test kit. These kits include stainless steel coupons, vials containing stain and rinse solutions, a timer, and a color comparator relating color intensity to biofilm mass.

continued

20 minutes to perform, with time between transfer of the samples and attachment of the HMB® instrument to perform other tasks.

The instrument’s digital readout is easy to read but somewhat difficult to interpret, with a rather narrow BMR range, representing moderate biofilm activity, and no guidance regarding what level of change in BMR represents a significant change in biofilm activity.

Biofilm samples exhibiting too much peroxidase activity will generate sufficient oxygen to release the rubber stopper from the top of the tube during the 15-minute incubation period, invalidating the result. Users will need to develop an experience base to relate HMB® BMR values to actual biofilm biomass on surfaces in their systems. Like ATP results, the HMB® test results also showed good reproducibility in analyses of replicate MRD studs. HMB® results usually agreed with ATP results on the direction of changes in biofilm population size/activity.

Evaluation of Biofilm Assessment Methods

The ATP and HMB® biofilm test methods, as applied in this study, were able to assess the presence and/or activity of one-month biofilm populations from four water systems.

Sampling and analysis of biofilm ATP on stainless-steel coupons and MRD studs using the UltraSnap™ Surface swabs were rapid (approximately 2 minutes) and completed without difficulty. ATP results were straightforward to read and interpret. ATP analyses of replicate MRD studs demonstrated particularly good reproducibility at three of the four testing locations.

Comparison of biofilm ATP results with the results of ATP analyses of water samples were consistent with the well-documented concept that measures of planktonic microbial population size/activity, including Cell-ATP and Free-ATP, are poor indicators of biofilm microbial populations in the same system.

HMB® analyses of biofilms on the HMB® perforated polycarbonate coupon and the stainless-steel mesh biofilm coupon, and of surface swabs or whole MRD studs, are straightforward to perform, requiring only transfer of the coupon, MRD stud surface swab or whole MRD stud to the reaction tube, followed 15 minutes later by attachment of the HMB® instrument. The entire sampling and analysis process requires less than 16

Results from this study indicate both ATP and HMB® can be used to monitor changes in growth/control of biofilms in a system. The decision to select one method rather than the other would be based on factors other than confidence in the method, factors such as testing time, equipment and per-test cost, and waste generation from the tests, among others.

HydroBio® biofilm stain test results were found to be straightforward to interpret in cases where the amount of biofilm was moderate, and uniformly distributed across the coupon surface. Patchy biofilm coverage at some locations made interpretation of stain results difficult or impossible (Figure 7).

As expected, this measure of biofilm biomass correlated poorly with measures of biofilm microbial population activity. In this investigation, the method was most useful as a visual check on low-to-moderate levels of biofilm on surfaces, but not as a quantitative biofilm assessment tool.

The HydroBio® test takes approximately 20 minutes to perform (including a 15-minute waiting period).

Equipment and Testing Material Costs

The cost of equipment, the cost of consumables, and the time to conduct onsite testing are important considerations when deciding if a new test will be a cost-effective the Analyst Volume 27 Number 4

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addition to a service visit. The added value of a testing program such as biofilm monitoring must be assessed by each company for every account. As background information for that assessment, a summary of the equipment and consumables needed to conduct this testing is also provided in Table A. Table A: Summary of Biofilm Testing Equipment, Consumables Equipment Type

Biofilm Growth/ Sampling Devices and Test Surfaces

Biofilm Analysis Equipment

Consumables

Test Type

Manufacturer

Item Code

Modified Robbins Device

Tyler Advanced Corrosion Technology

MPMR1006PVC

MRD studs

Tyler Advanced Corrosion Technology

MPM-CTSS

Corrosion coupon rack

Various

Various

Coupon Holder

Pacific Sensor LLC

L-9064

Stainless-steel coupon

Metal Samples

CC-0001-SS

Biofouling Mesh Screen Coupon

Metal Samples

CC-0006-BM

ATP Luminometer

Hygiena

SS3

HMB System

BioTech International

HMBX

HydroBio® Test Kit

Kurita

4950380

®

UltraSnap™ ATP Pens

Hygiena

US2020

Bacteria test kit for HMB®

Biotech International

HMB® 100XC

HydroBio® test kit*

Kurita

4950380

*Note that essentially the whole kit is landfill waste when the 10 tests are done.

Biofilm Monitoring Device and Biofilm Assessment Methods Conclusions

The consensus among participants in this study is that the use of stainless-steel coupons in a standard corrosion coupon rack with analysis by ATP swab testing provides the most reliable, accessible, and cost-effective approach to monitoring biofilm in small and moderate-size industrial water systems. The HMB® biofilm activity assessment method is a reasonable alternative or supplement to ATP analyses for those willing to invest the effort in developing an understanding the relationship between BMR values and biofilm presence/activity in a particular system of interest.

The HydroBio® biofilm stain was found to be difficult to interpret in systems that develop patchy biofilms.

This difficulty, encountered at two of the four locations included in this study, and coupled with the high cost per test compared to other methods, will limit its use at many facilities.

An alternative ultra-low cost means to monitoring biofilm is to visually monitor a stainless-steel mesh coupon in a coupon rack.

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Establishing a Biofilm Sampling/Testing Protocol

So, where does the water technologist begin? How do you set up a biofilm monitoring program and integrate it into your ongoing water chemistry and planktonic microbiology monitoring programs? Outlined here is the general approach used in the six-month biofilm field monitoring study on which much of the information in this article is based. The protocols described are from the work conducted at one facility but are based on the guidelines used in establishing biofilm monitoring protocols at all facilities monitored in the study. The protocols are easily adjusted to accommodate larger or smaller systems, single or replicate samples and analyses, single or multiple-month coupon exposure periods, among others.

First, a strong caution: All studs, stud holders, coupons, coupon holders, coupon/stud handling equipment, testing materials, and cleaning materials should be treated as biohazard material requiring disinfection before reuse or proper handling for disposal. The concentration of bacteria of unknown types in a biofilm will be orders of magnitude higher than in the same volume of water from the system. The presence of pathogenic organisms, such as Legionella pneumonphila, should the Analyst Volume 27 Number 4

Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

ATP tests can be conducted during the 15-minute HMB® incubation period.

be considered a possibility. Always take the proper precautions. For example: Use disposable gloves when performing biofilm testing.

Biofilm data that is collected supplements more standard cooling system water monitoring data that is likely to already be gathered as part of a complete water treatment program, including oxidant concentrations, pH, conductivity, temperature, oxygen reduction potential (ORP), dipslide, and free and total ATP for planktonic bacteria, for a more complete understanding of a system’s biological load.

The general testing protocol used in this study are as follows:

2. Collect water samples for chemical analyses.

3. Inoculate dipslides for planktonic bacteria count.

4. Conduct planktonic (water) ATP tests (if applicable).

5. Record readings for conductivity, pH, temperature, ORP, and other parameters 6. Record side-stream/bypass flowrate.

Stop side stream flow. Isolate MRD and corrosion coupon rack by closing valves upstream and downstream of the MRD and rack. The objective is to keep the MRD and coupon rack full of water while sampling so that stud/coupon surfaces do not become dry before they are tested.

8. Prepare materials for HMB® and ATP swab analyses.

9.

12. Remove MRD studs one at a time, and conduct the ATP and HMB® tests, as described in the next section.

13. Conduct biofilm stain tests on undisturbed biofilms on stainless-steel coupons or MRD studs as per instructions provided with the HydroBio® Biofilm Test kit.

HMB® Biofilm Test Protocol for Corrosion Rack Coupons

Here are the steps when conducting the HMB® Biofilm Test:

1. Record time/date.

7.

continued

Isolate the coupon rack. Conduct work on the uppermost coupon holder and work your way down so that the lowest coupons remain wet until pulled.

10. Remove the coupon holder/carrier with stainless steel, stainless-steel mesh, and HMB® perforated polycarbonate coupons from the coupon rack.

11. Conduct ATP and HMB® tests on coupons removed from the coupon rack, as described below.

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1. Prior to the service visit, prepare the required number of HMB® biofilm test tubes (one per coupon to be analyzed) as follows: Dispense 10 drops of HMB® 50C chelating reagent into each tube to be prepared. Add 10 milliliter (mL) of distilled water to each tube (tap or deionized water not to be used). Put the stopper into the tube and invert a couple of times to mix.

2. Remove the polycarbonate coupon from the rack without touching the surface of the coupon or touching the coupon to the inner surfaces of the rack piping. Place the coupon into one of the prepared test tubes from the HMB 100XMC-12 test kit (Figure 8).

3. Add 10 drops of HMB® 50R reagent and complete the HMB® analysis as per the manufacturer’s testing protocol. Record the reading on the HMB® instrument display.

4. Install a new, clean coupon, or clean the coupon just analyzed, rinse thoroughly in water from the system and reinstall.

5. Repeat Steps 1 through 3 to analyze the stainlesssteel mesh coupon and MRD stud samples.

This procedure is intended for use on site for the purpose of assessing the need for biocide adjustment/addition. It is expected that service personnel will perform the test on a regularly scheduled service visit. Since the frequency the Analyst Volume 27 Number 4

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continued

of visits is a variable, relative numbers, not absolute numbers, have the most significance. This means that records on each installation should be kept, and when a particular installation’s result changes, it is a call to action. Nevertheless, the manufacturer’s general guidelines should be considered: Readings of less than 0.27 BMR should be considered insignificant. Readings greater than 4.0 BMR indicate heavy contamination.

Figure 8: HMB® testing with the stainless-steel mesh coupon. Inserting the coupon into the reaction tube (left). Fifteenminute reaction period (middle). Inserting the HMB® measurement needle through the reaction tube stopper to detect change in oxygen partial pressure in the tube’s headspace (right).

ATP Swab Biofilm Test Protocol for Corrosion Rack Coupons

Here are the steps when conducting the ATP swab biofilm test with corrosion rack coupons.

1. Remove the coupon holder/carrier with stainlesssteel coupons from its position in the coupon rack.

2. Swab the outer surface (closest to the coupon rack pipe wall) of the stainless-steel coupon with an UltraSnap™ ATP Surface Test swab. The coupon area to be swabbed is shown in Figure 9. Because particulates can attach to the screw holding the stainless-steel coupon to the holder, avoid swabbing that area to measure only the biofilm associated with the flat coupon surface associated with a more laminar flow. As the results of these tests are relative, the actual number is less important than trendline data. However, it is important to attempt to minimize differences in the swabbed surface area to obtain comparable results on each test occasion.

After the coupon surface is swabbed, insert the swab into the tube and perform the (total) ATP test as per the manufacturer’s instructions. Record the results.

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3. Clean the coupon holders with a brush, alcohol wipes, and/or tissues and rinse with treated city water if available. Place new coupons on the coupon holders, using gloves to prevent contamination of the coupons with bacteria and oils from your hands, and reinstall.

Figure 9: Area of stainless-steel coupon to be swabbed for testing.

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ATP and HMB® Testing with MRD Studs Sampling from an MRD for biofilm ATP and HMB® analyses is like sampling for tests conducted on coupons from a coupon rack, but it requires additional steps as described here. The MRD (Figure 10) is fitted with six removal studs that can be used for replicate analyses for the same test, for several different test types, or for biofilms that have developed over more than one exposure period (e.g., one-month and three-month biofilms).

Hence, it is important to keep track of the history of each stud. For this reason, the stud holder positions on the MRD are numbered. Again, it is important to wear gloves to minimize contamination of the MRD studs by your hand, and vice versa.

Figure 10: Modified Robbins device.

continued

before a new stud is installed in the holder, and the holder+stud assembly is reinstalled in the manifold.

Handle all MRD stud holders in this manner.

4. Remove the MRD stud holder for Stud #2. Swab the MRD surface with a sterile cotton swab. Cut off and place the swab tip into the HMB® test tube.

Alternatively, in systems where no accumulation of biomass occurs on the sides of the stud tip, remove the MRD stud from the stud holder and place the stud in the HMB® test tube. Use the white nylon screw on the holder to push the stud out of the holder. Use forceps or small needle-nose pliers cleaned with an alcohol wipe to grip below the end of the stud for removal. Perform the HMB® analysis. Repeat the HMB® test on other studs as per the sampling schedule.

5. After ATP and HMB® biofilm sampling/analyses are complete, use the white nylon screws on the MRD stud holders to remove the studs from all tested stud holders. Place used studs in a small container to return to the lab for cleaning. These “biofouled” studs should be considered BIOHAZARD MATERIAL and handled only while wearing disposable gloves until disinfected. Used studs should be cleaned in a mild detergent solution in a sonication bath, or by scrubbing with a nylon bristle brush. Once the studs have been cleaned, they should be rinsed in distilled water, disinfected with alcohol, and allowed to dry in a sterile container until reinstalled in the MRD.

Here are the steps when testing for biofilm using an MRD stud holder: 1. Remove MRD stud holder from position #1 (top row). Inspect the stud surface for visible fouling.

2. Using an UltraSnap™ Surface ATP pen, swab the flat circular surface of Stud #1 and conduct the ATP analysis. Take care to swab only the flat surface.

Significant biomass may accumulate on the stud side/edge, as this part of the stud will be in the gap between the MRD stud holder fitting wall and the stud sidewall. Remove and analyze additional studs as per sampling schedule.

3. Place the MRD stud holder on a clean working surface. The MRD stud holder must be cleaned

6. The stud holders, MRD manifold ports, and all O-rings must be inspected and cleaned before reinstallation of new MRD studs. New/clean studs must be handled with gloves during installation to prevent contamination with bacteria and oils from the technologist’s hands.

7.

If the MRD was installed with pipe unions upstream and downstream, and all studs were removed for sampling in this sampling event, remove the MRD and use a bottle brush to clean the main manifold tube. Refit the MRD with the pipe unions.

“Sampling from an MRD for biofilm ATP and HMB® analyses is similar to sampling for tests conducted on coupons from a coupon rack.”

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8. Reinstall the MRD stud holders with new/clean studs in the MRD manifold.

9.

Restart flow through the coupon rack and MRD. Check/adjust flow.

Evaluating Biofilm Monitoring Program Data

As with all analyses, it is important to understand the factors that contribute to the variability of the microbiology findings used in a biofilm monitoring program. Both variabilities associated with the analysis (i.e., analytical precision) and variability associated with the growth of biofilms must be taken into consideration when evaluating biofilm analysis data. Biofilm growth is not a steady, linear process.

Biofilms naturally grow and shed, or “slough,” pieces of biofilm, resulting in greater heterogeneity over area/space and over time than is normally associated with planktonic microbial populations in water samples. Treatment chemicals (biocides, dispersants) applied over the monitoring cycle will promote variability in the size and activity of biofilm populations on samples collected and analyzed at the end of the monitoring period.

continued

For these reasons, we have included ATP and HMB® biofilm monitoring data from one testing location as examples of typical data and data variability obtained in a biofilm monitoring program. The planktonic (water sample) dip slide and free/cell ATP data for this location, a facility comfort cooling system using city water as makeup, are also provided (Figure 11). Planktonic microbial populations detected with dipslides were, over the course of the six-month study, consistently in the 102 to 103 colony-forming units per milliliter (CFU/mL) range, except for on the final sample collection/analysis date, when the dipslide result was recorded as Too Numerous to Count (TNTC). ATP analyses of water samples collected during the biofilm monthly biofilm sampling events consistently found mostly cell-associated ATP, with values in the range of 88 to 250 reliable light units (RLU), except for the sample collected on the final sampling date, for which the result was 724 RLU. With this as context, the biofilm ATP and HMB® results for this location are shown in Figures 12 and 13.

Figure 11: Planktonic microbial population Free ATP and Cell ATP, and dipslide in CFU/mL data for water samples collected during the monthly biofilm sampling events.

“Both variabilities associated with the analysis (i.e., analytical precision), and irregularity associated with the growth of biofilms must be taken into consideration when evaluating biofilm analysis data. Biofilm growth is not a steady, linear process.”

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continued

Biofilm ATP data (Figure 12) demonstrate good agreement between duplicate MRD studs, with similar month-tomonth trends observed on the stainless-steel coupons. Accepting that some additional error may be associated with the first biofilm sampling and analysis event, it appears that biofilm populations are relatively stable starting with the third sampling event. The high CFU/mL and cell ATP values recorded for water samples collected during sampling Event #6 are not reflected in the ATP data for the one-month biofilm sample retrieved and analyzed on that date. Similarly, significantly elevated biofilm ATP results were obtained for MRD studs and the stainless-steel coupon retrieved during sampling Event #2, whereas planktonic cell ATP and dipslide CFU/mL counts were not elevated for water samples collected and analyzed on this date. The results show particularly good agreement among replicate biofilm samples, but as expected, poor agreement with measures of planktonic bacteria population size/activity. The data suggest that typical one-month biofilm ATP levels at these locations are routinely in the 200 to 400 RLU per sample range, and a trend to ATP results above 400 RLU would be cause for additional investigation.

Figure 12: Biofilm ATP results for one-month biofilms on stainless-steel MRD studs exposed in the MRD and stainless-steel strip type corrosion coupon exposed in the corrosion coupon rack.

HMB® analysis results for one-month biofilms on MRD studs, the perforated polycarbonate coupon, and the stainless-steel mesh coupon (Figure 13) are reasonably consistent for samples retrieved and analyzed in each sampling event. The biofilm HMB® data show a pattern, which is like the biofilm ATP data for sampling Events #1 and #3 through #6, with values varying only moderately from month to month. With few exceptions, results generally fall within a 2 to 4 BMR range, suggesting, per the HMB® literature, moderate biofouling. As with the biofilm ATP results, the higher planktonic population dipslide and cell ATP values recorded for sampling Event #6 were not replicated in the HMB® biofilm results for sampling Event #6.

22

In contrast to the elevated biofilm ATP results observed in sampling Event #2, the HMB®/peroxidase activity in all samples for sampling Event #2 was lower than the activity of samples from sampling Events #1 and #3 through #6, reinforcing our understanding that the ATP and HMB® tests are measuring different aspects of microbial activity and can respond differently to system events. The observation that this increase in ATP or decrease in HMB®/peroxidase activity was not observed in subsequent sampling events, suggests this was associated with temporary conditions and/or treatment chemicals in the system during the period preceding sampling Event #2. A sudden significant decrease in biofilm activity levels as indicated by the HMB® data would the Analyst Volume 27 Number 4

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continued

normally trigger a review of treatment records and operating system physical/chemical data to determine the cause of the decrease in biofilm activity, and if the change(s) might be leveraged for improved biofilm control in the future.

Figure 13: Biofilm HMB® results for one-month biofilms on stainless-steel MRD studs exposed in the Modified Robbins Device, and the HMB® perforated polycarbonate coupon and stainless-steel strip type corrosion coupon exposed in the corrosion coupon rack.

Overall, the ATP and HMB® results for one-month biofilms that collect on MRD studs and a variety of coupon materials demonstrate that reproducibility of biofilm growth on these materials under these conditions and reproducibility of the ATP and HMB® analyses are more than adequate to detect moderate-to-significant changes in biofilms. Once a typical range of ATP and HMB® results is established, trends or sudden changes in the analytical results can be used to alert water technologists to changes in the system requiring their attention.

23

Using Biofilm Monitoring Data

Biofilm monitoring information can also provide useful energy demand insights. In Figure 14, we see the correlation between chiller approach temperatures and biofilm formation at our Midwestern industrial plant test site. The approach temperature is the difference between the Freon refrigerant condensing temperature and the temperature of the cooling water exiting the condenser.

So, an increasing condenser approach temperature is therefore indicative of a reduction in heat exchange (loss of efficiency), which in turn is caused by some form of fouling. Figure 14 shows good correlation between biofilm formation (as measured by the HMB® detection strategy) and chiller approach temperature in seven of the eight months this was tracked.

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continued

Figure 14: HMB® biofilm monitoring data and chiller approach temperatures at an industrial site.

Conclusions and Recommendations

From the field studies carried out and subsequent review of the data generated, several conclusions were drawn that support the use of passive biofilm collection and detection strategies as a field tool for water treatment professionals to implement.

Two of the collection platforms studied were found to be suitable. These methods were practical, consistent, and reproducible. Use of a corrosion coupon rack allows for convenient access to a flowing stream of bulk cooling water. Most/many locations already employ corrosion coupon racks for monitoring metal loss. As shown, modification of those racks can be readily completed to allow for monitoring biofilm.

The MRD is not as convenient to work with but offers the benefits of being able to collect biofilm from different zones of a pipe surface and the collection of multiple data points simultaneously. This method was found to be more expensive and more time consuming.

The stainless-steel corrosion coupon offers a single surface of known dimensions, where one sampling interval yields a single data point.

24

The MRD allows for collection of up to six data points on a specific sampling interval.

Similarly, two of the biofilm detection methods were found to fit the criteria established for the study. They were easy to operate, developed reproducible (digital) data, and functioned in a short amount of time and with relatively low expense.

ATP Detection HMB® Detection Each method offered situational benefits, but both were successful in producing a response that can be documented on a service visit, graphed over time and interpreted to allow for either validation of successful control or to provide the operator with insights to alter course in their PM program.

This study offers a ready-to-use approach for adaptation by the water treatment industry. The collection and measurement of biofilm allows for improved water system protection without the cost and complexity of the active techniques, or the online tools on the market. the Analyst Volume 27 Number 4

Biofilm Monitoring: A How-To Guide for Practical Cooling Water Management

Once set up and operational, passive biofilm monitoring is expected to add approximately one to 1.5 hours to the service visit. The basic steps involved are: 1. Extract the stainless-steel coupon from the rack for ATP testing, or the polycarbonate (or user supplied stainless steel) coupon for HMB® detection.

2. Swab the entire coupon surface using an ATP pen, or insert the coupon into the supplied test tube for detection by HMB®.

3. Test the ATP level using an ATP Luminometer or the BMR reading using the HMB® method.

4. Record the value for inclusion into service records.

5. Clean and replace the stainless-steel or polycarbonate coupon and restart flow.

6. Graph and interpret trend changes over time or at key operational intervals.

Water treaters are encouraged to take advantage of the prescriptive methods outlined. Data gleaned from field detection can be used to confirm program success, adjust biocide dosages, predict system cleaning requirements, stave off a looming problem, or evaluate a new microbial control method being employed.

Acknowledgements

The Cooling Water Subcommittee would like to thank AWT for sponsoring and funding this work and the key suppliers whose donations made this work possible (AquaPhoenix Scientific Inc. of Hanover, Pennsylvania, and Hygiena Corp. of Camarillo, California).

Special thanks are also extended to the authors of this article and their employers for their dedicated commitment in seeing this work through to completion.

25

continued

John Caloritis, CWT, holds a B.S. in chemistry and is the technical director of The Metro Group Inc. He has spent 37 years in water treatment in multiple roles, all with one firm. Mr. Caloritis has been active within AWT as both a member and chair of the Cooling Water Subcommittee, a member of the Legionella Task Force, and was recently elected to serve on the AWT board of directors. He can be reached at jcaloritis@ metrogroupinc.com.

Keith Johnson has been in the water treatment industry since 1978 and an independent consultant since 2011. He holds a B.Phil. degree from Miami University and was a graduate student in environmental engineering at the University of Cincinnati. He is a past chair of the AWT’s Cooling Water Subcommittee. He may be contacted at keithmjohn@gmail.com.

Richard Rosser, Ph.D., holds a doctorate in microbiology, and has worked on microbiology issues in industrial environments for 40 years. After 23 years leading oilfield microbiology R&D for Saudi Aramco, Dr. Rosser returned to the United States, and for the past 12 years he has worked with AMSA, Inc. on microbial biofilm control. He can be contacted at rrosser@ amsainc.com.

Derrick Vandenberg, CWT, holds a B.Sc. in chemistry and is the Edmonton District Manager of Guardian Chemicals Inc. He has 18 years’ experience in water treatment and thoroughly enjoys his career. Mr. Vandenberg is active within the AWT as a Cooling Water Subcommittee member, and recently accepted the role of chairperson. He may be reached at dvandenberg@ guardianchem.ca.

the Analyst Volume 27 Number 4

Introduction to Pharmaceutical Waters for U.S. Products T.C. Soli, Ph.D., Soli Pharma Solutions, Inc.

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the Analyst Volume 27 Number 4

Background

Water is prolifically used in the pharmaceutical industry.

Its applications range from preparing compendial grades of water to manufacturing active ingredients, excipients, and a wide variety of sterile and nonsterile finished products (including packaged sterile waters), as well as for testing of all those materials and for equipment and facility cleaning. This article will examine treatment methods, pharmaceutical water types, and uses.

The various pharmaceutical water grades in the United States begin with the minimum quality of drinking water (as specified in Drinking Water regulations for the United States, Europe, Japan, and the World Health Organization [WHO]) (Note, a water user must choose one of these areas for regulatory compliance). Pharmaceutical water is used for initial equipment cleaning as well as for manufacturing pharmaceutical ingredients unless a purer form of water is needed to meet product specifications. For equipment cleaning, the water quality used for the finished raw material or product must be the final equipment rinse unless a solvent is used. Bulkproduced United States Pharmacopeia (USP) Purified Water (PW) is used to make U.S.-marketed nonsterile products and some noninjectable sterile products. Bulkproduced USP Water for Injection (WFI) is used for making U.S.-marketed injectable products.

Most USP test methods require the minimum water quality to be USP PW, but other nonmonographed waters, often identified by a quality attribute or a method of production in its name, are specified for some analyses, often very dated. Sterile packaged versions of bulk PW and bulk WFI are not as pure as their bulk counterparts, primarily because of packaging leachables. USP plans to update the TOC specifications for sterile packaged waters (published in USP 2021 Issue 1, effective May 2021) to better control the level and safety of these packaging leachables.

Where Water Is Used in Pharmaceutical Manufacturing With few exceptions, by quantity, water is the most heavily used article in pharmaceutical manufacturing. It can be used as a cleaning agent; a reagent in laboratory tests; a manufacturing aid or solvent in the fermentation, synthesis, or purification of a pharmaceutical active or excipient ingredient; and an ingredient in a pharmaceutical product, and it can itself be a packaged

27

“With few exceptions, by quantity, water is the most heavily used article in pharmaceutical manufacturing.� pharmaceutical product. Needless to say, with all these possible uses, the necessary minimum purity of this water could be quite varied if not specifically required by the regional regulators and pharmacopoeia where the associated finished product will be marketed.

In this article, we will examine waters for products marketed in the United States, regulated by the U.S. Food and Drug Administration, and whose specifications are based on the USP, even when the product is manufactured in another country and sold in the United States. Where products are manufactured in the United States and marketed, for example, in Europe, compliance with the pharmacopoeia and regulatory expectations of the marketed country is required, unless the USP water quality exceeds that of the market country (e.g., USP PW exceeds the purity of the European Pharmacopoeia [EP] Purified Water). Please note that this article is an introduction to pharmaceutical water uses and treatment and it does not include specific discussion about treatment technologies used by the industry. However, to provide better context, Figures 1 through 4 show examples of pharmaceutical products in which water is an ingredient and treatment technologies used at facilities to make pharmaceutical-grade waters.

Making Purer Water From Drinking Water

Where water purities better than drinking water are required in pharmaceutical manufacturing, it is most usual for the manufacturing facility to have a validated onsite water purification process that consistently and reliably removes impurities from the starting water, which must minimally be Drinking Water quality.

According to USP, the quality of that Drinking Water must comply with all the specifications for one of the four allowed sets of drinking water regulations: 1. The U.S. EPA National Primary Drinking Water Regulations (NPDWR) 2. The Drinking Water regulations of the European Union the Analyst Volume 27 Number 4

Introduction to Pharmaceutical Waters for U.S. Products

continued

3. The Drinking Water regulations of Japan 4. The WHO Guidelines for Drinking Water Even though the latter guidelines are not considered to be mandatory by the WHO, if you are using this drinking water for any purpose in a pharmaceutical facility that manufactures product for sale in the United States, as will be discussed later, compliance with all the specifications within this guideline is not optional— they are mandatory. The same complete compliance rule is true of the other three; compliance with all the specifications within the chosen set of Drinking Water regulation options is mandatory. Refer to Table A for a comparison of the U.S. and WHO Drinking Water attribute specifications.

equipment’s material processing. The water does not have to comply with a specific compendial water grade unless the user specifies that it does. However, whatever water purification process is used to produce this water, that process must be validated to be consistent and reliable, just like any water purification system and every manufacturing process in a pharmaceutical setting.

Figure 1: Two examples of pharmaceutical products that require pharma-grade water at some point in their production process—eye drops and tablets.

The reason for only certain specified Drinking Waters being suitable is toxicological safety. The attributes in these four sets of Drinking Water regulations are vetted to be safe, nontoxic levels of water impurities. So, if the starting water is safe to drink because all potentially toxic inorganic and organic impurities are well below a level of concern, then none of those specific impurities need to be retested in the finished water, allowing the nonspecific tests of conductivity and total organic carbon (TOC) to be suitable quality tests for chemical purity and safety.

Making Active Pharmaceutical Ingredients

As varied as the kinds of active pharmaceutical ingredients (APIs) are, so are the purities of the water needed for the various stages in the synthesis or preparation of those APIs. It is globally recognized through ICH Q7A that the minimum water quality for these processes must be drinking water. According to that harmonization document, that means it meets the WHO Guidelines for Drinking Water. According to the FDA and USP, the water must comply with the specifications of any of the four drinking water options mentioned above.

Of course, if even purer water is needed to achieve the desired purity of the API or intermediate, a purer water must be used—as defined by the user. For processing equipment cleaning, the initial cleaning can be done with drinking water, but the final rinse, if it is with water, must be whatever purity of water is used in that 28

Making Non-Sterile Drug Products

If the product being made is a non-sterile drug, like a tablet, capsule, oral liquid, skin cream, suppository, or similar product, and water is used in the formulation, even if it is no longer present in the final product (such as with tablets and capsules), that water must be USP PW if the product is marketed in the United States.

See Table B comparing the attributes of USP’s various monographed waters.

“Of course, if even purer water is needed to achieve the desired purity of the API or intermediate, a purer water must be used—as defined by the user.” the Analyst Volume 27 Number 4

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Since water is often used for cleaning the equipment used to compound, manufacture, and package these products, the initial equipment cleaning may be accomplished with Drinking Water, but the final rinse must be the same water used in the product’s formulation—in this case, PW.

Making Sterile Drug Products

Because of the extremely sensitive or infection-prone nature of the location where a particular product is applied or introduced, the product may need to be sterile. It could be injected into sterile tissue or applied to abraded or compromised skin or mucous membranes or to other nonsterile tissues that are otherwise highly susceptible to infection. The quality of the water used for these sterile products, which are either sterilized in their packaging after they are manufactured or formulated with sterile materials and packaged in an aseptic manner that avoids contamination, depends on whether they are used externally on nonsterile tissue or injected into sterile tissue.

and usually bound to living bacterial cells), pyrogen (because one of the most noticeable pharmacological effects of the molecule is the generation of a fever), lipopolysaccharide (because this large, complex molecule contains both lipid and polysaccharide components), or LPS (for short).

Figure 2: WFI is the primary ingredient in IV liquids frequently administered in hospitals and other medical facilities.

Making Injectable Sterile Drug Products When a drug product is injected through the skin and into the body (a parenteral injection), such as into or just under the skin, into muscle tissue, into a sterile cavity, or into the blood stream, contaminating bacteria that could have been present in the formulation but killed by the product sterilization process could still release a bacterial cell component that is quite toxic to the human body. This toxic cell component is a structural macromolecule in the cell walls of some bacteria, particularly the bacteria that can grow as difficult-to-control biofilms in pure water systems as well as some products. After those bacteria have been killed in the process of sanitizing a water system or sterilizing a product, this toxic cellular component is released from the dead bacterial cell. It goes by various names, such as endotoxin (because it is a toxin found within

“Therefore, the water used as an ingredient for these injectable formulations must be USP WFI, which has an endotoxin specification that renders it safe for most parenteral applications.”

29

Therefore, the water used as an ingredient for these injectable formulations must be USP WFI, which has an endotoxin specification that renders it safe for most parenteral applications. To meet that specification, the WFI system producing this water needs to be as free from these bacteria and these already-freed endotoxin components as possible, in addition to being otherwise chemically pure enough for these sensitive uses.

By contrast, USP PW, which is not used for injectable products, has no endotoxin specification but is otherwise equally chemically pure (see Table B).

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Introduction to Pharmaceutical Waters for U.S. Products

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Just like with nonsterile products, the water used for initial cleaning of equipment used in their manufacturing may be accomplished with Drinking Water, but some firms choose for this initial cleaning to use purer water (e.g., PW, hot WFI) that contains fewer chemicals and microbial-related contaminants. Injectable products are generally aqueous and relatively easy to clean, so even though the WFI is more expensive to make than PW, and certainly more costly than drinking water, the mostly aqueous products usually render manufacturing equipment very cleanable, so relatively little water is needed to achieve a clean condition. However, the final equipment rinse must always be of the same water quality used in the product’s formulation—in this case, USP WFI. To avoid needing to do costly and time-consuming depyrogenation of large bulky equipment, it can be kept relatively apyrogenic or pyrogen-free by simply doing all cleaning with WFI and never introducing the possibility of endotoxin or microbial contamination from contact with less pure waters.

from other organizations, such as ASTM (American Society for Testing and Materials International), ISO (International Standards Organization), and CLSI (Cli nical and Laboratory Standards Institute). Just as with manufacturing equipment cleaning, less pure water, such as drinking water, could be used for initial cleaning of labware, but the final rinse must be at least PW quality.

Figure 3: Reverse osmosis is an important treatment technology used in the production of pharmaceuticalgrade waters.

Making Noninjectable Sterile Drug Products

There are a few pharmaceutical products that still need to be sterile because of the infection-prone locations where they are used. Examples are ophthalmic products, first aid products applied to abraded or inflamed skin, some optic treatment products, and inhaled liquid products for some debilitating lung diseases. But because these drugs are not injected, there are far fewer concerns regarding endotoxin in the product or water used to formulate these products. The skin and mucous membranes are resistant to the penetration of endotoxin molecules that could be in the ingredient water. Therefore, USP PW (which has no endotoxin specification) is generally adequate for formulating these products. The same waters for cleaning as used for nonsterile drug products can be considered, with the same caveat of using the same water quality as in the formulation for the final equipment cleaning rinse.

Performing Laboratory Analyses

USP requires that USP PW is the minimum quality of water that must be used in all analyses in the USP compendium, unless otherwise specified. Of course, there could be needs for water of greater purity for some trace level or otherwise sensitive analyses, compendial or not, and also for analyses performed in the laboratory 30

“Water” Means PW

In USP’s General Notices section, it in essence states that where the term “water” is used in the text of analytical chapters or monographs, USP PW is the “water” that must be used, unless otherwise specified.

Test-Specific Waters

Several tests within USP are quite dated, often being incorporated using the language of the innovator who submitted their test wording to the compendium for the Analyst Volume 27 Number 4

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Introduction to Pharmaceutical Waters for U.S. Products

continued

these ancient but still used products. The innovator’s name of the water could pre-date the switch to conductivity and TOC in the Purified Water and Water for Injection monographs (occurring in 1996) because, frankly, the original wet chemistry tests specified prior to that time for these monographs did little to delineate the water’s purity.

“Particle-Free Water”: PW that has been passed through a 0.22-micron (µm)-rated filter membrane.

Often the terms used either vaguely described an attribute or a preparation process with little other detail.

Sometimes, when the test was intended to detect trace levels of analyte “X”, the specified water would be “X-free water”. One can never be certain that there is absolutely zero “X” in the water because no analysis can detect the absolute and complete absence of any analyte, “X” or otherwise. There is always a limit of analytical detection for any analyte. So, the implication is that there is not enough “X” in the water to be detectable by or interfere with the test where it is specified.

Some mongrel waters are merely synonyms of others, such as: “Degassed Water”, which is presumably equivalent to “Deaerated Water”; “Nitrogen-Sparged Water”, presumably equivalent to “Carbon Dioxide-Free Water”; and “Filtered Water”, presumably equivalent to “ParticleFree Water”.

The author considers these waters to be “mongrel waters” since they are usually very poorly defined, compared to the monographed waters. Some of these waters at least have specifically defined preparation methods or rudimentarily defined attributes within the Reagents section of USP, such as: “Carbon Dioxide-Free Water”: PW that is either vigorously boiled for at least 5 minutes and cooled while protected from absorption of atmospheric carbon dioxide or PW with a resistivity of not less than 18 megohm centimeter (Mohm-cm).

“Deaerated Water”: PW that is treated to reduce the content of dissolved air by either vigorously boiling for 5 minutes and cooling, treated with ultrasonic vibrations, or other suitable means.

“Organic-Free Water”: PW that produces no significantly interfering peaks when chromatographed according to the Residual Solvents test in Chapter <467> of the UPS.

Other mongrel waters within the pages of USP are much less defined, include waters whose names describe how they are prepared. So, even without specific purity specifications, knowledge of the attributes bestowed by the purification process implies their purity to a degree, such as: “Distilled Water”, “Deionized Water”, “Double Distilled Water”, “Deionized Distilled Water”, “Freshly Distilled Water”, and “Degassed Filtered Water”, among others.

And still there are other pharmaceutical waters that are identified by the type of use they may have, such as: “Cell Culture Water”, “Bacterial Endotoxins Test Water”, and “HPLC Grade Water”.

The irony of many of these mongrel waters is that the purity implied by their names or even their preparation methods may not be important for their specified analytical uses. They may just be traditional. The most common offender is “Carbon Dioxide-Free Water”, which is by far the most specified non-monographed mongrel water.

When pure water contains dissolved CO2, it is acidic

Figure 4: A panoramic view of storage tanks and a water treatment system in a pharmaceutical plant.

32

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Introduction to Pharmaceutical Waters for U.S. Products

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near pH 6 or the high 5’s, and it contains bicarbonate ions from the dissolved and dissociated CO2, causing its equilibrium with carbonates and bicarbonates. But when it is truly CO2-free, it has a nearly neutral pH and very few bicarbonate ions. You would think that this water’s analytical uses would center around pH-sensitive analyses, acidity/alkalinity tests, or tests for carbonates, but it is specified in a wide variety of tests that are not impacted by its acidic pH, the presence of bicarbonate ions, or its minimal buffering capacity.

As it turns out, the preparation of Carbon DioxideFree Water is more of a chemistry lab tradition than it is an analytical necessity. Many older classically trained chemists have, in an abundance of precaution from training in schooling, always just used boiled and cooled water (supposedly making it carbon dioxide-free as well as temporarily degassing it) for preparing all reagents and performing traditional wet chemistry tests. It is an unnecessary tradition that continues to this day in many USP tests where this mongrel water is specified for use.

What these analysts may not realize is that carbon dioxide re-absorption by the water is almost immediate (though it does take some time to reach equilibrium) and difficult to completely avoid. Fortunately, it has negligible impact on the test results, even for pH-sensitive tests, but unfortunately, it creates unnecessary work for the lab analysts. In most cases, plain old ordinary PW, which has not been boiled and cooled and therefore contains some level of dissolved CO2, works just as well.

But you must use the water specified for a procedure, right? Even if it makes no sense, right? It is time for USP to change its procedures to what makes scientifically defensible sense.

As a Pharmaceutical Product

There are a number of monographs within USP for packaged and sterilized waters that are made from bulk-produced PW and WFI, each with its own packaging styles, limitations, intended applications, and chemical purity specifications: Sterile Purified Water, Sterile Water for Injection, Sterile Water for Irrigation, and Sterile Water for Inhalation are four of them (see Table B). All these packaged sterile waters originated as monographs long before the advent of conductivity and TOC being specified in the bulk water monographs for PW and WFI.

33

So, the original qualitative wet chemistry tests of yesteryear, some dating back to about 1900, were present until 2009 and replaced with a packaging size-based conductivity test. However, because of resistance from the manufacturers of these waters to an equally contemporary organic specification using TOC, the century-plus old test for organics, the Oxidizable Substances test, was retained as an alternative to the TOC test with a specification of 8 ppm. That archaic test option was always intended to sunset, leaving only TOC as a specification to control the organic content in those sterile packaged waters to a “safe’ level, whatever that level was.

As had evolved in the absence of a meaningful organic test, the contemporary plastic packages with desirable moldability, strength, shape conformance, and flexibility were developed. But these packages were very bad about leaching organic compounds and plasticizers from their inner surfaces into the water without the manufacturer’s knowledge because they still passed the archaic Oxidizable Substances test that could not detect these complex organic compounds.

So, in the absence of awareness of their presence by test, the TOC content of the more contemporary sterile packaged waters skyrocketed to levels many-fold higher than the bulk water filled into these packages, in some cases, as high as 100 parts per million (ppm). By contrast, the water put into these packages from a WFI system has a TOC specification of 0.50 ppm, but most firms produce WFI that is about 1/10th to 1/100th that level. And, even Drinking Water has TOC limits in the 2-ppm area. Something seemed intuitively wrong about such high TOCs in the sometimes-large doses of water going into your body intravenously from those contemporary packages!

So, USP is in the process of applying the contemporary and quantitatively meaningful product tests of conductivity and TOC to the sterile packaged pharmaceutical water industry that is accustomed to having few limitations on packaging organic leachables. Are high levels of these organics safe? All historical packaging safety tests that assess acute toxicity as well as the millions of supposedly uneventful users to date say they are. But evidence is emerging that certain of these leaching compounds may not be so safe to some populations (e.g., neonates and pregnant women) when chronically administered in large the Analyst Volume 27 Number 4

Introduction to Pharmaceutical Waters for U.S. Products

continued

“To be certain, the chemical purities of the bulk PW and bulk WFI are far and away better than the chemical purity of the sterilized packaged forms of those waters.” volumes, particularly from the leachable phthalate plasticizers that make some plastic packaging very flexible.

The USP will institute new TOC specifications and delete the Oxidizable Substances test option for these packaged sterile waters in May of 2021. These changes should better assure the safety of sterile packaged waters at what USP feels is a scientifically defensible and achievable level. These new TOC specifications are complexly worded with a set of limits that vary as a function of package size since the packaging surface-area-to-volume ratio varies so dramatically with the variety of packaging sizes now available (from pre-filled syringes of possibly less than 1 cubic centimeter (cc) to 2 liter (L) or larger bags and bottles). That TOC specification now contains wording that forces the vendor of these packaged sterile waters to assess the identity and safety of each organic species in the water if the total TOC level is higher than a threshold value. These various specifications for the various monographed USP waters are found in Table B. To be certain, the chemical purities of the bulk PW and bulk WFI are far and away better than the chemical purity of the sterilized packaged forms of those waters.

Those sterile water monographs state that aside from the sterility attribute, the bulk and sterile packaged forms of PW and WFI could be used interchangeably. However, in USP Chapter <1231>, that interchangeability statement is qualified by explaining the chemical purity differences between the non-sterile bulk and sterile packaged waters means that there could be performance differences between the bulk and packaged versions of the same type of water and that the user must assure the suitability for the intended use of the water they choose to use.

Microbiological Specifications for Compendial Waters

Little controversy exists over the required microbial attributes of the sterile packaged waters— they must 34

be sterile, assured by a validated terminal sterilization (usually by steam autoclave) of the final packaged product, and checked by sterility test.

However, a large controversy exists over the microbial content of the non-sterile bulk PW and WFI from which the sterile waters are made as well as the test method to assess it. The monographs for PW and WFI intentionally contain no mention of a microbial attribute.

This seemingly unfathomable oversight is explained in USP’s informational Chapter <1231> Water for Pharmaceutical Purposes (see USP-National Formulary [NF] 2020) as being because there are some uses of these waters where the microbial content is irrelevant, such as most laboratory applications and some cleaning applications, making any mandatory microbial testing requirement an inappropriate burden for those uses.

However, that means that there is no mandatory compendial specification and no specified test method in the PW and WFI monographs. But that does not mean that microbial content of these waters is unimportant for many of its applications. To the contrary, it is very impactful for manufacturing uses and in some system design and maintenance scenarios, difficult to control and difficult to properly sample so that sampling technique does not bias the test result.

The regulator’s expectation for the upper limit of microbial content is 100 Colony Forming Units per milliliter (CFU/mL) for PW and 10 CFU/100 mL for WFI. This “expectation” should be interpreted as a true specification since an OOS (Out of Specification) investigation is the required action of exceeding these values so that the cause of the high microbial count can be determined, mitigated, and prevented from recurring and its impact on finished product where the water has been used can be assessed.

The problem with high microbial counts in water samples is that often it is a poorly executed sampling procedure that causes what appears to be high microbial counts for what might otherwise be pristine water produced and delivered by the water system. This sampling issue is beyond the scope of this article but is discussed in detail in USP’s Chapter <1231>. The other issue, as mentioned above, is what test method (sample volume, growth medium, incubation temperature and duration) should be used to assess the microbial count in the water. As the Analyst Volume 27 Number 4

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with the specification issue, this microbial testing issue is also beyond the scope of this article and discussed in detail in <1231>.

Conclusions

What are the “take home” messages from this article?

Water is a prolifically used article in the pharmaceutical industry, for everything from the preparation of compendial grades of water, to manufacturing active ingredients, excipients, and a wide variety of sterile and non-sterile finished products (including several packaged sterile finished products itself), to testing of all those materials, to cleaning of the manufacturing and testing equipment as well as the facility.

Specific Drinking Water grades are required as the starting water for making purer compendial water grades that are intended for making specific classes of products, depending on the sensitivity of where the product is used on or in the body.

Pharmaceutical water grades could be as pure as WFI to as “impure” as Drinking Water (but only specific regional grades). Water complying with the four specified Drinking Waters do not have identical attributes or specifications but are all equivalently safe to consume.

In USP, there is intentionally no microbial specification or test specified in the PW and WFI monographs, but it is nevertheless important for many uses to know and control the microbial content of these waters. The non-mandatory informational Chapter <1231> contains a wealth of information regarding grades of pharmaceutical water, water system microbial control, validation, sampling, and test method choices.

In USP laboratory analyses, the minimum water purity needed is PW, unless otherwise specified. Test-specific purity requirements could be needed for some analyses, but they are usually not monographed and sometimes have poorly defined purities.

Sterile packaged forms of PW and WFI, though stated in USP monographs to be equivalently applicable to their respective bulk waters in usage, are not as pure as the bulk waters from which they are made due to packaging leachables, so be careful of the water chosen for a given application.

“T.C.” Soli is a Ph.D. microbiologist and president of Soli Pharma Solutions, Inc. and for the past 16 years has offered troubleshooting consulting and training services covering water systems, sterilization, sterile and non-sterile manufacturing, microbiological laboratories, and microbial and beta-lactam contamination control. Dr. Soli has a combined 42 years of pharmaceutical experience as a consultant and with operating companies, including DSM Pharmaceuticals, Catalytica Pharmaceuticals, Glaxo Welcome, Burroughs Wellcome, and Pfizer. For the past 20 years, he has served as a member of USP Expert Committees responsible for everything related to high-purity water in USP/NF. He continues to serve USP with his water expertise in the role of Expert Advisor. Before that, Dr. Soli previously served for 18 years on the PhRMA Water Quality Committee, whose achievements included creating the Water Conductivity and TOC specifications used in USP Purified Water and Water for Injection since 1996 (USP 23, Supplement 5). Dr. Soli may be contacted at tcsoli@earthlink.net.

Table A: Comparison of U.S. (NPDWR) and WHO Drinking Water Specifications US: 40 CFR 141 (2015)

WHO: Guidelines for Drinking Water 4th Ed (2011)

Attribute (as mg/L unless otherwise noted)

U.S.

WHO

Inorganic Chemical Contaminants: Antimony

0.006

0.02

Arsenic

0.01

0.01

Asbestos (as MFL [million fibers per L] > 10um long)

7

Barium

2

Beryllium

0.004

Boron

0.7 2.4

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Attribute (as mg/L unless otherwise noted)

U.S.

WHO

Cadmium

0.005

0.003

Chromium (total)

0.1

0.05

Copper

1.3 Action Level

2

Cyanide (as free Cyanide)

0.2

Fluoride

4.0

1.5

Lead

0.015 Action Level

0.01

0.002

0.006

Manganese

0.4

Inorganic Mercury Molybdenum

0.07

Nickel

0.07

Nitrate (US as N, WHO as NO3-)

10

50 (short-term)

Nitrite (US as N, WHO as NO2-)

1

3 (short-term)

Total Nitrate and Nitrite (as N)

10

Selenium

0.05

Thallium

0.002

0.04

0.03

Uranium

Organic Chemical Contaminants: Acrylamide (when used as flocculant at 1mg/L)

0.0005

0.0005

Alachlor

0.002

0.02

Aldicarb

0.003

Aldicarb sulfoxide

0.004

Aldicarb sulfone

0.002

Aldicarb (sulfoxide and sulfone)

0.01

Aldrin and Dieldrin (combined)

0.00003

Atrazine (plus chloro-s-triazine metabolites for WHO)

0.003

0.1

Benzene

0.005

0.01

Benzo[Îą]pyrene (PAHs)

0.0002

0.0007

Carbofuran

0.04

0.007

Carbon tetrachloride

0.005

0.004

Chlordane

0.002

0.0002

Chlorobenzene

0.1

Chlorotoluron

0.03

Chlorpyrifos

0.03

Cyanazine

0.0006

Dalapon

0.2

1,2-Dibromo-3-chloropropane (DBCP)

0.0002

0.001

0.6

1

1,2-Dibromoethane (Ethylene dibromide)

0.0004

o-Dichlorobenzene p-Dichlorobenzene

0.075

0.3

1,2-Dichloroethane (Ethylene dichloride)

0.005

0.03

1,2-Dichloroethene (Acetylene dichloride)

0.05

1,1-Dichloroethylene

0.007

cis-1,2-Dichloroethylene

0.07

trans-1,2-Dichloroethylene

0.1

Dichloromethane (Methylene chloride)

0.005

0.02

2,4-D (2,4-Dichlorophenoxy acetic acid)

0.07

0.03

2,4-DB (4-(2,4-Dichlorophenoxy) butanoic acid)

0.09

DDT and metabolites

0.001

Dichloroprop

0.1

1,2-Dichloropropane

0.005

1,3-Dichloropropene

0.04 0.02

Di(2-ethylhexyl)adipate

0.4

Di(2-ethylhexyl)phthalate

0.006

Dimethoate

0.008 0.006

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Attribute (as mg/L unless otherwise noted)

U.S.

Dinoseb

0.007

1,4-Dioxane

WHO 0.05

Dioxin (2,3,7,8-TCDD)

3.0 x 10 -8

1,2-Diphenylhydrazine Diquat

0.02

Edetic acid (EDTA free acid)

0.6

Endothall

0.1

Endrin

0.002

0.0006

Ethylbenzene

0.7

0.3

Ethylene dibromide (EDB)

0.00005

Glyphosate

0.7

Heptachlor

0.0004

Heptachlor epoxide

0.0002

Hexachlorobenzene

0.001

Epichlorohydrin (used as a flocculant at 20mg/L)

0.0004

Hexachlorobutadiene

0.0006

Hexachlorocyclopentadiene (HEX)

0.05

Hydroxyatrazine (Atrazine metabolite)

0.2

Isoproturon

0.009

Lindane

0.0002

MCPA ((4-Chloro-2-methylphenoxy) acetic acid)

0.002 0.002

Mecoprop

0.01

Methoxychlor

0.04

0.02

Metolachlor

0.01

Microcystin-LR (free + cell bound)

0.001

Molinate

0.006

Nitrilotriacetic acid (NTA)

0.2

Oxamyl (Vydate)

0.2

Pendimethalin

0.02

Pentachlorophenol

0.001

Picloram

0.5

Polychlorinated biphenyls (PCBs)

0.0005

0.009

Simazine

0.004

0.002

Styrene (Ethenylbenzene)

0.1

0.02

0.005

0.04 0.7

Terbuthylazine

0.007

Tetrachloroethylene (PCE) Toluene

1

Toxaphene

0.003

1,2,4-Trichlorobenzene

0.07

1,1,1-Trichloroethane

0.2

1,1,2-Trichloroethane

0.005

Trichloroethylene (Trichloroethene, TCE)

0.005

2,4,6-Trichlorophenol (a DBP)

0.02 0.2

2,4,5-Trichlorophenoxyacetic Acid (2,4,5-T, Trioxone)

0.009

2-(2,4,5-Trichlorophenoxy)propionic acid (2,4,5-TP, Fenoprop, Silvex)

0.05

0.009

Vinyl chloride (Chloroethylene)

0.002

0.0003

Xylenes (total)

10

0.5

â&#x2030;¤1

Trifluralin (Trifluron/Triflumuron)

0.02

Disinfection Byproducts (DBPs): Total Trihalomethanes (sum of four THMs as rolling quarterly avg)

0.080

Haloacetic acids (sum of five HAAs as rolling quarterly average)

0.060

Bromate

0.010

0.01

1.0

0.7

Chlorate

0.7

Chlorite

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Attribute (as mg/L unless otherwise noted)

U.S.

WHO

Chloroform (Trichloromethane, a THM)

0.3

Bromodichloromethane (a THM)

0.06

Dibromochloromethane (a THM)

0.1

Bromoform (Tribromomethane, a THM)

0.1

Dichloroacetic acid (a HAA)

0.05

Trichloroacetic acid (a HAA)

0.2

Monochloroacetic acid (a HAA)

0.02

Dibromoacetonitrile

0.07

Dichloroacetonitrile

0.02

N-Nitrosodimethylamine

0.0001

Radioactive Contaminants: Adjusted Gross alpha activity (as pCi/L, excl. Radon and Uranium)

15

Radium226 + Radium228 activity (as pCi/L)

5

Uranium (as mcg/L)

30

Total Beta and Gamma Emitters (as mrem/yr (in 730L or 2L daily))

4

Gross alpha particle activity (as Bq/L, excl. Radon)

0.5

Gross beta particle activity (as Bq/L)

1

Microbiological Contaminants: Heterotrophic Plate Count or HPC as CFU/mL

500 Action Level

Total Coliforms/100mL (% positives per month if >40 sites)

5

Total Coliforms/100mL (# positives per month if < 40 sites)

1

Fecal Coliforms and E. coli /100mL

0

Turbidity (per month as NTUs in daily samples):

0.3 (<95%), <1.0 (100%)

0

Miscellaneous Attributes: Total Organic Carbon (TOC, Rolling quarterly avg)

2.0

Disinfectant Residual: Chlorine (as Cl2, US minimum 0.2)

4.0

Chloramines (as Cl2, US minimum 0.2)

4.0

Monochloramine

5 3

Chlorine dioxide

0.8

Sodium Dichloroisocyanurate

50 (40 cyanuric acid)

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Table B: Specifications for USP Monographed Waters (Effective with USP-NF 2020 (except as noted) USP Water Monographs

Attribute

Relevant USP Test Chapter

Purified Water (bulk)

Water for Injection (bulk)

Sterile Purified Water

Sterile Water for Injection

Sterile Water for Irrigation

Sterile Water for Inhalation

Conductivity

<645>

1.3 µS/cma

1.3 µS/cma

25 µS/cmb 5 µS/cmb

25 µS/cmb 5 µS/cmb

25 µS/cmb 5 µS/cmb

25 µS/cmb 5 µS/cmb

32 mg/Lc 24 mg/Lc 8 mg/Lc

32 mg/Lc 24 mg/Lc 8 mg/Lc

32 mg/Lc 24 mg/Lc 8 mg/Lc

Total Organic Carbon

<643>

0.50 mg/L

0.50 mg/L

32 mg/Lc 24 mg/Lc 8 mg/Lc

Microbial

<71> (for sterile waters only)

None in monograph, but ≤100cfu/mL expected for mfgd

None in monograph, but ≤10cfu/100mL expected for mfgd

Sterile

Sterile

Sterile

Sterile

Bacterial Endotoxins

<85>

N/A

< 0.25 EU/mL

< 0.25 EU/mL

< 0.25 EU/mL

< 0.25 EU/mL

< 0.5 EU/mL

Particulates

<788>

N/A

N/A

N/A

Meets test

N/A

N/A

No size limit

Not more than 1 L

No size limit

No size limit

Packaging Size

N/A

N/A

Notes: a

Stage 1 raw conductivity limit at 25° C. Different values at other temperatures. Stage 2 equilibrated limit is 2.1 µS/cm.

b

25 µS/cm is limit for containers with nominal volume of ≤ 10 mL and 5 µS/cm for containers with nominal volume of > 10 mL

c

As of USP-NF 2021, Issue 1, effective May 1, 2021, these TOC specifications will become official. TOC is a two Limit specification, depending on 3 container size ranges. Limit 1 is 32 mg/L carbon for ≤ 5 mL containers; 24 mg/L carbon for >5 mL to ≤ 100 mL containers; and 8 mg/L carbon for >100 mL containers. If measured TOC is less than Limit 1, the test passes. If the measured TOC is greater than Limit 1, but less than the Limit 2 values of 48 mg/L, 36 mg/L, or 12 mg/L, respectively, then individual TOC contributing species present at > 0.20 mg/L carbon must be identified and patient toxicological safety referenced for the patient dose received of each identified organic species for the test to pass. If the contributing organic species cannot be identified or no toxicology information exists for one or more of the organic species or the measured TOC is higher than Limit 2, the test fails.

d

A microbial specification is intentionally absent from these monographs since microbial content is typically irrelevant for some uses. But when used for manufacturing, regulators expect the testing of microbial samples from points of use to meet these limits or otherwise perform an OOS investigation. USP-NF Chapter <1231> has more discussion of this issue.

39

the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs Steven Dunn, Process Performance Management LLC

40

the Analyst Volume 27 Number 4

Introduction

The treatment of water in fossil-fired boilers using phosphate-based materials dates back to the early 1900s. The low feedwater quality at the time caused many boilers to fail because of heavy scale deposition. Calcium and magnesium scales formed on hot heat transfer surfaces, reducing energy transfer and creating conditions for metal failure as increased firing was required to overcome the thermal insulating properties of the scale.

These scales are exceedingly difficult to remove, as they are practically chemically inert and physically hard.

Having the need to reduce costly boiler failures and to reduce extended downtimes for mechanical scale removal, experiments were started to create softer sludge materials by substituting sodium ions for calcium and magnesium ions (water softening). It was known that sodium materials were mechanically softer and more water soluble than their calcium/magnesium counterparts. At about the same time, it was determined that maintaining higher pH levels in the boiler water reduced iron-based metal corrosion (Figure 1).

Figure 1: pH levels and their impact on metal corrosion.

Source: AdamMunich.com

History of Treatment Approaches

Experiments in the early 1900s centered on the use of sodium carbonate. The expectation was that the sodium carbonate would precipitate the calcium and magnesium as carbonate salts that could then be blown down.

However, in actual practice, the precipitated carbonate salts tended to precipitate on the hot boiler internals like the previous calcium and magnesium oxides.

Although the carbonate materials were easier to remove by chemical or mechanical means, it did not solve the deposition problem.

In the 1920s, experiments with combinations of sodium hydroxide and sodium phosphate were proving to be beneficial in reducing calcium and magnesium salt deposition. The calcium and magnesium formed a fairly soluble salt with the phosphate, allowing for most of the calcium and magnesium to be blown down. At the same time, the sodium hydroxide raised the pH of the boiler water into the minimum iron/steel corrosion range. This treatment process worked well in the low-pressure boilers of time; most were less than 800 pounds per square inch gauge (psig) operating pressure. Phosphate levels could be as high as 100 milligrams per liter (mg/L), and the pH, with the difficulty in analysis at the time, generally ranged from 9 to 13; hydroxide levels were not monitored or calculated.

In the 1930s and early 1940s, boiler pressures were increasing to as much as 1,500 psig. Boiler makeup treatment had greatly improved, so boiler deposit formation was no longer the primary cause of boiler failures, and corrosion failures started to take over as the principal cause of boiler failures. The low-pressure phosphate treatment parameters were brought forward and applied to these boilers. There were a number of catastrophic boiler failures due to caustic-induced stress corrosion cracking. Many steam drums at the time had riveted heads; stress around the rivets caused the steel to crack, allowing for large steam explosions in the powerhouse.

Attempts were made to limit hydroxide concentration by adopting what were called conventional phosphate treatment standards: phosphate 30 to 60 mg/L, pH 11 to 12, and hydroxide 20 to 350 mg/L. In the 1950s, boiler pressures continued to increase, and 1,500 to 1,800 psig was not uncommon. Boiler failures increased as the pressures increased and conventional

41

the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

“These actions did reduce boiler failures until boilers again increased in pressure during the late 1960s and early 1970s, when boiler failures increased again.”

Figure 2: Corrosion damage in a high-pressure drum boiler.

Source: B&W Plant Service Bulletin 25

phosphate treatment standards were carried forward to these boilers. It was clear that phosphate treatment was not well understood and that increased research was required to reduce boiler failures. The concept of coordinating the sodium-to-phosphate ratio was introduced to try to reduce sodium hydroxide levels.

The phenomenon of phosphate hideout was also starting to appear, causing wild swings in boiler chemistry during pressure-change events. The new phosphate treatment program was called coordinated phosphate treatment.

Phosphate was limited to 5 to 25 mg/L, pH to 9.0 to 10.5, sodium-to-phosphate ratio to 2.85:1 to 3.0:1, and hydroxide to a trace to a few mg/L. These actions did reduce boiler failures until boilers again increased in pressure during the late 1960s and early 1970s, when boiler failures increased again. Boiler pressures were raised to as high as 2,400 psig. It was still thought that sodium hydroxide was the main culprit in boiler corrosion and that phosphate hideout, which had become a big problem by this time, was more of a nuisance than a cause of boiler tube failures. A treatment program called congruent phosphate treatment was introduced to reduce phosphate hideout and reduce hydroxide levels to near zero. Phosphate was limited to 2 to 5 mg/l, pH to 8.8 to 9.4, sodium to phosphate ratio to 2.3:1 to 2.6:1, and hydroxide to 0 to a trace.

Boiler pressures continued to increase during the 1980s to as high as 3,000 psig. Under congruent treatment, high-pressure boiler failures dramatically increased.

In 1986, while trying to maintain congruent control, a drum boiler operating at 2,650 to 2,750 psig started showing extensive corrosion damage after only nine months of operation. After three years of operation, the boiler was nearly completely destroyed, requiring millions of dollars in repairs (see Figure 2).

42

With hydroxide levels essentially zero under congruent phosphate treatment standards, something other than sodium hydroxide had to be causing the extensive corrosion damage. After considerable investigation, it was determined that the corrosion was caused by acidic phosphate conditions caused by low sodium-to-phosphate ratios and/or low pH from phosphate hideout return. The above boiler failure caused a great deal of re-examination of corrosion mechanisms in high-pressure boilers using phosphate treatments.

In the 1990s, phosphate treatment evolved to a concept called equilibrium phosphate treatment. To minimize the corrosive effects of low sodium-to-phosphate ratios and caustic conditions, the boiler is basically allowed to establish its own phosphate equilibrium between dissolved and solid phases. Phosphate levels were again reduced to minimize hideout effects, and sodium-to-phosphate ratios were strictly limited. With equilibrium phosphate treatment, boiler pressures are limited to about 2,200 psig. At pressures above 2,200 psig, all-volatile (ammonia) or oxygenated treatment has to be used because the solubility of phosphate above 2,200 psig is nearly zero. Under equilibrium phosphate treatment, phosphate levels are generally 0.2 to 3.5 mg/L and are allowed to drift with boiler pressure changes within this range, meaning the hard phosphate level requirements are gone. The pH range is 9.0 to 9.6 in conjunction with the sodium-to-phosphate ratio controlled to 3.0 to 3.0 + 1 mg/L hydroxide. Specific and cation conductivity

“After considerable investigation, it was determined that the corrosion was caused by acidic phosphate conditions.” the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

“The sodium-to-phosphate ratio in the boiler determines if the boiler water will have corrosive phosphate conditions.”

should be controlled to 15 microsiemens per centimeter (µS/cm) or less.

Phosphate Characteristics

Phosphate has reverse solubility: the higher the temperature, the lower the amount of phosphate that can be maintained dissolved in solution. If the amount of phosphate dissolved in boiler water is driven above saturation by increasing temperature, the excess phosphate forms a solid precipitate with the iron in the boiler. With every change in temperature, there is a new equilibrium established between the phosphate in the dissolved phase and phosphate in the solid phase. If there is a decrease in boiler water temperature, phosphate becomes more soluble, and some of the solid phosphate returns to the boiler water solution.

The phosphate equilibrium now shifts to more phosphate being dissolved in solution, with less phosphate being in the solid phase. This equilibrium shifting is commonly referred to as “phosphate hideout.” This is because the phosphate appears to hide out at high temperatures, only to return as the temperature drops.

It is important to understand that there is always phosphate equilibrium between the dissolved phase and the solid phase in the boiler, depending on the temperature of the boiler water. With every change in boiler water temperature (higher or lower), there will be a change in the phosphate equilibrium to re-establish maximum solution solubility for phosphate.

Today, most boilers are only fed trisodium phosphate.

Trisodium phosphate has a sodium-to-phosphate ratio of 3:1, which is three sodium atoms to one phosphate ion.

43

When dissolved in water, one sodium atom is released from the trisodium phosphate compound and forms a sodium hydroxide molecule. This formation of sodium hydroxide molecules increases the pH of the solution, making the solution less corrosive to iron-based materials in the boiler (Figure 1). The pH of a 1% solution of trisodium phosphate dissolved in deionized water is approximately 12. A sodium-to-phosphate ratio of 3:1 in boiler water is highly desirable to prevent the formation of corrosive acidic phosphates while balancing against excessive formation of corrosive sodium hydroxide.

However, when trisodium hides out, it does not return to the boiler with the same 3:1 ratio. Phosphate that hides out and returns generally has a sodium-to-phosphate ratio of 2.2:1 to 1.0:1. Low sodium-to-phosphate ratios are acidic, depressing the boiler water pH and increasing the corrosivity of the boiler water. The pH of a 1% solution of monosodium phosphate (a ratio of 1:1) dissolved in deionized water is approximately 4.2 to 4.8.

Sodium-to-Phosphate Ratios

The sodium-to-phosphate ratio in the boiler determines if the boiler water will have corrosive phosphate conditions. The lower the sodium-to-phosphate ratio, the more corrosive the boiler water solution becomes.

To minimize corrosive phosphate or corrosive caustic conditions, current recommendations are to maintain the sodium-to-phosphate ratio between 3.0:1 and 3.0:1 + 1 mg/L sodium hydroxide. Figure 3 shows a sodium-to-phosphate ratio chart compiled from data from the Electric Power Research Institute and the International Association for the Properties of Water and Steam publications.

the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Figure 3: Sodium-to-phosphate ratio chart.

Figure 4 is a more simplified version of the Figure 3 chart, showing the corrosive areas that should be avoided to minimize corrosion in the boiler.

Figure 4: Simplified sodium-to-phosphate ratio chart.

Figure 5 is a chart that illustrates what happens to the sodium-to-phosphate ratio when phosphate increases in the boiler water with no change in boiler water pH. Note that the sodium-to-phosphate ratio is driven into acidic phosphate ranges, thereby increasing the potential for corrosion in the boiler.

44

the Analyst Volume 27 Number 4

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Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Figure 5: How increases in phosphate levels in boiler water impact the sodium-to-phosphate ratio.

What is generally observed during a drop in boiler pressure/temperature hideout incident is illustrated in Figure 6.

As the pressure/temperature drops, phosphate that was â&#x20AC;&#x153;hiding outâ&#x20AC;? is able to return to the boiler water due to the increased solubility of lower temperature water. Because the returning phosphate has a sodium-to-phosphate ratio less than 3.0:1, the acidity of the returning phosphate depresses the boiler water pH. The chemistry equilibrium is shifted from being in the minimum corrosion zone to being in the corrosive phosphate zone. The quickest way to restore the boiler water chemistry to where it was at the start is to increase the temperature/pressure back to the original values.

The phosphate will again hide out, lowering the phosphate in solution, and the pH will rise as sodium is freed up to form sodium hydroxide.

Figure 6: How a drop in boiler pressure and temperature generally impacts boiler water chemistry.

48

the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Chemists and/or operators frequently try to respond to the low-pH condition by increasing the feed of trisodium phosphate. Trisodium phosphate can increase the pH back within limits, but the undesirable effect will be the increase in phosphate. Due to the increase in phosphate, the sodium-to-phosphate ratio may never reach the minimum corrosion zone. If the boiler then returns to the previous temperature/pressure, phosphate will hide out, freeing up sodium that will form sodium hydroxide, causing the pH to rise, possibly high enough to push it into the caustic corrosion range, requiring the boiler to be blown down to restore the boiler chemistry back to the starting point. If there are frequent boiler load swings, the chemist and/or operator can find themselves caught in an endless cycle of feeding chemicals and opening the blowdown to try to respond to a constantly shifting chemistry equilibrium (see Figure 7).

Figure 7: Effect of attempting to correct boiler chemistry conditions during a load reduction by the addition of trisodium phosphate.

Chemists and/or operators may also try to correct a low-pH condition by adding a sodium hydroxide spike to the boiler. Although this is a better method for correcting the chemistry than adding trisodium phosphate (no increase in phosphate from the chemical feed), corrosive chemical conditions may not be eliminated. If the boiler then returns to the original pressure/temperature, phosphate will hide out, freeing up sodium that will form sodium hydroxide, raising the pH, possibly raising the pH high enough to be in the caustic corrosion zone, where the boiler has to be blown down to return to the original chemistry point. If the boiler pressure/temperature remains stable, however, excess phosphate can be blown down while remaining within the minimum corrosion zone as the pH and phosphate levels will drop in coordination. But as before, if there are frequent boiler load swings, the chemist and/or operator can find themselves caught in an endless cycle of feeding chemicals and opening the blowdown, trying to respond to constantly shifting boiler water chemistry (Figure 8).

49

the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Figure 8: Effect of correcting boiler chemistry conditions during a load reduction by the addition of sodium hydroxide.

Figure 9 is an actual case where a sudden reduction in temperature/pressure took the boiler on a wild chemistry journey deep into the acidic phosphate zone and then when the pressure/temperature returned, into the caustic corrosion zone before being returned back within control limits. Note that the incident occurred over a period of 104 hoursâ&#x20AC;&#x201D;approximately 4.3 daysâ&#x20AC;&#x201D; in 1998. During most of that time, the boiler chemistry was in a corrosive condition, either acidic phosphate or caustic. As shown on the chart, before the incident started, the chemist/operator was raising the pH of the boiler water, most likely using trisodium phosphate.

Because the boiler was at high-pressure/temperature, little phosphate was able to stay dissolved in solution.

Any phosphate added during this time immediately formed a solid precipitate with the iron on the surface of the boiler steel components.

When the pressure/temperature sharply dropped, large quantities of phosphate were able to re-dissolve in the boiler water, causing the pH to be depressed by the low sodium-to-phosphate ratio of the returning phosphate.

The chemist/operator may have tried to recover the pH by feeding even more trisodium phosphate, which would have added even more phosphate to the boiler, shifting the phosphate equilibrium further in the wrong direction.

50

As the pressure/temperature started to increase, phosphate started to hide out, freeing up sodium that became sodium hydroxide, which in turn started raising the pH. As the pressure/temperature continued to increase, most of the phosphate in solution hid out again with the freeing up of more sodium, forming additional sodium hydroxide and causing the pH to be pushed up into the caustic corrosion zone. Blowdown was then most likely used to drop the pH back within the minimum corrosion zone.

While the boiler was in acidic phosphate conditions, below 2.2:1, iron would have been rapidly dissolving (corroding) into the boiler water solution from the boiler steel components. As the pH started to rise, the iron would have become more and more insoluble, forming solid deposits on the boiler steel components.

The deposits would not have been uniform, as heavier deposits would have formed in high heat transfer zones, as compared to cooler areas of the boiler.

Above pH 9, almost all the iron that had been dissolved would now be solid deposit on the boiler components. As the boiler water pH was driven into the caustic corrosion zone, sodium hydroxide could have formed under the iron deposits, causing corrosive conditions to remain under the deposits long after the bulk boiler water the Analyst Volume 27 Number 4

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Keys to Working With Phosphate Boiler Water Treatment Programs

continued

returned to normal chemistry. Due to the underdeposit isolation from the bulk water, chemistry conditions under deposits can be vastly different than the chemistry in the bulk water. This single incident could have set up the boiler for many future boiler-deposit-related component failures, including underdeposit corrosion, hydrogen damage, caustic gouging, and long-term overheating damage. This is why it is important to maintain boiler chemistry conditions within the minimum corrosion zone as much as possible.

Figure 9: Example where sudden reduction in temperature and pressure sent boiler water chemistry into an out-of-control situation.

Achieving Minimum Corrosion Conditions

Because modern power plant boilers generally have high-pressure temperature conditions, only a small amount of phosphate is able to remain dissolved in the boiler water, generally 0.2 to 1.5 mg/L. Trying to force the boiler to higher levels than what the temperature equilibrium will allow causes the excess phosphate to hide out. With any change in boiler pressure/temperature, new phosphate equilibrium will be established between the dissolved phase and the solid phase. To minimize phosphate hideout effects, the phosphate level should not try to be forced above the pressure/temperature equilibrium level. Attempting to force the dissolved phosphate level above the pressure/temperature equilibrium point, will only cause the phosphate to hide out and increase the chemistry effects in the boiler water when the hideout returns.

52

The boiler phosphate level should be allowed to drift (within reason) to changes in phosphate equilibrium caused by pressure/temperature changes. Phosphate additions should be avoided during boiler pressure/ temperature changes to prevent pushing the sodium-to-phosphate ratio into corrosive regions. It is recommended that sodium hydroxide be used to control the boiler water pH, so that additional phosphate will not be added above the phosphate equilibrium point, increasing phosphate hideout. The pH of the boiler water

â&#x20AC;&#x153;Phosphate additions should be avoided during boiler pressure/ temperature changes to prevent pushing the sodium-to-phosphate ratio into corrosive regions.â&#x20AC;? the Analyst Volume 27 Number 4

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Summary

should only be lowered through the use of blowdown.

The addition of acidic phosphate (monosodium phosphate) to lower the boiler pH should never be used, as boiler corrosion rates will increase dramatically.

There are a number of advantages to boiler water phosphate treatment:

The boiler water phosphate level should be maintained at the equilibrium level only by the addition of trisodium phosphate. The use of other phosphate materials may cause unintended chemical excursions. The phosphate equilibrium point can be determined by feeding phosphate until there is no increase in dissolved phosphate, indicating that any additional phosphate added will hide out. Avoid chasing the boiler chemistry during pressure/ temperature changes as much as possible. Chemistry additions during boiler pressure/temperature are likely to make chemistry conditions worse. Experience has shown that a continuous feed chemical tank mixture of four parts sodium hydroxide to one part trisodium phosphate will generally keep the boiler water chemistry within the minimum corrosion zone. Over time, the mixture can be fine-tuned to keep the boiler chemistry in the center of the minimum corrosion zone.

For accurate boiler water chemistry corrosion zone evaluations, the boiler water pH should be corrected for the ammonia in the boiler feedwater. It is the solid alkalinity portion of the measured pH that is required to accurately determine where the boiler chemistry is located on the sodium-to-phosphate ratio chart. If the boiler water is being monitored for cation conductivity, the cation conductivity has to be corrected for the phosphate at about 2 µS/cm per 0.5 mg/L of phosphate. The phosphate converts to phosphoric acid when passing through the instrument resin column, causing the reading to be high.

53

The boiler feedwater can be oxidizing or reducing.

Acid-forming anions (chloride and sulfate) are neutralized by the sodium in the solution.

Scale-forming cations (calcium and magnesium) tend to form softer phosphate scales as opposed to oxide scales.

Some pH buffering occurs due to the weak acid/ contingent base reactions of the phosphate.

There is some protection from sodium hydroxide carryover in steam provided by the phosphate distribution ratio in steam.

The principal disadvantages of boiler water phosphate treatment are: Phosphate hideout return, possibly creating corrosive chemistry conditions in the boiler due to low pH and/ or low sodium-to-phosphate ratios.

Possible iron phosphate deposition under certain conditions due to solid alkali feed to the boiler.

Remember that there is always an equilibrium between the phosphate dissolved in the boiler water and the phosphate that is in solid form with the iron in the boiler that is determined by the pressure/temperature of the boiler at any given point in time. Be aware that any changes in boiler pressure/temperature will cause the phosphate equilibrium to shift, possibly moving the boiler chemistry into corrosive conditions.

the Analyst Volume 27 Number 4

Bulk 2020.pdf 1 4/23/2020 3:56:54 PM

Keys to Working With Phosphate Boiler Water Treatment Programs

continued

Bibliography

Babcock & Wilcox (1994). “Boiler Water Phosphate Chemistry,” plant service bulletin, Babcock & Wilcox, Barberton, Ohio.

Baghni, M.; Zwebek, I. (2009). Using of Congruent Phosphate as Equilibrium Phosphate Boilers Water Treatment, Wit Press, Southampton, U.K., ISSN 1743-3509.

Buecker, B. (November 2015). “Steam Generating Chemistry: Correcting Outdated Beliefs and Misconceptions,” Power Engineering 119(11).

Buecker, B. (2000). Fundamentals of Steam Generation Chemistry, PennWell Corp., Tulsa, Oklahoma, ISBN 10: 0-87814-750-0.

Christophersen, D. (February 2004). “History of Industrial Water Treatment,” originally published in CSTN. EPRI (2011). "Comprehensive Cycle Chemistry Guidelines for Fossil Plants" (1021767), Electric Power Research Institute, Palo Alto, California.

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Steve Dunn is a semi-retired (2014) power plant chemist still consulting part time on power plant chemistry issues. He has more than 45 years of experience in managing coal-fired power plant boiler, pre-boiler, and cooling water system chemistries. Mr. Dunn has authored a number of presentations for power plant chemistry conferences and several magazine articles over the years. He graduated from Peru State College (Peru, Nebraska) in 1980 with a B.S. in physical science. Mr. Dunn can be reached at sdunn@ppmconsults.com.

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54

the Analyst Volume 27 Number 4

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58

the Analyst Volume 27 Number 4

Abstract

A failure to control scaling and corrosion in industrial water treatment systems can lead to loss of efficiency or equipment failure. These problems can quickly compound to result in lost production time, increased maintenance costs, and, in a worst-case scenario, a complete shutdown of operations. Phosphorus has been a primary tool of the water treatment industry, ranging from inorganic phosphates (orthophosphate and polyphosphates) to organic phosphonate chemistry to control scaling and corrosion. Polymers containing phosphorus either as a terminal group or as part of the backbone are also used in the industry. However, there is a growing push within the United States and abroad to move away from phosphorus to reduce point sources of phosphorus to watersheds. We report here on the current state of zero and low-phosphorus regulations and legislation as well as offer a range of current solutions to challenging water conditions in the absence of phosphorus.

Introduction

Mineral scale deposition is a challenge in most industrial cooling water processes. The buildup of deposits in both open and closed recirculating cooling systems as well as boilers creates a myriad of problems, which ultimately increase operating costs and decrease overall profitability.

These problems include but are not limited to impaired heat transfer efficiency, unexpected downtime, costly asset repair, and replacement and increased energy costs.

Within each cooling system the potential exists for a wide range of deposits, ranging from mineral scale to corrosion products or microbiological foulants. All effective water treatment programs must be able to address these deposits as well as suspended insoluble materials.

Water treatment formulations are seldom created for use in single applications. Ideally the formulating chemist generates multipurpose blends capable of handling the wide-ranging environments present in process water.

There are a few common scaling/deposition species that are generally considered as benchmarks for a successful blend to inhibit:

Calcium carbonate (CaCO3) Calcium sulfate (CaSO4) Calcium phosphate (Ca3(PO4)2, Ca 5(PO4)3(OH), additional polymorphs) Silica and silicates (SiO2 and MgSiO3 respectively) Iron oxide The formulator’s goal is to leverage their available chemistry to exploit the following scale inhibitor mechanisms: Threshold inhibition: The ability of a polymer or formulation to slow crystal growth or precipitation at sub-stoichiometric levels. A good benchmark for threshold performance is a material that will provide inhibition at less than 10 parts per million (ppm) in an aqueous environment.

Crystal modification: Crystal growth modification occurs when an additive adheres to, and disrupts, the growth of scale crystals. This action either slows the kinetics of crystal growth or weakens the structure of the growing crystal, or both.

Chelation/sequestration: Chelants and sequestering materials bind scaling ions in stoichiometric (1:1 or 1:2) amounts, forming water-soluble complexes. These complexes deactivate the ion (Ca 2+, Fe2+, etc.) from reacting with other elements and subsequently forming scale.

Dispersion: Like crystal growth modification, the inhibiting material adheres to a crystal surface and presents a uniform particle charge. Charge repulsion then reduces the incidence of additional scaling species to approach and form a larger particle or hardened scale.

When approaching a modern water treatment formulation, the chemist is looking to apply the most complete number of scale inhibitor mechanisms with a toolbox of materials that include one or more of the following:

“A good benchmark for threshold performance is a material that will provide inhibition at less than 10 parts per million (ppm) in an aqueous environment.”

59

the Analyst Volume 27 Number 4

Formulating for a Zero or Low-Phosphorus Environment continued

“Phosphonates are among the most effective threshold inhibitors available to a formulator.”

Polyphosphates (sodium pyrophosphate, sodium tripolyphosphate, hexametaphosphate, etc.)

Phosphonates (ATMP, HEDP, PBTC, HPA, etc.)

Polymers (polyacrylic, polymaleic, phosphinoacrylic, sulfonated, co-, ter-, etc.)

Polyphosphates (Na4P2O7 and Na 5P3O10 in particular) are among some of the original scale inhibitors. They were applied to primarily inhibit calcium carbonate scale via a threshold mechanism. These materials typically are not used in modern antiscalant formulations because the advent of organic phosphates created far more effective treatment chemistries. Also, polyphosphates are prone to reversion to orthophosphate, which, in the presence of calcium, can generate calcium phosphate scale.

Phosphonates are among the most effective threshold inhibitors available to a formulator. They are extremely effective at dealing with multiple scale types, are not as prone to reversion by hydrolysis, and can offer some corrosion inhibition properties. The phosphonates are not without their drawbacks, as some are very sensitive to calcium precipitation and/or degradation by oxidizers.

Polymers provide a dizzying array of capabilities to the modern water treatment formulator. They can function as scale inhibitors, dispersants, or both, depending on the polymer functionality. They are available as homopolymers, copolymers, terpolymers, and even tetra polymers.

They have been designed as broad application materials capable of handling several scaling species well, or as specialized materials capable of handling singular functions extremely well. Among the polymer families, polyacrylates and polymaleic polymers form the backbone of many broad-spectrum cooling water formulations.

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The inclusion of nonionic or sulfonated functionality increases the capability of these polymer families. The inclusion of phosphorus in either the polymeric backbone or as a terminal group functionality has created some of the most potent weapons in the formulator’s arsenal.

Sulfonated phosphino carboxylates, phosphino carboxylate, and phosphono carboxylates have been applied in all water types as highly effective scale inhibitors, dispersants, and, in some circumstances, corrosion inhibitors.

The modern formulator has all the tools at their disposal to handle most challenging water conditions.

Through the careful application of pH control, cycle management, and pretreatment, a water treater need only select the right formula to manage those scaling species that remain. However, the historical toolbox of the formulator is gradually shrinking, particularly in the United States.

Phosphorus

Phosphorus is a critical nutrient required by all life. The most common form of phosphorus used by organisms is phosphate (PO42-), which plays a role in cellular energy pathways, and the formation of cell membranes and DNA. Phosphorus is considered a limiting nutrient in an aquatic ecosystem. When it is available in appropriate quantities, it is used by vegetation and microbes alike for normal growth. However, too much available phosphorus can disrupt this natural balance and lead to ecological damage from toxic algal blooms or eutrophication.

In the last 20 years, the number of states that have implemented legislation pertaining to phosphorus and/or nitrogen criteria has more than doubled. Figure 1 shows changes in the number of states with total nitrogen or total phosphorus criteria between 1998 and 2018.

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Formulating for a Zero or Low-Phosphorus Environment continued

Figure 1: Number of states with total nitrogen or total phosphorus criteria.

The U.S. Environmental Protection Agency (EPA) reports phosphorus (and nitrogen) criteria progress by level of increasing rigor, with Level 1 representing the least restrictive guidelines for phosphorus and Level 5 representing the most restrictive guidelines (see Table A): Table A: Levels Used by EPA to Determine Criteria Progress for Phosphorus and Nitrogen Level

Explanation

Level 5

Complete set of N and P criteria for all water types

Level 4

Two or more water types with N and/or P criteria

Level 3

One water type with N and/or P criteria

Level 2

Some waters with N and/or P criteria

Level 1

No N and/or P criteria

The level represents the number of water types that have some level of criteria. This ranges from very rigorous (statewide phosphorus or nitrogen criteria) to moderate (partial phosphorus or nitrogen criteria) to no criteria. There are three identified water types: 1. Lakes/reservoirs, 2. Rivers/streams, and 3. Estuaries. In general, if there is any legislation present it impacts lakes/reservoirs first, followed by rivers/streams, and finally by estuaries.

The breakdown of the state-by-state progress toward developing numeric water quality criteria for phosphorus (P) and nitrogen (N) is shown in Figures 2 and 3.

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Formulating for a Zero or Low-Phosphorus Environment continued

Figure 2: United States map illustrating regulation levels (1â&#x20AC;&#x201C;5) of nitrogen and phosphorus.

Figure 3: Graph showing changes over past 20 years in the number of states following phosphorus and nitrogen criteria by level.

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Formulating for a Zero or Low-Phosphorus Environment continued

As can be seen in Figure 3, progress toward widespread criteria on all water types is slow, but it is progressing.

The rate of decrease in states with no total N and/or P criteria closely mirrors the rate of increase in states with some N and/or P criteria (Level 2). The increase in states with more widespread requirements (i.e., Levels 2 to 5) is negligible. This is further evidence that progress is being made, although the drive towards greater restriction on phosphorus is slow.

Given the importance of organic phosphorus (phosphonates and polymers) to a water treatment formulation chemist, a further analysis of what constitutes phosphorus criteria is warranted. A deeper dive into the specifics of phosphorus criteria reveals a complicated reality as there are three classes of phosphorus criteria: statewide criteria, partial criteria, and no criteria. The easiest scenario is no criteria. This does not mean there will never be a limitation on the usage of phosphorus.

The EPA reports progress and projected progress out to 2021. The national trend is heading in the direction of complete phosphorus restrictions nationwide. However, observing the slow progress over the last 20 years, it is unlikely to arrive without enough time for formulators to develop solutions that are entirely independent of organic phosphorus, or greatly reduce its important. Partial criteria are where the guidelines become challenging.

Partial criteria can be broken into categorical and site specific, among others. This varies from state to state.

For example, South Carolina is a Level 3 state. A quick glance at the restrictions reveals a very stringent total phosphorus requirement for lakes/reservoirs of 0.02 milligrams per liter (mg/L). However, this requirement is solely for the Blue Ridge Mountains Ecoregion. By way of comparison, Nevada is a Level 2 state with partial criteria as well. However, there are several hundred distinct criteria, ranging from acceptable phosphorus levels as phosphate for individual rivers/streams to total phosphorus for specific lakes/reservoirs.

The third classification, statewide criteria, is equally convoluted. The complicating factors for the statewide restrictions reveal themselves in the form of the actual allowable phosphorus values, which can range from single digit parts per billion (ppb) to 100 ppm.

In general, the statewide guidelines follow total phosphorus, but not always. The P content can be reported as phosphate, orthophosphate, dissolved inorganic phosphorus, or total phosphorus. A breakdown of the number of states with no, partial, or statewide phosphorus criteria for lakes/reservoirs and rivers/streams is shown in Figure 4. Estuaries are left off the chart, as more than half of the states do not possess the relevant water type.

Figure 4: Number of states with phosphorus criteria by surface water type in 2018.

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the Analyst Volume 27 Number 4

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References

1. Lucas CE, Taylor TH Jr, Fields BS. Accuracy and precision of Legionella isolation by US laboratories in the ELITE program pilot study. Water Res. 2011;45(15):4428–4436. doi:10.1016/j.watres.2011.05.030 2. Petrisek R, Hall J. Evaluation of a most probable number method for the enumeration of Legionella pneumophila from North American potable and nonpotable water samples. J Water Health. 2018;16(1):25–33. doi:10.2166/wh.2017.118 3. Spies K, Pleischl S, Lange B, et al. Comparison of the Legiolert/Quanti-Tray MPN test for the enumeration of Legionella pneumophila from potable water samples with the German regulatory requirements methods ISO 11731-2 and ISO 11731. Int J Hyg Environ Health.

2018;221(7):1047–1053.doi:10.1016/j.ijheh.2018.07.006 4. Sartory DP, Spies K, Lange B, Schneider S, Langer B. Evaluation of a most probable number method for the enumeration of Legionella pneumophila from potable and related water samples. Lett Appl Microbiol. 2017;64(4):271–275. doi:10.1111/lam.12719 5. Barrette I. Comparison of Legiolert and a conventional culture method for detection of Legionella pneumophila from cooling towers in Québec. J AOAC Int. 2019;102(4):1235–1240. doi:10.5740/jaoacint.18-0245

© 2020 IDEXX Laboratories, Inc. All rights reserved. • 2485785-00 • All ®/TM marks are owned by IDEXX Laboratories, Inc. or its affiliates in the United States and/or other countries. The IDEXX Privacy Policy is available at idexx.com.

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Formulating for a Zero or Low-Phosphorus Environment continued

The data show that most states have no phosphorus restrictions for lakes and rivers, so what does this mean for the water treatment formulator? Is it time to remove all phosphorus from antiscalant and corrosion inhibition packages? Does the low number of states with partial or statewide criteria indicate the opposite (i.e., wholesale use of organic phosphorus in all formulations)?

Formulation Strategy

A meta-analysis of the current state of phosphorus criteria in the United States reveals the following: The number of states with some degree of P criteria is gradually increasing.

The criteria are widely varied across states and water types.

The number of states with partial or statewide total P criteria represent the minority.

How does the modern formulation chemist approach the challenges presented in the beginning of this article?

When approaching the benchmark scaling species (e.g., CaCO3, CaSO4, SiO2) with a toolbox that includes phosphates, organic phosphates, and polymers, how does one proceed? The answer is to take a strategic approach to an overall formulary that blends materials with full awareness of the increasingly complicated environmental requirements. It would be irresponsible to ignore the trend towards total P regulation. It would also be a mistake to completely remove some of the most proven

and effective chemistry from the formulator’s toolbox because of a slow-moving trend.

There is a need to be deliberate and judicious when including a phosphonate in a formula. If presented with the choice between a phosphonate and a polyphosphate, it is not enough to consider a cost-versus-performance relationship. It is more important to have a strategy that weighs factors such as cost, performance, environmental impact, and broad application across water types, scale, and product stability. The same can be said when deciding between inclusion of a phosphino-type polymer in a formulation.

The relative amount of total phosphorus present in the molar equivalents of a phosphinocarboxylate required to inhibit scale versus the same amount of required phosphonate is important. Unfortunately, the regulations for phosphorus do not generally specify the P source.

Eutrophication is a product of excessive orthophosphate in water, not the mere presence of elemental phosphorus in the water. However, Total P includes phosphorus built into the backbone of a polymer as equivalent to orthophosphate, even though orthophosphate is more readily bioavailable.

Strategically, it is important to create material “buckets” that allow a formulator to quickly assess whether a chemistry can be broadly applied, or if it must be targeted. Table B represents a broad sampling of tools within a water treatment formulator’s toolkit.

“There is a need to be deliberate and judicious when including a phosphonate in a formula. If presented with the choice between a phosphonate and a polyphosphate, it is not enough to consider a costversus-performance relationship.”

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Formulating for a Zero or Low-Phosphorus Environment continued

Table B: Core Polymer and Phosphonate Chemistries Available to Water Treatment Formulators Chemistry Type Homopolymers

Examples Polymaleic acid (PMA) Polyacrylic acid (PAA) Carboxymethy inulin (CMI)

Natural Derivatives

Tannins Starches Sulfonated polyacrylic acid (AA/AMPS)

Copolymers

Acrylate-maleic (AA/MA) Maleic acid-sulfonate styrene (MA/SS) Maleic-based

Terpolymers

Acrylic-sulfonated styrene-sulfonate (AA/SS/AMPS) Acrylic-sulfonate-t-butyl acrylamide (AA/AMSP/t-BAM) Phosphino carboxylic acid (PCA)

Phosphorus Polymers

Sulfonated phosphino Carboxylic Acid (S-PCA) Phosphono carboxylic acid (POCA) ATMP

Phosphonates

HEDP PBTC HPA

When presented with a challenging water, the first questions are generally a request for a water analysis, process details, and temperature, among others. Due to the growing restrictions on phosphorus, the initial survey should include an inquiry into the ultimate destination of the process water. Is it bound for a lake/reservoir or a river/stream?

Are there any P criteria (partial or statewide) that need to be considered?

Table C illustrates every state that has some form of statewide or partial criteria for at least one water type. If the treated water is in any of the states and/or water types listed in the next table (Table D), it does not instantly rule out the inclusion of phosphonates or phosphorus-based polymers. However, it should force the formulator to ask, “Can I solve this problem with an alternate technology?”

“When presented with a challenging water, the first questions are generally a request for a water analysis, process details, and temperature, among others.”

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Formulating for a Zero or Low-Phosphorus Environment continued

Table C: Degree of Regulatory Oversight by State for Surface Water Types and Estuaries State

Lakes/Reservoirs

Rivers/Streams

Estuaries

Arizona

Partial

Partial

N/A

California

Partial

Partial

Partial

Colorado

Partial

None

N/A

Florida

Statewide

Partial

Statewide

Georgia

Partial

None

None

Hawaii

N/A

Statewide

Statewide

Illinois

Partial

None

N/A

Massachusetts

Partial

None

None

Minnesota

Statewide

Statewide

N/A

Missouri

Partial

None

N/A

Montana

None

Partial

N/A

Nebraska

Partial

None

N/A

Nevada

Partial

Partial

N/A

New Jersey

Statewide

Statewide

None

New Mexico

Partial

Partial

N/A

New York

Statewide

Statewide

None

Oklahoma

Partial

Partial

N/A

Oregon

Partial

None

None

Rhode Island

Statewide

None

None

South Carolina

Partial

None

Statewide

Vermont

Partial

Partial

N/A

Virginia

Partial

None

None

West Virginia

Statewide

None

N/A

Wisconsin

Statewide

Statewide

N/A

When faced with the complicated array of phosphorus limitations and criteria, it is encouraging to note that many of the materials listed can be universally applied. If faced with phosphorus restrictions, it is never wrong to include to include a PMA or an AA/AMPS, assuming they provide the needed performance. These two materials, along with several others, such as CMI, PAA, AA/AMPS/t-BAM, etc., are acceptable in every state and are P-free. When faced with any state that has a statewide P criteria, the formulatorâ&#x20AC;&#x2122;s challenge is not insurmountable, but it does not allow for gratuitous usage of phosphonates or phosphorus-based polymers. Table D is a summary of the previously mentioned water treatment chemicals and in which states, if any, those materials may have restricted use. The states highlighted in bold have statewide P criteria.

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Table D: List of Water Treatment Chemicals and States With Restricted Use Treatment Material

Examples

Homopolymers

Polymaleic acid (PMA)

Restrictions?* All States – No Restriction

Polyacrylic acid (PAA) Carboxymethy inulin (CMI) Natural Derivatives

All States – No Restriction

Tannins Starches Sulfonated polyacrylic acid (AA/AMPS)

Copolymers

All States – No Restriction

Acrylate-maleic (AA/MA) Maleic acid-sulfonate styrene (MA/SS) Maleic

Terpolymers

Acrylic-sulfonated styrene-sulfonate (AA/SS/AMPS)

All States – No Restriction

Acrylic-sulfonate-t-butyl acrylamide (AA/AMSP/t-BAM) Phosphino carboxylic acid (PCA) Phosphorus Polymers

Sulfonated phosphino carboxylic acid (S-PCA) Phosphono carboxylic acid (POCA)

AZ, CA, CO, FL, GA, HI, IL, MA, MN, MO, NE, NV, NJ, NM, NY, OK, OR, RI, SC, VT, VA, WV, WI

ATMP Phosphonates

AZ, CA, CO, FL, GA, HI, IL, MA, MN, MO, NE, NV, NJ, NM, NY, OK, OR, RI, SC, VT, VA, WV, WI

HEDP PBTC HPA

*Note: Bolded states have statewide P criteria A final consideration for a water treatment formulator is the fact that information available from the EPA is in a constant state of flux. States with no EPA restrictions may have sites with phosphorus limitations. It is important to review the projected progress of P-criteria for any body of water that will serve as the destination of the water treater’s chemistry. Strategically, it makes little sense to generate a solution that will be obsolete in the near term.

Conclusion

Historically, the water treatment formulation chemist has possessed multiple chemistries to address scale and corrosion challenges in cooling water. However, the modern formulator is becoming more challenged, as one of the best tools—organic and inorganic phosphates—is becoming limited. Limits on total phosphorus in our waterways have progressed at a slow but steady pace over the last 20 years, and there is no sign this trend will change. This forces a formulator to be strategic and judicious regarding the use of phosphorus moving forward.

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If P must be included in a formula, one needs to be selective. It is not enough to reach for the bottle of HEDP because that is what has always been used. It is important to ask if a non-P polymer can accomplish the same task. Can a PCA or POCA accomplish the task of a phosphonate and reduce the overall P content while retaining some of its many benefits?

The final task of a formulator is to be honest about the limitations of P-free options. There are few materials better than inorganic phosphates and phosphonates for corrosion inhibition. There is room for innovation and growth in respect to phosphorus reduction and alternate chemistries. However, until the next generation of P-free scale and corrosion inhibitors arrives, the burden of innovation falls on the formulator.

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Formulating for a Zero or Low-Phosphorus Environment continued

Brandon Beyer currently works as a technical development manager for Italmatch Chemicals covering North America. After finishing his M.S. in organic chemistry from the University of Wisconsinâ&#x20AC;&#x201C;Madison, he began work at Ecolab/Nalco in core R&D in product development and commercialization. He then moved to Dow Chemical, managing the MPQ labs globally for FilmTec, supporting the R&D and quality functions in the manufacture of reverse osmosis elements and membrane flat sheet. In 2017, he began work with BWA Water Additives, which was later purchased by Italmatch and has held the role of technical development manager acting as customer-facing technical support and business development for the following business segments: industrial water treatment (cooling water, boilers, reverse osmosis), HI&I, pulp and paper, agriculture, and geothermal. He may be reached at b.beyer@italmatch.com.

This paper was presented at the 2019 AWT Annual Convention, which was conducted September 11â&#x20AC;&#x201C;14, 2019, in Palm Springs, California.

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the Analyst Volume 27 Number 4

Association News

Following is an update on the four outcomes of the AWT strategic plan.

Outcome 1—Training and Education: AWT volunteers are hard at work on many projects. The following are just a few examples.

The Source Water Working Group, a subgroup of the Cooling Subcommittee, would like to invite AWT members to test for Legionella and related parameters in water at the point of entry into buildings where they are providing water treatment. They may then submit the data to be aggregated so that AWT members and other stakeholders have more insights into the quality of water as it enters premise plumbing systems. You can learn more about the project here (link to: https://www.youtube.com/watch? v=ZH1aLAbOOc8&feature=youtu.be). To participate, please contact Angela Pike at apike@awt. org or (240) 404-6477.

The AWT Business Owners Meeting (https://www. awt.org/events/business-owners-meeting/) is typically held in February; however, in 2021, the meeting will be pushed back to be held in conjunction with the Annual Convention and Exposition in Providence, Rhode Island. More details will follow in the coming months.

AWT is reviewing the schedule for the 2021 Technical Training Seminars (https://www.awt.org/events/ technical-training-seminars/). More information will be sent shortly regarding these meetings.

ASSE has created standard 12080, Professional Qualifications Standard for Legionella Water Safety and Management Personnel. AWT has developed a task force to create training for this certification program. The goal is to offer the training in May 2021.

Work continues on the updates to the Raw Materials Manual as well as the Technical Reference and Training Manual (TR&TM). We anticipate new versions of the manuals to be out soon.

The Cooling Subcommittee has developed a paper and template called “Improving Cooling Water Treatment Performance and Vendor Liability Concerns through the Implementation of a Shared Responsibility Management Agreement,” which can be found on the members only portion of the website. https://www.awt.org/pub/ BFD5C0A9-1866-DAAC-99FB-067BBADDC2E9 Outcome 2—Member and Industry Advocate: The AWT STEM kit on water hardness and scaling can be purchased in the AWT bookstore at https://www.awt. org/awt-bookstore/.

Outcome 3—An Engaged Membership: The Governance Task Force continues to look at our membership structures and opportunities. As their work progresses, we will share their progress. A focus of their work in 2021 will be on international membership.

Finally, be on the lookout for your 2021 dues invoice.

Please note that dues will remain the same for 2021.

Outcome 4—Charity: Thanks to your great efforts, AWT members raised $13,060 through the silent auction for Pure Water for the World. Members raised an additional $6,877 for the new AWT-sponsored community in El Rodeo, Honduras. You can support the community here: https://impact.purewaterfortheworld.org/campaign/ awt-2020-community-el-rodeo/c300106

Thanks to the work of some dedicated AWT members, work is progressing on the development of a water treatment exhibit at the Museum of Industrial History. (link to: http://www.nmih.org/)

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Industry Notes

H2O Brenntag Opens New Distribution Facility in Toledo

Located in the Great Lakes region, Brenntag North America's new facility comprises approximately 230,000 square-feet and will be used for storage and distribution of commodity products, solvents, surfactants, specialties, and food ingredients. In addition to having a 7-acre tank farm on an adjacent property, the location will have both interior and exterior rail service to serve all Brenntag industries.

Safety is the number one priority at Brenntag. To further support this core value, the facility is equipped with the most modern technology to ensure a safe, controlled environment. The redevelopment has been established in collaboration with the Ohio rail development commission, as well as other agencies, and is projected to bring in over 40 new driver, warehouse, and production job opportunities to Lucas County by 2022.

Brenntag is a global market leader in chemical and ingredients distribution. Headquartered in Essen (Germany) and with regional headquarters in Philadelphia, Houston, and Singapore, Brenntag operates a unique global network with more than 640 locations in 77 countries.

Grundfos Aids the Philippines’ Flood and Wastewater Management Efforts

With the growth of the economy and rapid urbanization in the Philippines, the country is facing significant challenges in terms of water and sanitation. Around 7 million rely on unsafe and unsustainable water sources and 24 million lack access to improved sanitation. As the government of the Philippines has geared up to address the issues of universal water and sanitation services coverage by 2028, reliable and intelligent technology will play a critical role in enabling this transformation.

Grundfos Philippines, a global leader in advanced pump solutions and water technologies, has launched its 73

Prefabricated Pumping Stations (PPS) to help meet the country’s growing flood and wastewater management needs. The PPS is a sustainable turnkey solution that substantially reduces installation time, commissioning costs, and the space requirement.

H2SO4

The PPS is designed to be energy efficient and operate reliably in the long run. Traditional pumping stations are made of concrete casted on site, which means that it is susceptible to corrosion and leakage over time. With PPS being made of hard-wearing plastic, its greater durability paired with an advanced control system means optimized operations, and in turn greater energy savings.

Jonathan Breton, general manager at Grundfos Philippines, said “The PPS also only requires a short construction timeframe. Compared to traditional pumping stations, PPS is produced in the Grundfos factory and sent to the site as a complete package, making installation easier and usually completed within 24 hours. This reduces installation time by as much as 80%, ensuring minimal disruption to people and infrastructure. With the lockdown due to the COVID-19 pandemic, the PPS solution will significantly help complete the installation faster and avoid potential additional costs and delays.”

In addition to flood control, another key application for PPS is in wastewater management. Playing a key role in the wastewater management process, pumping stations are designed to collect and transport wastewater, and PPS’ high durability ensures minimal disruption to any water system. This solution can play a key role in urban as well as remote areas and create a reliable decentralized wastewater management system.

The PPS is an ideal solution for wastewater management at tourist destinations and hotels. Grundfos has recently installed its first PPS solution at Lio, a tourism estate whose water and wastewater facilities are owned the Analyst Volume 27 Number 4

Industry Notes continued

and operated by Manila Water’s Business Unit, Estate Water (EW), which is located in El Nido, Palawan.

Commenting on why EW opted for Grundfos’ solution, Benson Cruz, technical services head, said “Lio constantly raises the bar for sustainable tourism.

Therefore our obvious choice was Grundfos’ Prefabricated Pumping Stations as it helps helped us decrease not only our overall environmental footprint but the project cost as well. It also has a smaller footprint—the original lift station design was sized at 60 square meters (m2)and Grundfos’ PPS and controller has taken only 36 m2.”

made the move to Camden, including American Water and Subaru of America.

The new high-tech facility is the largest of its kind on the East Coast and the first new U.S. plant built to produce ion exchange resins in over 30 years. Sized to produce up to 1 million cubic feet of strong-acid cation resin a year, the plant can be expanded to meet the demands of the growing market.

Commenting on the efficiency of PPS, Jon Remulla, WU segment manager, Grundfos Philippines said, “As the PPS features the Variable Frequency Drive and dedicated controls, it also helps reduce the power consumption and energy costs by 30% and 35%, respectively.”

With over 40 years’ experience globally, Grundfos’ PPS solution has demonstrated its highest quality and effectiveness in several projects for various applications in Southeast Asia. Outside of Southeast Asia, China has over a thousand installations of PPS to address the high demand resulting from the country’s fast-growing urbanization for various applications, including sewage pumping, drainage, and flood control.

ResinTech Opens New Cation Resin Plant and Global HQ

Aerial view of ResinTech Global Headquarters and Cation Resin production plant.

ResinTech Inc. announced that is has officially moved into its new global headquarters in Camden, New Jersey. The $138.8 million development project includes 353,000 square feet of new construction on a 27-acre campus just 2 miles from Center City Philadelphia. The company is among several other global brands that have

74

ResinTech complex features a total of 39 loading docks supporting 363,000 square feet.

The building features a larger world-class laboratory with even more sensitive equipment for water and resin testing. "We've nearly doubled the size of our lab operations and purchased equipment capable of measuring PFAS and other contaminants at parts per trillion levels," said ResinTech president Larry Gottlieb. "The new capabilities will provide customers with a greater understanding of their water's composition than ever before."

ResinTech has also moved its Aries Filterworks division, makers of POU filters and lab water systems, to the same complex. By manufacturing these products in the same building where the key media ingredients are made, ResinTech believes it will increase operational efficiencies and time-to-market. The company plans to bring its resin regeneration division, ACM Technologies, to New Jersey before the end of the year as well.

ResinTech's CEO, Jeff Gottlieb, discussed the company's excitement about moving to their new community and bringing manufacturing back to the United States: “This project brings so much excitement and reason for optimism on many levels. Locally, we're bringing jobs to New Jersey and to Camden specifically, a community

the Analyst Volume 27 Number 4

Industry Notes continued

that really need them. At the national level, there's excitement about us making resin in the U.S. We are producing solvent-free, environmentally-friendly ion exchange resins using state-of-the-art production technology, highly-efficient manufacturing techniques, and low-cost solar energy—the combination of which will empower us to compete globally and employ locally for the foreseeable future.”

fully integrated polymer and sulfonation production plant built in North America in more than 30 years."

Mr. Gottlieb continued, "When I think back to when I started this company out of my home, I never dreamed we'd be able to produce the incredible volume of resin and cartridges the plant is capable of producing. To do it with my sons and to create hundreds of jobs for people along the way is incredibly gratifying."

Mike Gottlieb, ResinTech's chairman who founded the company out of his home in 1986, continued, "The water treatment community understands the significance of this project. They recognize that this is the first

The new solar-powered complex is already employing nearly 250 people, many of them local Camden residents.

At peak capacity, the plant hopes to have as many as 400 employees.

Elektra Connecting you to your chemical dosing pump 24/7 – wherever you are SEKO’s IoT-enabled Elektra allows you to monitor and manage your dosing equipment wherever you are via PC, laptop or smart device for a new world of operational efficiency and accessibility.

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Visit www.seko.com/us or call (215) 945-0125 to find out more.

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CWT Spotlight

Brad Allen, CWT Pace Solutions Regina, Saskatchewan, Canada

What prompted you to obtain the CWT and when did you begin the process by taking the test?

I was introduced to the water treatment industry by a CWT when he hired me almost six years ago. I quickly made it my goal to obtain my certification when I qualified. I felt that obtaining the certification would provide my customers with proof of my abilities and usefulness to them as a water treatment advisor. The company that I work for now strongly encourages their employees to make this certification their goal. I began the process by taking the exam at the end of May 2020.

How did you prepare for the exam?

My employer arranged for me to attend multiple technical training seminars in preparation for certification.

In addition to attending the seminars, I read Boiler Water Treatment Volumes I and 2 and worked through the AWT Technical Reference and Training Manual, using the training questions to test myself. I also read many of the online training articles and took the quizzes on the AWT website. Finally, when provided the mock exam after registering, I poured over it and wrote it several times on my own.

Why do you feel this credential is important to have?

Although sales is an integral part of my job, I did not want to be just a salesman peddling a product. I felt that to be a professional, I needed to educate myself—to understand the whys and hows of water treatment— particularly when considering how my recommendations could have major ramifications for my customers. Only then could I be a real partner and problem-solver for my customers. The CWT credentials testify for me, telling my customers that I have done my part: I have demonstrated the dedication, acquired the knowledge, and have access to the resources they are looking for.

What do you think are the most prominent issues facing the water industry today?

Public health and the environment. The COVID-19 pandemic is leaving victims with lasting health complications and weakened immune systems. This leaves them even more susceptible to waterborne pathogens such as Legionella, V. cholerae, and E. coli. With more immunocompromised neighbors than ever before, we will need to step up and ensure that anyone directly or indirectly affected by our processes is safe.

Water is a precious commodity that can’t be wasted, particularly with the environmental changes we are experiencing. We need to work with our customers to ensure their processes, methods, and treatment programs are utilizing this resource as economically as possible— working to limit waste, reuse, and recycle.

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Making a Splash

Semra Gul, M.Sc. Syntec Corporation New Castle, Delaware

What prompted you to start volunteering with AWT? I highly believe that we have a responsibility to society, to our work, to ourselves. Water treatment is one of the most important fields and is growing in scope. Because of the changing environment and market conditions, there are always things to make it better. I think we have so many responsibilities, such as creating projects, trainings, and/or sharing our experiences. Volunteering is one of the best ways to make contributions and be part of improving the market. I have been volunteering in so many organizations back in Europe, including both professional and nonprofit organizations. After I got involved in AWT and heard about ongoing projects, I wanted to be volunteer. Although I am a bit new in the organization, I am already excited about future projects.

What has been the most rewarding thing about volunteering?

Being part of the solutions, helping to improve, and continuing to learn are the most rewarding things for me. I feel this since it gives me a greater purpose of my profession, that I actually use my skills and knowledge to also make a brighter future.

How has volunteering improved your professional career?

As part of the nature of the job, you can always learn or improve yourself when you face new problems or examine/troubleshoot different facilities and systems.

Experience contributes highly to our skills and careers.

AWT has many valuable members in different areas.

In other words, when you volunteer, you are involved in many projects, and you have a chance to have different experiences and solve problems. The project research, brainstorming, meetings, and shared experiences are important resources for me. They not only help me to keep up to date but also help to improve myself.

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Why would you encourage others to become a volunteer?

Our job requires continual learning and growing. To improve our market, we must produce new projects.

Since water treatment is a wide field, we always need new volunteers to be part of the solution or to improve.

Being a volunteer on projects also helps with personal career development.

Tell us about a current project you or your committee is working on?

I am member of the Technical Committee and Cooling Committee and just joined the Pretreatment Committee.

I am one of the newer members in the organization and on the committees. The Cooling Committee is very active.

Although I haven’t been involved directly in any projects, there are so many exciting ongoing projects—Biofilm 2020 Analyst article, shared Cooling Water Program, Worker Protection in the Presence of Legionella, Source Water Legionella Study, TRTM Manual, Biocide Use Surveys, Non-Chemical/Non-Traditional Water Treatment.

What is a past project that your committee produced that you feel has had the greatest impact on AWT and why?

I am pretty new both to the United States and AWT. My observation is that the water treatment manual is one of the most important resources for not only water treaters but also customers.

How have you been able to utilize the expanded business connections you’ve made while volunteering?

Although being part of AWT family has already helped for networking and expanding business connections, volunteering is one of the best ways to be in contact with the professionals. Committee meetings, projects, and research are good opportunities for expanding business connections. the Analyst Volume 27 Number 4

Financial Matters

October 2020 Economic Update U.S. Markets Stocks dropped in September as investors worried about stalled fiscal stimulus talks in Washington, the upcoming election, and new coronavirus cases in Europe.

What Investors May Be Talking About in October The housing sector has been a bright spot in a challenging year and has seen strong consumer demand thanks to historically low interest rates.

The Dow Jones Industrial Average, which lagged this year, slipped 2.28%. The S&P 500 Index lost 3.92% and the Nasdaq Composite declined 5.16%.

Home building and home sales have set new records in recent months, while home builder confidence is at an all-time high. The National Association of Home Builders/Wells Fargo Housing Market Index posted a reading of 83 out of a possible 100 in September, well above its previous record high of 78.

Tech Stocks Under Pressure After a strong rally in August, investor sentiment quickly turned negative as technology stocks dragged down the overall market.

The retreat in the technology sector gathered steam as the month wore on, sending the tech-heavy Nasdaq Composite into correction territory over a three-day span following a recent record high. A correction is defined as a decline of at least 10% but not more than 20% from a recent high.

A Few Bright Spots The month did offer moments of optimism, however, that sparked brief rallies, such as an increase in merger and acquisition deals and further reported progress on a COVID-19 vaccine. However, concerns about the November election, the fading hopes for a fiscal stimulus bill, and an increase in European COVID-19 cases weighed heavily on investor sentiment.

As September came to a close, the market cut its losses, surging on the final two days of trading as legislators appeared to reopen fiscal stimulus talks.

Sector Scorecard All 11 industry sectors were lower in September, with losses in Communication Services (−6.61%), Consumer Discretionary (−3.15%), Consumer Staples (−3.71%), Energy (−17.56%), Financials (−6.35%), Health Care (−3.87%), Industrials (−2.04%), Materials (−1.52%), Real Estate (−4.05%), Technology (−6.03%), and Utilities (−0.37%).

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Housing accounts for 15% of the nation’s gross domestic product, so investors may watch for the sector to retain its momentum in the fourth quarter and into 2021.

World Markets International markets struggled amid more coronavirus cases in Europe and concerns over the tensions between the United States and China. The MSCI-EAFE Index fell 2.20% in September.

European markets were broadly weaker. France dropped 2.91%, Germany lost 1.43%, and the U.K. slipped 1.68%.

Pacific Rim stocks were mixed as Australia fell 4.04% and Hong Kong declined 6.82%. Japan notched a solid gain, tacking on 9.68%.

Indicators Gross Domestic Product: The final reading of the second-quarter GDP showed an annualized decline of 31.4%.

Employment: The unemployment rate dropped to 8.4% as employers added 1.4 million jobs in August.

Retail Sales: Retail sales growth slowed in August, rising only 0.6% as the supplemental unemployment benefits expired at the end of July. The benefits helped buyers in prior months.

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Financial Matters continued

Industrial Production: Industrial output rose 0.4%, below economistsâ&#x20AC;&#x2122; expectations of a 1% increase.

Fed officials also stressed the importance of additional fiscal stimulus.

Housing: Housing starts fell 5.1% after sharp gains in the previous three months. Single-family home starts increased by 4.1%, but the overall result was dragged down by a 22.7% decline in multi-family starts.

Fed officials adjusted their outlook for unemployment, predicting it would average between 7 and 8% in the final three months of the year. Previously, Fed officials had expected unemployment of between 9 and 10% in the final calendar quarter of 2020.

Existing home sales rose 2.4% from July and were 10.5% higher than August of last year.

MARKET INDEX

Y-T-D CHANGE

September 2020

DJIA

-2.65%

-2.28%

Sales of new homes rose to their highest level in almost 14 years, posting a 4.8% increase from the previous month.

NASDAQ

24.46%

-5.16%

S&P 500

4.09%

-3.92%

BOND YIELD

Y-T-D

September 2020

Consumer Price Index: Consumer prices jumped 0.4% in August, led by the sharpest increase in the cost of used cars and trucks in more than 50 years. On a yearover-year basis, inflation rose 1.3%.

10 YR TREASURY

-1.24%

0.69%

Durable Goods Orders: For the fourth straight month, durable goods orders rose, increasing by 0.4% in August.

New orders for nondefense capital goods, excluding aircraft, jumped 1.8%.

Sources: Yahoo Finance, September 30, 2020 Indices are unmanaged, do not incur fees or expenses, and cannot be invested into directly. These returns do not include dividends. 10-year Treasury real yield = projected return on investment, expressed as a percentage, on the U.S. governmentâ&#x20AC;&#x2122;s 10-year bond.

The Fed The Federal Reserve signaled that interest rates would likely not increase until 2023 following its two-day Federal Open Market Committee (FOMC) meeting that ended on September 16.

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Capital Eyes

Despite Election Results, Either Administration Has Lots to Tackle As press time Election Day was less than a week away. No matter who ends up winning the presidency, however, the administration and Congress will have to immediately address some critical issues after the election and in the first year. Below are some of those issues.

Social Security funding by 2026. No matter who wins the election, there will be pressure on the Congress and president to figure out a solution to this problemâ&#x20AC;&#x201D; whether it be changes to both programs to make them more sustainable or a bailout.

Appropriations/Budget

Energy/Environment

The fiscal year ended on September 30, and spending bills for fiscal year 2021 have not yet been approved.

Instead the current Congress and the president signed bills that cover spending through mid-December.

Therefore, appropriations bills will have to be approved and signed into law in a lame duck session after the election. Failure to do so will result in a government shutdown right before the December holidays.

Depending upon what is approved in December, early in 2021, Congress and the administration will have to start working on spending bills for fiscal year 2022 and possibly another bill for the remainder of fiscal year 2021. However, the current funding caps that were put into place in 2011 will have expired, so there will no longer be mandatory caps on discretionary spending.

If the GOP sweeps the elections, then we can expect that spending will be focused on a southern border wall and defense. If the Democrats sweep, then it is likely that spending priorities will be on health care and green energy initiatives.

Second, with no end in sight for the pandemic, the pressure for more spending relief will be at the forefront next year for whoever is president. This will become even more critical if another stimulus bill is not signed into law during the lame duck session.

Finally, the next president will have to deal with the issue of the trust fund depletion. It is estimated that Medicare funding will run out of money by 2024 and

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It will be critical that the next Administration tackle the extreme damage this year from a brutal year of natural disasters, such as wildfires, hurricanes, and floods.

Cleanup from all these devastating disasters will be high on the agenda for 2021.

Transportation/Infrastructure

There are three top issues in this category that must be addressed by the next administration. The first is the fact that the pandemic has decimated all modes of transportation industries. With the continuing COVID-19 crisis, these industries are depending on the federal government to help. The next president will have to implement a plan to keep these struggling industries from going under.

Second, the next administration will have to figure out a sustainable way to pay for highways, bridges, and transit whether by substantially raising the gas tax or finding a new way to pay for these critical structures.

Thirdly, while both candidates support an infrastructure initiative to repair our damaged transportation fixtures, the next president will have to present a clear plan for how to rebuild and how to pay for it.

In the End

This is obviously a contentious election year, but we have to unite and work together in 2021 to overcome the many problems that arose during 2020. To quote the Queen of England, this has certainly been an

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Capital Eyes continued

“annus horribilis” for our nation on many fronts. But we must look ahead with whoever is in the White House and work to solve the problems cited above and others that might arise.

To all the readers of this column, I say “stay safe, stay sane, and may the holidays offer you a relaxing respite.”

Janet Kopenhaver is president of Eye on Washington and serves as the AWT Washington representative. She can be reached at (703) 528-6674 or janetk@eyeonwashington.com.

Save the Date

Education

CaSO 4 +

Advocacy

Networking SO 4 H + X 2 a C H X –> 2

2021

Annual Convention & Exposition SEPTEMBER 22-25, 2021

Rhode Island Convention Center | Providence, Rhode Island

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Tales From the Waterside

How PTSA and Remote Monitoring Protected a Cooling Tower System From Gross Chemical Overfeed

By Gene Tonetti, CWT, Water Systems Management

(Editor’s note: “Tales From the Waterside” is a new column in the Analyst that will feature real-life experiences as shared by water treatment experts and how they approached problems or important lessons they learned.)

PTSA (1,3,6,8 pyrenetetrasulfonic acid, sodium salt) is a fluorescent molecule that was marketed as TRASAR™ and patented by Nalco Chemical Company in 1988 as a chemical treatment monitor. In 1991, Nalco received a second patent for the use of PTSA for continuous on-stream monitoring of cooling tower water. PTSA has since gained wide acceptance by water treatment chemical suppliers because of the ease of testing and the ability to continuously monitor treatment levels from remote locations.

A few years ago, I made a sales call on an old customer who was recently promoted to plant manager at a CO2 plant that was adjacent to a large ethanol plant. The customer had a very expensive custom-built, modular cooling tower controller that monitored conductivity, pH, and oxygen reduction potential (ORP). The controller was about 17 years old, and all of the sensor probes had been replaced several times. The new plant manager at this CO2 plant wanted to replace the old controller system with a new, more reliable, state-ofthe-art controller system; however, when he received quotes from his current chemical supplier, he realized he did not have money in the budget to cover the price.

with remote monitoring capabilities for pH, conductivity, ORP, and corrosion inhibitor without purchasing it from his capital budget, he was willing to change water treatment suppliers. The owner of the company I worked for at the time agreed to provide the new controller, the inhibitor chemical (with PTSA added), and the new chemical storage tanks. This offer was accepted by the plant manager, and preparations were made to get the new program underway.

The new controller was manufactured by Walchem and was equipped with software provided by H2Tronics. The PTSA sensor was an in-line fluorometer. The controller could be accessed via a modem. A field rep or anyone who had password access could remotely monitor pH, conductivity, PTSA, and ORP (see Table A). Figure 1 shows the cooling tower control panel at the plant, and Figure 2 shows the facility’s cooling tower.

Figure 1: Monitoring panel for cooling tower.

In addition, the corrosion inhibitor chemical control was poor because the inhibitor was added during tower blowdown (bleed and feed), and the plant operators were lax in testing the treatment level on a routine basis. If the plant manager could get a more reliable controller 82

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Tales From the Waterside continued

Remote monitoring is a great idea; however, it should not eliminate the need for periodic plant water testing.

In this case study, the field rep should be testing for free chlorine and comparing the test result to the ORP value at the time of testing. Also, the PTSA values should be compared to the zinc corrosion inhibitor valuesâ&#x20AC;&#x201D;again when the test occurs.

Figure 2: Plant cooling tower.

The ethanol fermentation process produces a significant amount of carbon dioxide that the ethanol plant did not have the ability to recover, and it did not want the CO2-laden waste stream to go to the wastewater treatment plant. The waste stream from the ethanol plant was sent to the CO2 plant for processing before being returned to the ethanol wastewater treatment plant. The CO2 plant installed a rebuilt, single-cell Marley cooling tower to cool the plant ammonia condenser, the CO2 condenser, the compressor oil coolers, and the after cooler heat exchanger.

A trend graph could be viewed and downloaded over a given period of time. In addition, the amount of on/off time that relays were functioning could also be trended.

In other words, you could determine how many minutes a bleach pump, acid pump, inhibitor pump, or cooling tower blowdown valve was activated. You could also monitor makeup water and tower blowdown volumes if the system was equipped with the proper water meters.

Any alarm set points could be adjusted to send a call-out signal to a mobile phone or laptop computer. In other words, you could basically observe how a cooling tower water treatment system was functioning from the comfort of your home.

My company delivered 110 gallons of an all-organic scale inhibitor/zinc-based corrosion inhibitor product containing PTSA to a mini-bulk storage tank located near the cooling tower. Since there was a concern about discharge of phosphorus from the plant, we could not add any phosphonate scale inhibitor chemical to the inhibitor blend.

New chemical feed piping was installed prior to installation of the new controller and delivery of our blended inhibitor chemical. One of the old injection tees and the injection nozzles, as well as the old chlorinated polyvinyl chloride (CPVC) chemical feed piping where the injectors were located, were discarded by the plumbing contractor. The customer was anxious to get the program started, so our service rep decided to temporarily feed the inhibitor chemical directly to the concrete tower basin.

The basin was below ground level and was also several feet below the chemical pump outlet. This turned out to be a big mistake, as there was no anti-syphon valve on

â&#x20AC;&#x153;Remote monitoring is a great idea; however, it should not eliminate the need for periodic plant water testing.â&#x20AC;?

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Tales From the Waterside continued

the discharge tubing. An anti-syphon valve is basically a one-way valve that prevents liquid from syphoning through a pump after it shuts off. Anti-syphon valves are required if the point of chemical injection is below the chemical pump discharge.

The evening after the new inhibitor chemical feed was initiated, the service representative arrived home and used his laptop to access the controller. He noticed an alarm for high PTSA. He checked the controller inhibitor pump relay to determine if it was energized and discovered that it had been off for several hours. He then looked at the controller PTSA trend graph and noticed it was continuing to increase! At that point, he realized the inhibitor was syphoning through the pump since there was no anti-syphon valve on the inhibitor pump discharge tubing. A call was placed to the plant operator to remove the inhibitor feed line from the tower basin location and to temporarily place it in the minibulk tank. When the hose was removed from the tower basin, this “broke” the syphon, and the feed of corrosion inhibitor stopped.

The service rep visited the plant the next day with the correct fittings and injection nozzle in order to feed the inhibitor chemical into the CPVC controller bypass line downstream of the controller sensors. No further incidents involving inhibitor chemical overfeed have occurred.

If it was not for the PTSA alarm callout features and remote monitoring capability of the controller, the entire 110 gallons of inhibitor could have been added to the system in less than 24 hours. Not a good way to start a new program with a new customer!

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Closing Thought

The use of PTSA and remote monitoring are excellent applications for cooling tower water systems. This story illustrates the value of these technologies. As a word of caution, there is always a chance of controller sensor failure, sensor fouling, and damage to controller electronics caused by power surges and other unforeseen conditions. Controller sensor calibration should be checked on a routine basis, preferably at least monthly. In addition, chemical actives should be checked (in this case zinc) and compared to PTSA values.

Table A: New Monitoring System Parameters Sensor

Purpose

Range

pH

Acid feed

7–7.4

Conductivity

Blowdown

1,800–2,000

PTSA

Inhibitor feed

60–80 ppb

ORP

Bleach feed

600–650 mV

Free chlorine*

Bacteria/algae control

0.15–0.30 ppm

*The controller does not directly monitor free-chlorine level.

Gene Tonetti, CWT, is the founder of Water Systems Management. He has worked in the water treatment field for more than 41 years and has expertise in wastewater and high-purity, boiler, and cooling tower water. His experience in treating water includes treatment chemicals, chlorine dioxide, reverse osmosis, and process controllers. Tonetti is a 1973 graduate of RoseHulman Institute of Technology with a B.S. in biological engineering.

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T.U.T.O.R.

Technical Updates, Tips, or Reviews

Why Do Materials of Construction Matter?

By Mike Henley

Corrosion. Leaching. Safety. These are three of many concerns one might list that will drive decisions when engineers and other decision-makers select the materials used for a plantâ&#x20AC;&#x2122;s water treatment system. The purpose of this short article is to provide initial background as to why materials of construction are important. The nature of this discussion is general, but at the close of the article, we will provide a list of resources for those wishing to learn more specifics about this important area.

Normally, materials of construction are primarily associated with piping, valves, and gaskets. However, another area of concern can be system components such as storage tanks, pumps, and filters. It should be noted that some materials are critical to ensuring the water purity or protecting the operations of the end-user that needs the treated water. These two aspects will be the focus of the remainder of this discussion.

the purity of the high-purity water because it does not leach out contaminants nor shed particles. This is particularly important in the semiconductor industry where plant operators are concerned that particles or dissolved solids in the water can either precipitate or land on a chip line and later lead to defective products. Figure 1 shows an example of PVDF piping at a photovoltaic (solar) panel manufacturing plant near Portland, Oregon.

Figure 1: Example of PVDF piping in a microelectronics plant. The smaller diameter pipes on the left are used to carry hot ultrapure water, while the two pipes on the right side carry deionized water.

Wetted Parts Ultrapure Water Particularly within the high-purity water world, the choice of materials of construction used in the treatment equipment and for piping systems is critical. Besides piping and valves, other areas where attention may be given to the use of specialty materials include pumps, pressure vessels, gaskets, heat exchangers, instrument sensors, ultraviolet sleeves, and even filters and membranes, among others.

One concern is that the chosen material not accidentally become the source of contaminating the treated water.

For example, in a semiconductor plant, great care is given to ensure that piping systems and pump surfaces do not leach ionic contaminants back into the water or shed particles.

It is for those reasons that, at least in the microelectronics industries, polyvinylidene fluoride (PVDF) is widely used for valves and distribution systems for ultrapure water.

PVDF is considered an inert material that will maintain 85

In the microelectronics world, PVDF is widely usedâ&#x20AC;&#x201D; particularly in the ultrapure loop. Not only is it considered an inert material that will not contaminate the the Analyst Volume 27 Number 4

T.U.T.O.R. continued

water, but one that can withstand sanitization by ozone and other chemical agents like hydrogen peroxide.

However, in areas not requiring the highest purity water, piping made from polyvinyl chloride (PVC) can also be found in plants. Metallic piping (e.g., stainless steel, steel, copper) is not used because it will leach ionic contaminants, shed particles, and can corrode.

Other Factors Impacting Choices Besides material purity, other reasons to select a particular material used in water can be the ability to withstand higher temperatures, structural strength, or compatibility with other materials used in the facility.

Cost can also be a factor but is often a lesser concern, especially if the cheaper piping, valves, or other items can negatively impact plant operations.

Stainless steel has easily met those needs. However, in recent years, the major pharmacopeias have been amended to also allow the use of reverse osmosis (RO) to produce WFI. RO systems use ambient temperature water, which opens the possibility of using thermoplastic piping for these applications. Note: A pharmacopeia is a document that provides guidelines on different aspects of pharmaceutical manufacturing, including water quality requirements.

Figure 2 shows stainless steel piping in a pharmaceutical plant, and Figure 3 is an example of stainless-steel tanks, such as might be found in a pharmaceutical plant.

Figure 2: Stainless steel piping in a pharmaceutical plant.

Pharmaceutical-Grade Waters Generally, pharmaceutical plants will have stainless steel for their water distribution systems and tanks. A key reason is that this material does not contribute contaminants to the treated water. It can withstand hot water temperatures such as found in Water for Injection (WFI) loops, where distillation is widely used. To control formation of microorganisms, WFI loops circulate, and the temperature is normally maintained at 80 °C. WFI is a type of pharmaceutical water that is considered to be microbial free and is used to manufacture products such as IV fluids and other products that must meet particular sterility requirements because the final product may be injected into the human body.

Figure 3: Stainless steel tanks such as may be found in a pharmaceutical plant. Photo courtesy of Joe Manfredi, GMP Systems, Inc. (Fairfield, New Jersey).

Pharma plants normally have chosen stainless steel because it can be used with hot water and can withstand sterilization with hot water or steam and retain its structural integrity. Please note that PVDF is also used to carry hot ultrapure water, but that at high temperatures, the piping will sag and must have additional structural support.

There is some movement to using thermoplastics in pharmaceutical plants, but this trend is still limited.

Historically, distillation has been the prescribed treatment technology for WFI production, so this production method has required piping capable of withstanding hot water/steam sterilization temperatures as well as carrying the hot water flows during normal loop operations.

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Boiler Water Applications

In power stations and other industrial water applications, steel piping is common for water distribution systems.

For boiler tubes, copper is commonly used. Plant operators are concerned that the treatment system piping and the boiler tubes be durable and resist corrosion (although copper and related tubing materials also corrode).

Corrosion protection is accomplished by treatment chemicals, which are often selected based on metallurgy.

Safety is another concern. Because boilers operate at high temperatures and pressures, tubing is especially prone to scaling that can plug tubes. Scaling can plug tubes, and corrosion can weaken boiler tubes and cause leaks. These two factors can contribute to boiler explosions that can endanger workers and damage power plants, sometimes forcing shutdowns.

Closing Thought

This aim of this brief discussion is to provide an initial understanding of the important role materials of construction play in water treatment and cooling water systems. As the treated water touches the piping and other elements, it either retains its purity, or is contaminated by the pipes, gaskets, pump surfaces, etc. But other factors also play a role when deciding on a material of construction. Those decisions my be impacted by temperature requirements, structural strength, and ability to withstand water treatment/system cleaning protocols.

In the “Digging Deeper” section is a small listing of technical articles that examine some different aspects of materials of construction.

Hanselka, R.; Williams, R.; Bukay, M. “Materials of Construction for Water Systems Part 1: Physical and Chemical Properties of Plastics,” Ultrapure Water Journal 4(5), pp. 46-50 (July/August 1987).

Hanselka, R.; Reinzuch, K.J.; Bukay, M. “Materials of Construction for Water Systems Part 2: Real-life Failure Modes of Plastics,” Ultrapure Water Journal 4(6), pp. 50-53 (September 1987).

Hanselka, R.; Williams, R.; Bukay, M. “Materials of Construction for Water Systems Part 3: Proper Selection of Elastomers,” Ultrapure Water Journal 4(8), pp. 52-55 (November 1987).

Harfst, W.F. “Piping Materials of Construction”, Ultrapure Water Journal 30(6), p. 24 (November/ December 2013).

Howell, A.G. “Hydrogen Damage Mitigation by Boiler Chemical Cleaning”, Ultrapure Water Journal 31(3), pp. 21-25 (May/June 2014).

Libman, S.; Buesser, D.; Ekberg, B. “Next Generation of UPW Distribution System for the Next Generation of Semiconductor Fabs,” Ultrapure Water Journal 29(1), pp. 23-30 (January/February 2012).

Roll, D.L.; Ekstrand, B.J. “Surface Chemistry Improvement on 316L Stainless Steel Weld Zones Using a Gelled Citric Acid-Based Passivation Agent,” Ultrapure Water Journal 25(8), pp. 24-28 (November 2008).

Wermelinger, J.; Mueller, H.; Burkhart, M. “New 450-mm PVDF Piping Systems for Conveying High-Purity Water in Semiconductor Plants,” Ultrapure Water Journal 28(7), pp. 15-24 (July 2011).

Digging Deeper

Biressi, G.; Haggard, K.; Neubauer, B. “Fluoropolymer Applications in High-Purity Water Distribution Systems,” Ultrapure Water Journal 30(6), pp. 15-18 (November/December 2013).

Biressi, G.; Neubauer, B. “Part 2: Ozone Sterilization of PVDF Piping Systems for High-Purity Water Distribution,” Ultrapure Water Journal 29(6), pp.

18-22 (November/December 2012).

Biressi, G.; Neubauer, B. “Part 1: Steam Sterilization of PVDF Piping Systems for High-Purity Water Distribution,” Ultrapure Water Journal 29(3), pp.

13-16 (May/June 2012).

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Business Notes

5 Principles to Guide Adaptive Leadership

By Ben Ramalingam, David Nabarro, Arkebe Oqubuy, Dame Ruth Carnall, and Leni Wild

The COVID-19 pandemic is constantly evolving, with leaders facing unpredictability, imperfect information, multiple unknowns and the need to identify responses quickly, all while recognizing the multidimensional (health-related, economic, social, political, and cultural) nature of the crisis.

Responding to the crisis requires adaptive leadership, which involves what we refer to as the four A’s: ANTICIPATION of likely future needs, trends, and options; ARTICULATION of these needs to build collective understanding and support for action; ADAPTATION so that there is continuous learning and the adjustment of responses as necessary; ACCOUNTABILITY, including maximum transparency in decision-making processes and openness to challenges and feedback.

How can we make sure that this kind of adaptive leadership is properly implemented as our communities and businesses confront the pandemic? We have identified five common principles to guide action: 1. ENSURE EVIDENCE-BASED LEARNING AND ADAPTATION: Adaptive leadership means teams and organizations need to constantly assess their modus operandi, recognizing that they will have to iterate and adapt their interventions as they learn more about the outcomes of decisions. This requires clear processes for determining the best options; collecting, interpreting, and acting on evidence, including defining a set of key measures for determining success or failure; ensuring ongoing collection of operationally relevant data; and setting out a clear process for how changes in data and trends will trigger changes in action.

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Putting social learning and adaptation at the center of crisis response has been found to be crucial in recent disease outbreak management, most notably in dealing with Ebola in West Africa. An analysis of the successful eradication of smallpox has also shown that the success was attributable to processes of strategic adaptation and learning—more than any other single factor.

2. STRESS-TEST UNDERLYING THEORIES, ASSUMPTIONS AND BELIEFS: Just as institutions such as banks regularly undergo stress testing to ensure they can deal with future crises, the assumptions and hypotheses guiding an adaptive response need to be subject to robust and rigorous reflection and examination, including through the simulation of different possible future scenarios.

One of most systematic and rigorous approaches to COVID-19 scenario planning has been developed

by Boston Consulting Group. Drawing on military approaches to strategic learning, they advocate that firms establish an integrated model of “anticipation, intelligence and response.” Using such an approach, different scenarios have been developed for use by the automotive, fashion, and luxury goods sectors. These scenarios account for critical uncertainties in the public health situation, the impact of government measures, the wider economic environment and business-specific demand forecasts, and they make use of real-time monitoring as the basis for decision-making.

3. STREAMLINE DELIBERATIVE DECISIONMAKING: A major challenge faced by leaders is that the data on COVID-19 is changing all the time and is often contradictory. When decision-makers feel threatened, they are much more likely to revert to risk-averse and siloed responses to ensure the degree of safety that results from narrowly defined targets.

To avoid that, leaders at different levels therefore need to be clear about what they are basing their assumptions and the Analyst Volume 27 Number 4

Business Notes continued

hypotheses on. They need to explain what is being done and why, and how a decision was made, so that if errors are identified, trust can still be maintained in the process.

4. STRENGTHEN TRANSPARENCY, INCLUSION, AND ACCOUNTABILITY: People around the world have been asked to make major behavioral changes, and this brings significant costs for society, businesses, and governments. Because the stakes are so high, there is a need to examine how early decisions were made, bearing in mind the information available at the time. Ongoing real-time assessment of the response is needed to maximize learning. Such assessments should include all relevant stakeholders—from professionals to affected populations.

The best adaptive leaders—from business leaders to policymakers to community organizers—recognize mistakes are likely to be made and actively use the information to identify shared learning opportunities. The European Centre for Disease Control and Prevention has advocated the use of after-action reviews and similar processes to assess how public health decisions were taken at different points and on what basis.

Given the fact that the pandemic response is increasingly being viewed as a marathon and not a sprint, it is vital to assess what has happened so far, to identify strategic priorities and to exchange lessons learned. This means leaders need to commit to sharing their thinking and soliciting feedback at every stage in the spirit of openness, candor and transparency.

5. MOBILIZE COLLECTIVE ACTION: The COVID-19 crisis is not just a public health crisis; it’s also an economic, social, and political crisis. It is a “complex systems” problem that requires changes in behaviors, incentives, and relationships between different groups and organizations. Effective responses therefore need to build on collaboration across different sectors, industries, and professionals and between international, national, and local levels.

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Adaptive leadership has a crucial role to play in helping to identify shared alignment of objectives and scope for collective action across different silos and levels of the response. In the U.K., shared awareness of the existing health care capacity underpinned a landmark deal to commission rapidly all private-sector hospitals for use by the National Health Service, leading to an accelerated scaling up of available beds and equipment.

Civil society and citizen groups have also played a central role in mobilizing inclusive approaches to the pandemic, especially in resource-constrained settings.

Local responses have emerged in the form of community-led support for the most vulnerable in Bhopal, India; the repurposing of manufacturing capability to enable locally produced personal protective equipment across the United States; and the strengthening of “social economy” approaches to rebuild disrupted economies from the bottom up in Canada and numerous European countries.

What we do in this crisis response will have repercussions for years and decades to come. The five principles of adaptive leadership are not just vital to guide our immediate responses; they will also be crucial as we shape longer term recovery and resilience plans. Our collective future may be uncertain, but uncertainty is at the very heart of human creativity.

Ben Ramalingam is a senior research associate at the Overseas

Development Institute. David Nabarro is the special envoy of the World Health Organization’s director general on COVID-19 and co-di-

rector of the Imperial College Institute of Global Health Innovation at Imperial College London. Arkebe Oqubuy is senior minister and

special adviser to the prime minister of Ethiopia. Dame Ruth Carnall

is managing partner of Carnall Farrar, a trustee of the Kings Fund and

the former chief executive officer of the National Health Service London.

Leni Wild is a senior research associates at the Overseas Development Institute.

© 2020 Harvard Business School Publishing Corp.

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