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New edition covers the latest practices, regulations, andalternative disinfectants Since the publication of the Fourth Edition of White'sHandbook of Chlorination and Alternative Disinfectants morethan ten years ago, the water industry has made substantialadvances in their understanding and application of chlorine,hypochlorite, and alternative disinfectants for water andwastewater treatment. This Fifth Edition, with its extensiveupdates and revisions, reflects the current state of the science aswell as the latest practices. Balancing theory with practice, the Fifth Edition coverssuch important topics as: * Advances in the use of UV and ozone as disinfectants * Alternative disinfectants such as chlorine dioxide, iodine, andbromine-related products * Advanced oxidation processes for drinking water and wastewatertreatment * New developments and information for the production and handlingof chlorine * Latest regulations governing the use of differentdisinfectants For each disinfectant, the book explains its chemistry,effectiveness, dosing, equipment, and system design requirements.Moreover, the advantages and disadvantages of each disinfectant areclearly set forth. References at the end of each chapter guidereaders to the primary literature for further investigation. Authored and reviewed by leading experts in the field of waterand wastewater treatment, this Fifth Edition remains anideal reference for utilities, regulators, engineers, and plantoperators who need current information on the disinfection ofpotable water, wastewater, industrial water, and swimmingpools.
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CONTENTS
Preface
Authors
List of Contributors and Reviewers
List of Abbreviations
Acknowledgments
1 Chlorine: History, Manufacture, Properties, Hazards, and Uses
Historical Background
Manufacture of Chlorine
Electrolytic Cell Development
Other Chlorine Manufacturing Processes
Impurities in the Manufacture of Chlorine
Physical and Chemical Properties of Chlorine
Hazards from Chlorine Vapor and Liquid
Chlorine Leaks
Calculating Chlorine Leak Rates
Summary
USEPA Risk Management Programs (RMPs)
Chlorine Transport Accidents
Notable Consumer Accidents
Production and Uses of Chlorine
References
2 Chemistry of Aqueous Chlorine
Dissolution and Hydrolysis of Chlorine
Dissociation of Hypochlorous Acid
Chlorine Speciation in Concentrated Solutions
Hypochlorite Solutions
Oxidation States of Chlorine
Free, Combined, and Available Chlorine
Chlorine and Nitrogenous Compounds
The Chemistry of Chlorine in Seawater
Oxidation–Reduction Reactions of Chlorine Compounds
ORP Measurements
Reactions of Chlorine with Selected Constituents
Chlorine Demand
Germicidal Significance of Chlorine Residuals
References
3 Determination of Chlorine Residuals in Water and Wastewater Treatment
Historical Background
General Considerations
Amperometric Titration
DPD Method
FACTS (Syringaldazine) Method
Iodometric Method I
Iodometric Method II (Wastewater)
Iodometric Electrode Method
Leuco Crystal Violet (LCV) Method
Methyl Orange (MO) Method
Orthotolidine Method
References
4 Chlorination of Potable Water
Microbes in Water Supplies
Waterborne Diseases
Chlorine as a Disinfectant
Disinfection Requirements under (Provisions of the) Safe Drinking Water Act (SDWA)
Disinfection of Drinking Water with Clorine
Disinfection with Chloramines
Distribution System
Disinfection of New Infrastructure
Other Uses of Chlorine in Water Treatment
Chlorination in the United Kingdom
Chlorination in Germany
Treatment Strategies
Acknowledgments
References
5 Chlorination of Wastewater
Introduction
Odor Control
Chlorine and Biological Treatment
Other Uses of Chlorine in Wastewater Treatment
Industrial Waste Treatment Applications Using Chlorine
References
6 Disinfection of Wastewater
Introduction
Viruses
Methods of Wastewater Disinfection
Chemistry of Wastewater Disinfection by Chlorine
Formation of DBPS
Other Disinfection Considerations
Wastewater Reuse
References
7 Chlorine Contact Basin Design
Introduction
Design Elements
References
8 Chlorine Feed Systems
Cylinders
Ton Containers
Tank Trucks/Tank Cars
Storage Tanks
Liquid Chlorine Feed
Appurtenances
Chlorine Feeders and Eductors
Reference
9 Hypochlorination — Sodium Hypochlorite
Background and History of Hypochlorites
Sodium Hypochlorite
Degradation
Impact on Treatment Process
Tank Selection
Transfer and Feed Equipment
Sodium Hypochlorite Piping
Sodium Hypochlorite Valves
Sodium Hypochlorite Facility Layouts
Calcium Hypochlorite
Lithium Hypochlorite
References
10 On-Site Sodium Hypochlorite Generation System
Historical Background1
Raw Material Quality
On-Site Generation of Sodium Hypochlorite
System Components
On-Site Sodium Hypochlorite Generation System Design
System Manufacturers
References
11 Dechlorination
Introduction
Sulfur Dioxide
Sulfite Compounds
Other Dechlorination Chemicals
Dechlorination Facility Design
References
12 Process Controls for Chlorination and Dechlorination
Introduction
Background
Online Analytical Measurements
Online Analyzers for Chlorination
Online Process Control Overview
Chlorination Process Control
Dechlorination
Online Analyzers for Dechlorination
Blending Chemistry with Process Control
Control System O&M
Record Keeping and Regulatory Issues
References
13 Operation and Maintenance
General
Chlorine Gas Systems
Sodium Hypochlorite Systems
Dechlorination Gas Systems
Dechlorination Liquid Systems
Operator Training and Safety
Storage Systems
Regulatory Requirements
14 Chlorine Dioxide
Introduction
Chemical and Biologic Properties
Equipment and Generation
Use in Drinking Water and Wastewater Disinfection
Other Disinfection Applications
Other Uses for Chlorine Dioxide in Water Treatment
Analytic Methods for Chlorine Dioxide and its Oxychlorine By-Products
Health and Safety
Regulatory Issues
Summary
Acknowledgments
References
15 Ozone
Introduction
History and Application
Chemical Properties
Inorganic Compound Treatment
Organic Compounds
Disinfection
Ozone DBPS
Use in Water and Wastewater Treatment
Equipment and Generation
Process Calculations
Quench Chemicals
Analytical Methods
Health and Safety
Regulatory Issues
References
16 Bromine, Bromine Chloride, BCDMH, and Iodine
Bromine (Br2)
Use of Bromine in Water Treatment Processes
Bromides: On-Site Generation of Br2
Bromine Chloride (BrCl)
BCDMH
Iodine (I2)
Summary
References
17 Ultraviolet Light
Introduction
Chemical and Biological Properties
Guidelines
UV Equipment
Water Quality Issues
UV System Sizing Tools
Operation and Maintenance Activities
Troubleshooting Strategies
Health and Safety for Water And Wastewater UV Systems
References
18 Advanced Oxidation Processes
Introduction
Chemistry of AOPs
Uses in Drinking Water and Wastewater Treatment
Factors Affecting System Performance
Regulations
Equipment and Generation
References
Appendix
Index
Copyright © 2010 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New JerseyPublished simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
White’s handbook of chlorination and alternative disinfectants. – 5th ed./Black & Veatch Corporation.p. cm.Rev. ed. of: Handbook of chlorination and alternative disinfectants/Geo. Clifford White. 4th ed. 1999.Includes bibliographical references and index.ISBN 978-0-470-18098-3 (cloth)1. Water–Purification–Chlorination. 2. Sewage–Purification–Chlorination.3. Water–Purification–Disinfection. I. White, George Clifford. Handbook of chlorination and alternative disinfectants. II. Black & Veatch. III. Title. IV. Title: Handbook of chlorination and alternative disinfectants.TD462.W47 2010628.1'662–dc222009022484
This Fifth Edition of the Handbook of Chlorination and Alternative Disinfectants is dedicated to George Clifford White for his lifetime commitment to the disinfection industry.
PREFACE
Over the years, the science and practice of disinfection has provided innumerable health benefits, although the general public is unaware of many of them. With the recognition of infectious organisms such as Cryptosporidium in our raw water supplies, along with the detrimental chronic health effects associated with disinfection by-products, it is critical to balance the extent of their inactivation with the concentrations of disinfection by-products. Many water and wastewater utilities are implementing the use of multiple disinfectants in order to optimize the results while minimizing unwanted side effects.
The four previous editions of this handbook have proven to be a valuable resource to countless utilities, regulators, engineers, and operators for information on disinfection of potable water, wastewater, industrial water, and swimming pools. George Clifford White’s efforts in compiling these editions are invaluable; and much of the information he has gathered is included in this current edition; some of it is retained solely to provide a historical perspective.
Since the publication of the fourth edition, the water industry has gained a substantial amount of experience with chlorine, hypochlorite, and alternative disinfectants through research, development, and regulation. Consequently, this handbook has been extensively revised and updated to reflect the most current understanding and practices. The reader will find substantial and important information not only on chlorination but also on alternative disinfectants such as ozone, chlorine dioxide, bromine-related products, and ultraviolet light. In addition, the global focus on reuse to address the issue of water scarcity has elevated the use of advanced oxidation practices, and that chapter has therefore been updated to reflect today’s environment.
Each chapter has been prepared by experts and reviewed by their peers in an effort to impart accurate, complete, and current knowledge on the subject being discussed. Black & Veatch considers it a privilege to present this updated resource on chlorination and alternative disinfectants for the water and wastewater industries.
It is our intention that this handbook continue to be the disinfection reference of choice for designers, operator, engineers, students, and regulators.
CINDY WALLIS- LAGEBlack & VeatchEditor
AUTHORS
Chapter 1 Chlorine: History, Manufacture, Properties, Hazards, and Uses
Leland L. Harms, PhD, P.E., Black & Veatch (Retired)
Walter J. O’Brien, ScD, P.E., Black & Veatch (Retired)
Chapter 2 Chemistry of Aqueous Chlorine
Stephen J. Randtke, PhD, P.E., University of Kansas
Chapter 3 Determination of Chlorine Residuals in Water and Wastewater Treatment
Stephen J. Randtke, PhD, P.E., University of Kansas
Chapter 4 Chlorination of Potable Water
Holly Shorney-Darby, PhD, P.E., Black & Veatch
Leland L. Harms, PhD, P.E., Black & Veatch (Retired)
Chapter 5 Chlorination of Wastewater
Edmund A. Kobylinski, P.E., Black & Veatch
Alok Bhandari, PhD, P.E., Iowa State University
Chapter 6 Disinfection of Wastewater
Edmund A. Kobylinski, P.E., Black & Veatch
Alok Bhandari, PhD, P.E., Iowa State University
Chapter 7 Chlorine Contact Basin Design
Neil S. Massart, P.E., Black & Veatch
Trevor H. Cooke, P.E., Black & Veatch
Chapter 8 Chlorine Feed Systems
Edward D. Vogt, P.E., Black & Veatch
Chapter 9 Hypochlorination-Sodium Hypochlorite
Kenneth A. Lewis, P.E., Black & Veatch
Chapter 10 On-Site Sodium Hypochlorite Generation Systems
Erin R. Briggeman, P.E., Black & Veatch
Chapter 11 Dechlorination
Neil S. Massart, P.E., Black & Veatch
Ladan Holakoo, PhD, P.E., P.Eng., Black & Veatch
Chapter 12 Process Controls for Chlorination and Dechlorination
Edmund A. Kobylinski, P.E., Black & Veatch
Timothy A. Holmes, P.E., Black & Veatch
Chapter 13 Operations & Maintenance
Neil S. Massart, P.E., Black & Veatch
Chapter 14 Chlorine Dioxide
Robert C. Hoehn, PhD, Professor Emeritus, Virginia Polytechnic Institute & State University
Holly Shorney-Darby, PhD, P.E., Black & Veatch
Jeff Neemann, P.E., Black & Veatch
Chapter 15 Ozone
Nick L. Burns, P.E., Black & Veatch
Chapter 16 Bromine, Bromine Chloride, BCDMH, and Iodine
Gary L. Hunter, P.E., Black & Veatch
Hua Jiang, PhD, P.E., Black & Veatch
Chapter 17 Ultraviolet Light
Gary L. Hunter, P.E., Black & Veatch
Bryan R. Townsend, Black & Veatch
Chapter 18 Advanced Oxidation Processes
Rick Bond, P.E., Black & Veatch
LIST OF CONTRIBUTORS AND REVIEWERS
MARC-OLIVIER BUFFLE, PhD, Sustainable Asset Management AG, Chapter 18
MICHAEL F. COUGHLIN, PhD, Johnson Diversey, Chapter 14
DOUG ELDER, P.E., Black & Veatch, Chapter 7
WILLIAM FEHRMAN, Severn Trent Services, Chapter 8
DAVID H. FRIESS, Black & Veatch, Chapter 13
ALBERTO GARIBI, Siemens Water Tech., Chapter 10
JULIA V. GASS, P.E., Black & Veatch, Chapter 15
DON GATES, PhD, Consultant, Chap ter 14
DAN C. GAY, P.E., Black & Veatch, Chapter 9
ALI GITI, Severn Trent Services, Chapter 10
GILBERT GORDON, PhD, Professor Emeritus, Miami University, Ohio, Chapters 2 and 3
LELAND L. HARMS, PhD, P.E., Black & Veatch (Retired), Chapter 2
ROBERT A. HULSEY, P.E., Black & Veatch, Chapter 15
SAMUEL JEYANAYAGAM, PhD, P.E., DEE, Malcolm Pirnie, Chapters 5, 6 and 17
KARL G. LINDEN, PhD, University of Colorado, Chapter 17
DAN W. MEYER, P.E., Black & Veatch, Chapter 1
ROGER D. MILLER, Layne Christensen Company, Chapter 4
JEFF NEEMANN, P.E., Black & Veatch, Chapter 15
GARY W. NEUN, Black & Veatch, Chapter 13
GUSTAVO FM QUEIROZ, P.E., Black & Veatch, Chapter 10
KERWIN L. RAKNESS, Process Applications, Inc., Chapter 15
STEPHEN J. RANDTKE, PhD, P.E., University of Kansas, Chapter 4
DON D. RATNAYAKA, CEng, Black & Veatch, Chapters 4 and 14
ANDREW R. SHAW, P.E., Black & Veatch, Chapters 3 and 12
HOLLY SHORNEY-DARBY, PhD, P.E., Black & Veatch, Chapter 2
EDWARD D. VOGT, P.E., Black & Veatch, Chapters 9, 10 and 11
ELLIOTT WHITBY, PhD, Calgon Carbon Corp., Chapter 17
TIMOTHY J. WHITE, P.E., Black & Veatch, Chapter 4
LIST OF ABBREVIATIONS
ACalternating currentACCAmerican Chemical Council; automatic control centerACGIHAmerican Conference of Governmental Industrial HygienistsAIHAAmerican Industrial Hygiene AssociationANSIAmerican National Standards InstituteAOBammonia oxidizing bacteriaAOCassimilable organic carbonAOPadvanced oxidation processAOXPadvanced oxidation processASanalog subsystemATEXexplosive atmosphere directive (UK)AWTadvanced wastewater treatmentAWWAAmerican Water Works AssociationAwwaRFAmerican Water Works Association Research FoundationBACbiological activated carbonBDOCbiodegradable dissolved organic carbonBFbaffling factorBOCABuilding Officials and Code Administrators, InternationalBODbiochemical oxygen demandB-PbreakpointCAcellulose acetateCAAchloracetic acidCACcombined available control systemCANUTECCanadian Transport Emergency CentreCCCScentral computer control systemCFDcomputational fluid dynamicsCHEMTRECChemical Transportation Emergency CenterCIChlorine InstituteCODchemical oxygen demandCOMAHcontrol of major accident hazard (U.K.)CPchloropicrinCPRVchlorine pressure-reducing valveCRCcombined residual chlorineCScontrol systemCSBChemical Safety and Hazard Investigation Board (U.S.)CSOcombined sewer overflowCTchlorine residual x contact timeCTCcentral terminal controlD/DBPRDisinfectants/Disinfection Byproducts RuleDBPdisinfection byproductDCdirect currentDEdiatomaceous earthDIWdeionized waterDNAdeoxyribonucleic acidDOdissolved oxygenDOCdissolved organic carbonDOTDepartment of TransportationDPDdiethyl-p-phenylenediamineDPHDepartment of Public HealthDPPdifferential pulse polarographyDSAdimensionally stable anodesDXAAsdihaloacetic acidsEBCTempty bed contact timeEDelectrodialysisEDCendocrine disrupting compoundEDPethyl dibromideEESemergency service specialistEFVexcess flow valveEPAEnvironmental Protection Agency (also USEPA)EPDMethylene propylene diene monomerEPSextracellular polymer substancesERPGEmergency Response Planning GuidelinesFACfree available chlorineFACTSfree available chlorine test – syringaldazineFASferrous ammonium sulfateFCfecal coliformFIAflow injection analysisFPAflavor profile analysisFRCfree residual chlorineFRPfiberglass-reinforced plasticGACgranular activated carbonGOXgaseous oxygenGUDIgroundwater under the direct influenceGWRGroundwater RuleHAAhaloacetic acidHAA5five regulated HAAsHANhalo acetonitrileHFFhollow fine fiberHPCheterotrophic plate countHRThydraulic retention timeHSEHealth and Safety Executive (U.K.)ICion chromatographyICRInformation Collection RuleIDLHimmediate danger to life and healthIESWTRInterim Enhanced Surface Water Treatment RuleIFCIInternational Fire Code InstituteIXion exchangeLCRLead and Copper RuleLOXliquid oxygenLSLlower sensitivity limitLT1ESWTRLong-term 1 Enhanced Surface Water Treatment RuleLT2ESWTRLong term 2 Enhanced Surface Water Treatment RuleMCAManufacturing Chemists AssociationMCLmaximum contaminant levelMCLGmaximum contaminant level goalMDLmethod detection limitMFmicrofiltrationMFImodified fouling indexMIB2-methylisoborneolMLVSSmixed liquor volatile suspended solidsMPNmost probable numberMRDLGmaximum residual disinfectant level goalMSDSmaterial safety data sheetsMWCminimum water columnMWDmaximum water depth; Metropolitan Water District; minimum water depthNDMAN-nitrosodimethylamineNFnanofiltrationNFPANational Fire Protection AssociationNMWnominal molecular weightNOBnitrite-oxidizing bacteriaNOMnatural organic matterNPDESNational Pollutant Discharge Elimination SystemNSFNational Sanitation FoundationNTSBNational Transportation Safety BoardORPoxidation-reduction potentialOSHAOccupational Safety and Health AdministrationOTorthotolidineOTAorthotolidine-arsenitePACpowdered activated carbonPAOphenylarsine oxidePCprogrammable controllerPCBpolychlorinated biphenylPCSprocess control softwarePDWFpeak dry weather flowPFUplaque-forming unitPICSprocess instrument control systemPLCprogrammable logic controllerPPCPpharmaceutical and personal care productPSApressure swing adsorptionPSMprocess safety managementPSSpoint summation sourcePSUpower supply unitPTFEpolytetrafluoroethylenePVCpolyvinyl chlorideRAArunning annual averageRASreturn activated sludgeRCPreinforced concrete pipeRMPrisk management programRMPPrisk management protection planROreverse osmosisRSIRailway Supply InstituteRTKright-to-knowRTUremote terminal unitSCFshort circuiting factorSDHsuccinic dehydrogenaseSDIsilt density indexSDWASafe Drinking Water ActSETIQSistema de Emergencies en Transporte para la Industria QuimicaSFPCStandard Fire Prevention AssociationSHMPsodium hexametaphosphateSLSsodium lauryl sulfateSMCLsecondary maximum contaminant levelsSOCsynthetic organic compoundSPCstandard plate countSSsuspended solidsSTELshort-term exposure limitSWspiral woundSWTRSurface Water Treatment RuleTCtotal coliformTCAtrichloroacetic acidTCEtrichloroethyleneTCEPtris (2-chloroetlyl) phosphateTDDtriple distilled deionizedTDHtotal dehydrogenase; total dynamic headTDStotal dissolved solidsTFCthin-film compositeTHMtrihalomethanesTHMFPtrihalomethane formation potentialTLVthreshold limit valueTOCtotal organic carbonTONthreshold odor numberTOXtotal organic halidesTRANSSCAERTransportation Community Awareness and Emergency ResponseTRCtotal residual chlorineTSStotal suspended solidsTTCEtetrachloroethyleneTTHMtotal trihalomethaneTWAtime weighted averageUBCUniform Building CodeUFultrafiltrationUFCUniform Fire CodeUPUnion PacificUSEPAUnited States Environmental Protection Agency (also EPA)USGSUnited States Geological ServiceUVultravioletUVAultraviolet absorbance at 254 nmVOCvolatile organic carbon/compoundVSAvacuum swing adsorptionWEFWater Environment FederationWPCFWater Pollution Control FederationWTPwater treatment plantWWTPwastewater treatment plantACKNOWLEDGMENTS
We give special thanks to Alan Ingham and Dan Wright for assistance with graphic arts. We are also grateful for the assistance and compilation efforts of Rhonda Hoyt.
1
Chlorine: History, Manufacture, Properties, Hazards, and Uses
HISTORICAL BACKGROUND
Elemental Chlorine
Chlorine is an element of the halogen family, but it is never found uncombined in nature. It is estimated to account for 0.15% of the earth’s crust in the form of soluble chlorides, such as common salt (NaCl), carnallite (KMgCl3 · 6H2O), and sylvite (KCl). In nature, it exists only as the negative chloride ion with a valence of −1. Because its properties in the gaseous, liquid, and aqueous states differ widely, each phase will be discussed separately.
Chlorine Gas
Medieval Arab chemist Geber must have known this element (ca. 720–810). Chlorine was discovered, in its gaseous state, in 1774 by Karl W. Scheele, a Swedish chemist, when he heated manganese dioxide with hydrochloric acid.1
(1.1)
Scheele called the gas he discovered “dephlogisticated muriatic acid” on the theory that manganese had displaced “phlogiston” (as hydrogen was then called) from the muriatic acid (HCl). Scheele also observed that the gas was soluble in water, that it had a permanent bleaching effect on paper, vegetables, and flowers, and that it acted on metals and oxides of metals.
During the decade following Scheele’s discovery, Lavoisier attacked and, after a memorable struggle, completely upset the phlogiston theory of Scheele. Lavoisier was of the opinion that all acids contained oxygen. Berthollet found that a solution of Scheele’s gas in water, when exposed to sunlight, gives off oxygen and leaves behind muriatic acid. Considering this residue proof of Lavoisier’s theory, Berthollet called it oxygenated muriatic acid.2 However, Humphry Davy was unable to decompose Scheele’s gas. On July 12, 1810, before the Royal Society of London, he declared the gas to be an element, in which muriatic acid is combined with hydrogen. Therefore, Lavoisier’s theory that all acids contain oxygen had to be discarded. Davy proposed to name the gas “chlorine” from the Greek chloros, variously translated “green,” “greenish yellow,” or “yellowish green,” in allusion to its color.
Pelletier in 1785 and Karsten in 1786 succeeded in producing yellow crystals of chlorine hydrate by cooling Scheele’s gas in the presence of moisture. From this, they inferred that it was not an element. In 1810, Davy proved that the crystals could not be formed by cooling the gas even to −40 °F in the absence of moisture. It is now known that these crystals are in fact chlorine hydrate (Cl2 · 8H2O) and will form under standard conditions with chlorine gas in the presence of moisture and at a temperature of at least 49.3 °F.
Chlorine Liquid
In 1805, Thomas Northmore noted that Scheele’s gas became a yellowish amber liquid under pressure, and upon release of the pressure it volatilized rapidly and violently into a green gas. He further noted that it had a pungent odor and caused severe damage to machinery.
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