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Copy of Biofilm Seminar Presentation-- 11-04

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    DREW

    INDUSTRIAL

    CONTROLLING

    MICROBIOLOGICALLYINFLUENCED CORROSION

    AND BIOFOULING

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    2

    Microbiological Control Is The Key To Success

    Or Failure In Cooling Water Treatment Programs

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    3

    How Biofilms Form

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    Biofilms Must Be Controlled

    Will provide insulating barrier andreduce heat transfer rates

    Will trap debris and promote plugging

    Concentration cell forms beneath and

    corrosion accelerates (MIC)

    Provides a host for anaerobicbacteria such as SRBs and otheracid formers

    How MIC occursHow MIC occurs

    Biofilm on exchangerBiofilm on exchanger

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    5

    Biofilms Must Be Controlled

    Top layer Aerobic bacteria Nitrifying, iron oxidizing and

    manganese bacteria aretypical

    Middle layer Facultative bacteria

    Prefer aerobic, but survive inanaerobic conditions

    Denitrifying

    Bottom layer Anaerobic SRB, iron reducing

    Provides protective barrier for all types of microorganisms and

    creates environment to enable all species to flourish

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    Pitting

    Biofilm provides anaerobic environment for SRB proliferation

    SRB attack in anaerobic environments results in pitting in all

    metallurgy

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    Chlorination

    Cl2 +H2O HCl + HOCl

    HOCl H+ + OCl-

    Lowest cost alternative in right systems-- Narrow pH

    range below ~8.5

    Uncontaminated systems

    Attacks nucleus not slime layer Poor biofilm penetrant

    Reacts with organics and loses ability to kill bacteria

    Reacts with NH3, forming chloramines

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    Chlorine and Ammonia

    Cl2 reacts in 10:1 ratio to form

    chloramines

    Far less effective than HOCl

    and OCl-

    Initially forms

    monochloroamine

    Positive FRC reading Significantly lower ORP Much lower killing power

    121NH2Cl

    412OCl-

    200100200HOCl

    VirusSporesBacteria

    Relative Effectiveness

    (Related to Kill Time)

    ff f C C

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    Effect of Free Chlorine and Chloramines

    on ORP (pH = 7.5)

    Effect of Free Chlorine and Chloramines

    on ORP (pH = 7.5)

    200

    250

    300

    350

    400

    450

    500

    550

    600

    650

    700

    750

    800

    0.00 0.01 0.10 1.00 10.00 50.00 100.00

    Free Available Halogen

    ORPm

    V

    NH2Cl HOCl

    Target min ORP Target max ORP

    Area of

    optimum

    kill

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    Chloramines Are Very Poor Biocides

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    Effects Of Over-Chlorination

    Acceleration of corrosion rates

    Increased chloride-- SCC of SS

    Aggressive to copper

    Delignification of wood

    Reaction/deactivation of some

    inhibitors/ deposit control agents

    Lower cycles of concentration when

    chloride is limiting factor for COC

    Severe delignification

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    Bromination

    Very effective at pH 8+ in uncontaminated systems

    Most economical is to activate a sodium bromidesolution with chlorine source

    NaBr + Cl2 + H2O NaCl + HOBr + HCl

    At higher pH levels:

    HOBr OBr- + H+

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    0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    100

    6.5 6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5 8.7 8.9

    pH

    Percentdissociation

    HOCl

    HOBr

    Br2Better Than Cl2at Higher pHBr2Better Than Cl2at Higher pH

    B i H V L H lf Lif d Fl h

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    Bromamines Have Very Low Half Life and Flash

    Off Over the Tower

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    Chlorine Dioxide

    Overcomes the Problems

    Associated with Chlorine

    and Bromine

    OO

    OO

    ClCl

    OO

    OO

    ClCl

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    What is Chlorine Dioxide?

    Powerful and highly effective oxidizer

    Not affected by pH because it is a dissolved gas Wont react with many organic contaminants - including

    ammonia compounds

    Excellent biofilm removal - rapidly penetrates and oxidizes

    biofilms

    Can destroy odors caused by microorganisms and organics

    Does not form disinfection by-products such as

    trihalomethanes and oxidized aromatics

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    Why ClO2 Is Effective In Biofilm Removal

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2

    ClO2ClO

    2

    ClO2

    ClO2 enters cells un-depleted & kills from within

    Stops protein production by disrupting DNA

    Once DNA is disrupted, life ceases

    Low O2 pH

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    Many Organics Do Not React With ClO2

    Ammonia

    Ammonium salts

    Primary amines

    Alkanes

    Alkenes

    Alcohols

    Glycols

    Diols

    AldehydesKetones

    Ethers

    Acids

    Unsubstituted aromatics

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    Non-Oxidizing Biocide Effectiveness

    S

    accharomyc

    escerevisi

    n

    Staphylococcusaureu

    Psue

    domones

    aeneginone ChlorineDioxid

    AcidifiedQuatern

    ar

    QuaternaryAm

    moniu

    SodiumHypochlorit

    Glutaraldehyde

    0

    500

    1000

    1500

    2000

    2500

    Dosage Required For 99.999% Kill (5-Log Reduction) in 60 Seconds

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    0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    100

    6.5 6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5 8.7 8.9

    pH

    Percentdissociation

    HOCl

    HOBr

    ClO2

    ClO2 Not pH DependentClO2 Not pH Dependent

    Bromine Vs Chlorine Dioxide In Presence of

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    Bromine Vs Chlorine Dioxide In Presence ofAmmonia- ORP & Dose Rate Vs % Kill

    200

    250

    300

    350

    400

    450

    500

    550

    600

    650

    700

    750

    800

    0.0 1.4 2.7 5.4 6.8 8.1 13.5 20.0 30.0 40.0 50.0

    ORPmV

    0%

    10%

    20%

    30%

    40%

    50%

    60%

    70%

    80%

    90%

    100%

    ATP:%

    kill

    Bromine ORP ClO2 ORP

    Target min ORP Target max ORP

    Bromine % kill ClO2 % kill

    Oxidizing Biocide Requirements in

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    Oxidizing Biocide Requirements in

    Contaminated Systems

    Demand (mg/l) Refinery(with minor

    leaks)

    Petrochemical(hydrocarbon

    leakage)

    Fertilizer (~5mg/l NH3)

    Grain Processing (highorganic loading in recycle

    water used as MU)

    Chlorine 1.0 15.5 23.8 280.0Bromine - 5.5 12.4 88.0

    Chlorine Dioxide 0.2 2.1 2.8 1.5

    Demand in mg/l

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    Gaseous Chlorine Generation

    2NaClO2 + Cl2 2ClO2 + 2NaCl

    Sodium Chlorine Chlorine Sodium

    Chlorite Dioxide Chloride

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    Bleach Generation

    GENEROX III

    2NaClO2

    + NaOCl + 2HCl 2ClO2

    + 3NaCl + H2O

    Sodium Sodium Hydrochloric Chlorine Sodium Water

    Chlorite Hypochlorite Acid Dioxide Chloride

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    Advantages Of Chlorine Dioxide

    Remains gas in water--no hydrolyzation

    Wont react with NH3 or

    organics

    Better MB control

    Not as corrosive as Cl2

    Effective over wide pH ranges

    Lower dosage, less SCC

    problems, no chance of

    delignification, more effective

    than chlorine

    Excellent on algae, SRB, other

    anaerobes and slime

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    Advantages Of Chlorine Dioxide

    Safe to operate and use

    Completely

    environmentally friendly

    and safe

    50 years of experience

    Built in safety features

    Extensively used in drinking

    water and food processingapplications

    No THM & AOX formation

    No harmful by-products

    No air emissions

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    Biodispersants Effectively Penetrate Biofilm

    Biodispersants are molecules with surface acting properties

    Enhance ability of biocides to better penetrate biofilm

    Important to use when applying chlorine and bromine

    May not be required with ClO2 programs

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    DREW

    INDUSTRIAL

    The Next

    Generation of

    Microbiological andBiofilm Control

    Ultrasonic Microbial ControlUltrasonic Microbial Control

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    No chemical biocide usageNo chemical biocide usage

    Superior microbial controlSuperior microbial control

    Excellent Legionella controlExcellent Legionella control Improved heat transferImproved heat transfer

    Reduced maintenanceReduced maintenance

    Ultrasonic Microbial ControlUltrasonic Microbial Control

    SONOXIDE Ultrasonic Treatment

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    SONOXIDE Ultrasonic Treatment

    Development

    Initial work and patent

    for the application of

    ultrasound in medical research

    In 1999, discovered effectiveness on algae andbacteria in water systems

    bles

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    SONOXIDETechnology Highly

    RecognizedMedicine honors

    Apoptosis workMIT Professor among those

    honoredThreescientistsreceivedthe2002NobelThreescientistsreceivedthe2002NobelPrizeforMedicinePrizeforMedicine

    fordeterminingthatorganismsdevelopand

    fordeterminingthatorganismsdevelopandmaintainmaintain------

    Quorumsensing

    enables

    bacteriatocoord

    inatetheir

    behavior

    Programmedcelldeathhasallowed

    expertstounderstandthemechanismsat

    playwithvirusesandbacteria

    Chemical & Engineering News/Science Weekly Archive/Microbe Warfare: Bacterial Communication

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    SONOXIDE Ultrasonic System

    Patented

    Low-powerHigh-frequency

    Special orientation

    Air microbubbles

    System water Air Bubbles

    Emitters

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    The SONOXIDE Unit

    Ultrasonic

    Treatment

    Cell

    Venturi

    air inlet

    Water inlet

    (Tower sump)

    Water outlet

    (Opposite

    side of inlet)

    Sonoxiderecirculating

    pump

    Electrical

    & controls

    panel

    Transparent

    pipe showing

    air bubbles

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    Cavitation

    Intense bubbleformation and collapse

    Necrosis Immediate destruction of cell

    Apoptosis Programmed cell death

    Inability to reproduce Produces signaling proteins

    SONOXIDE Bio Control Mechanisms

    Healthy cells before treatmentHealthy cells before treatment

    Sick cells after treatmentSick cells after treatment

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    Healthy Cell

    Programmed Cell Death is

    triggered by low energy high

    frequency ultrasound Signaling molecules are released

    which affects healthy cells and

    removes biofilm in remote areas

    of water system (QuorumSensing)

    Treated Cell

    SONOXIDE

    Low powerHigh frequency ultrasound

    + microaeration

    Initiates PCD

    Signaling Molecules

    Healthy Cell Biofilm

    Quorum Sensing

    Sonoxide: Mechanism - Apoptosis

    A t i

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    System water Air Bubbles

    Apoptosis

    Healthy bacterial cells exposed to: Frequency, Power Ultrasound

    Micro bubble aeration

    Bacterial cell is genetically altered

    Apoptotic cells exit chamber

    Biofilm cells subjected to programmed celldeath

    Ultrasonic

    Treatment

    Chamber

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    Total Bacteria Control

    Total Bacterial Counts

    100

    1000

    10000

    100000

    1000000

    10000000

    12/2 12/12 12/22 1/1 1/11 1/21

    Start SONOXIDE

    Sonoxide Effect on Green Algae

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    0

    2

    4

    6

    8

    10

    0 1 2 3 4 5Days

    Algaeco

    ncentration

    (106)

    No Treatment Under Sonoxide Treatment

    Sonoxide Effect on Green Algae

    Bi fil d Al C t l

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    Biofilm and Algae Control

    Before SONOXIDE treatmentBefore SONOXIDE treatment 3 week of SONOXIDE treatment3 week of SONOXIDE treatment

    No evidence of biofilm or algaeVisible biofilm & algae

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    SONOXIDE T t t Bi fil C St d

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    SONOXIDE Treatment Biofilm Coupon Study

    Condition of biofilm coupon upon start-up of

    SONOXIDE system. Biofilm is evident.

    Condition of biofilm coupon upon start-up of

    SONOXIDE system. Biofilm is evident.Same biofilm coupon removed after 4 months

    of SONOXIDE operation. No evidence of slime.

    Same biofilm coupon removed after 4 months

    of SONOXIDE operation. No evidence of slime.

    Biofouling study using biofilm coupons. Biofilm coupon was examined prior

    to SONOXIDE start-up and re-examined after 4 months of SONOXIDE

    operation. All biofilm was cleaned up and no evidence of slime exists.

    S S

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    ST Microelectronics, Singapore

    Wafer fab plant

    Chiller tower system

    RR = 1,400 m3

    /yr V = 43 m3

    SONOXIDE replaced program

    comprised of continuous bleachaddition with intermittent feed of

    non-oxidizing biocide

    Unit installed on tower without any

    precleaning

    ST Mi l t i Si

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    ST Microelectronics, SingaporeTo tal B acteria C ou nt R ead ing s D ur ing S ON OX ID E App lication

    1

    10

    100

    1,000

    10,000

    25/3/04

    8/4/04

    20/4/04

    29/4/04

    13/5/04

    19/5/04

    3/6/04

    17/6/04

    30/6/04

    14/7/04

    28/7/04

    11/8/04

    18/8/04

    1/9/04

    15/9/04

    6/10/04

    20/10/04

    Date

    TBC(cfu/ml) SONOXIDE Commissioned

    Legionella Bacteria Counts

    82

    31 36

    2 7 1 00

    20

    40

    60

    80

    100

    14/5/04 6/3/04 30/6/04 7/7/04 21/7/04 1/9/04 6/10/04

    Date

    LBCount(c

    fu/ml)

    SONOXIDE S t Ad t

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    Performance Improvements Reduction in bacteria counts No visible biofilm Improved corrosion rates

    Improved heat transfer Control of algae Reduced maintenance costs Potential to increase COC

    Quality Improvements Eliminate biocide Improved reliability Reduced corrosion potential

    EH&S Benefits Better Legionella compliance Eliminate biocide discharge issues

    Improved risk management Improved personnel safety

    SONOXIDE System Advantages

    Some of Our Many Customers Who Have

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    yBenefited From SONOXIDE

    Ford Motor

    Bridgestone Firestone

    AGA Gases

    Kodak

    Hines Properties

    Cummins Engine

    Ashland Chemical

    Bayer

    Procter and Gamble

    Roche

    Sasol Wax

    MIT

    BMW

    Schiphol Airport

    Alcoa

    Daimler Chrysler

    Kraft Foods

    Superfos

    BASF

    Owens Corning

    Use Of ORP To Enhance Control Of

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    Oxidizing Biocides

    What Is ORP?

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    What Is ORP?

    Measures the oxidizing or

    reducing ability of a solution

    Correlates death rate of

    organisms

    All systems are different-- Must

    relate ORP vs. bacterial countsfor specific cooling system

    Why Use ORP Technology?

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    Why Use ORP Technology?

    ORP allows you to achieve optimum MB control

    ORP allows you to continuously control halogenfeed

    ORP responds to changes in system conditions pH, demand, sunlight, etc. contribute to higherMB loading

    Prevents under and overdosing

    ORP allows you to find system leaks

    Simple to Automate and ControlSimple to Automate and Control

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    Simple to Automate and ControlSimple to Automate and Control

    Output &

    control of

    halogen

    Controllerwith ORP

    ORP probe

    ORP Controls Biofouling

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    ORP Controls Biofouling

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    350.00

    400.00

    450.00

    500.00

    550.00

    600.00

    650.00

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    Time

    OR

    -200

    -150

    -100

    -50

    0

    50

    10 0

    15 0

    200

    ORP

    FOULING

    Effect Of pH on ORP in Chlorinated

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    440.00

    450.00

    460.00

    470.00

    480.00

    490.00

    500.00

    510.00

    520.00

    530.00

    ORP

    6.60

    6.65

    6.70

    6.75

    6.80

    6.85

    6.90

    6.95

    7.00

    pH

    ORP

    PH

    p

    Systems

    ORP Allows Better Control At Reduced Cost And

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    Chemical Usage

    Halogen fed onHalogen fed ondemanddemand

    Tight ORP ControlTight ORP Control

    Examples of ORP Control Systems

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    Examples of ORP Control Systems

    Summary

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    Summary

    Microbiological control is the key to success in cooling water

    treatment programs

    Classical oxidizing biocides (i.e., Cl2 and Br2) work well in theright types of systems

    Unique chemical technology ClO2 provides excellentmicrobial control in high pH and contaminated systems

    New SONOXIDE ultrasonic treatment controls

    microorganisms without the use of chemicals

    Oxidation Reduction Potential (ORP) is an excellent tool to

    control feed of oxidizing biocides

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    DREW

    INDUSTRIAL

    ThankYou


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